JP3056655B2 - Aniline-based conductive polymer film and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aniline-based conductive polymer film having excellent chemical stability and a method for producing the same. The aniline-based conductive polymer film of the present invention is applicable to various antistatic applications, various sensors, battery electrode materials, capacitor electrode materials, and the like.

[0002]

2. Description of the Related Art Aniline-based polymers are easily obtained by electrical or chemical oxidative polymerization using aniline as an industrial raw material, and are easily doped with a protic acid such as hydrochloric acid or sulfuric acid to obtain a relatively high conductivity. It has attracted attention as a conductive polymer because of its properties. When polymerized under protonic acid conditions using ammonium peroxodisulfate as an oxidizing agent, a high molecular weight product is obtained, which is treated with aqueous ammonia or the like to give N, N-dimethylformamide or N-methyl-2. -It is reported that a polymer soluble in a polar solvent such as pyrrolidone can be obtained (Synth.
Met. , 18, 285 (1987), Synth. M
et. , 18, 317 (1987); Chem. S
oc. Chem. Commun. , 22,1736
(1989)) and its film (thinning)
Applications are being developed for this purpose. When trying to obtain a conductive polymer film using an aniline-based conductive polymer, the aniline-based conductive polymer is converted to a undoped state,
Generally, a method of dissolving in a polar organic solvent such as N, N-dimethylformamide or N-methyl-2-pyrrolidone, forming the solution into a film by spin coating or casting, and then doping is used.

Conventionally, an inorganic salt such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and an organic acid such as p-toluenesulfonic acid and dodensylbenzenesulfonic acid have been added to an aniline-based conductive polymer film as a dopant. Things are known. In the aniline-based conductive polymer film having these low-molecular dopants, a large amount of the dopant is doped into the polymer film, but the dopant easily moves through the aniline-based conductive polymer film or is subjected to heat treatment. There is a problem that it is easily scattered and desorbed due to, for example, and it is hard to say that it is physically and chemically stable.

Therefore, in recent years, a polymer having an alkanesulfonic acid having 5 or more carbon atoms as a dopant (Japanese Unexamined Patent Publication No.
163263), a conductive material having as a dopant a polymer acid such as polystyrenesulfonic acid, polyvinylsulfuric acid, polyvinylsulfonic acid, polyallylsulfonic acid, polymethacrylsulfonic acid, and poly (2-acrylamido-2-methylpropanesulfonic acid). Organic polymer thin film composite and method for producing the same (JP-A-02-169525), sulfonated polyethylene as a dopant,
A conductive polymer composition using a polymer anion such as sulfonated polystyrene, sulfonated poly (2,5-dimethylphenylene oxide), and sulfonated polyvinyl alcohol, and a method for producing the same (JP-A-59-98165).
Has been proposed. However, these compounds have low doping to the undoped aniline-based polymer and are non-uniform. Therefore, there is a problem that the aniline-based conductive polymer film has low conductivity. Further, heat resistance and weather resistance are not sufficient.

Further, the solution containing the above-mentioned inorganic salt, organic acid or polymer acid used in the doping method shows strong acidity, is highly corrosive, and cannot be said to be industrially suitable.

In addition, there has been proposed a method of producing a conductive polymer composite in which sulfonic acid is polymerized after compounding undoped polyaniline or a derivative thereof with a polymerizable sulfonic acid (JP-A-06-32845). However, there are still problems such as the necessity of a polymerization step of sulfonic acid after film formation and complicated operation, and the fact that the polymerized sulfonic acid as a dopant shows strong acidity in the film.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a chemically and physically stable aniline-based conductive polymer film exhibiting high conductivity and excellent heat resistance and weather resistance, and a method for producing the same. Is to provide.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a sulfone group and / or
Alternatively, a soluble aniline-based conductive polymer having 70% or more of an acidic group-substituted aniline having a carboxyl group or the like as a repeating unit exhibits excellent performance as a doping agent, and can increase the conductivity of an aniline-based polymer film. Further, it has been found that the obtained aniline-based conductive polymer film in a doped state has extremely excellent chemical and physical stability such as heat resistance and weather resistance. The present invention has been achieved based on such findings.

That is, the first aspect of the present invention is the general formula (1)

Embedded image (Wherein, R _{1 to} R ₁₈ are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a nitro group, an amino group, and a halogen atom. X represents an arbitrary number of 0 to 1, n represents a degree of polymerization, and 2 to 50.
Aniline-containing aniline having a sulfone group and / or a carboxyl group, or an alkali metal salt thereof, on the undoped aniline-based polymer membrane (m) represented by , An ammonium salt and / or a substituted ammonium salt as a repeating unit, a soluble aniline-based conductive polymer (a) having a weight average molecular weight of 1900 or more and being a solid at room temperature is added as a dopant. And a aniline-based conductive polymer film.

The aniline-based polymer film (m) constituting the aniline-based conductive polymer film of the present invention is an undoped aniline-based polymer represented by the structural formula of the above general formula (1). Is preferably a thin film. Examples of the aniline-based polymer include polyaniline, poly (methylaniline), poly (ethylaniline), poly (n-propylaniline) poly (iso-propylaniline), poly (n-butylaniline), and poly (iso- Butylaniline), poly (sec-butylaniline), poly (alkyl-substituted aniline) such as poly (t-butylaniline), poly (N-methylaniline), poly (N-ethylaniline), poly (N-n -Propylaniline) poly (N-iso-propylaniline), poly (Nn-butylaniline), poly (N-iso-butylaniline), poly (N-sec-butylaniline), poly (N
Poly (N-alkyl-substituted aniline) such as -t-butylaniline), poly (methoxyaniline), poly (ethoxyaniline), poly (n-propoxyaniline), poly (iso-propoxyaniline), poly (n- Poly (alkoxy-substituted aniline) such as butoxyaniline), poly (iso-butoxyaniline), poly (sec-butoxyaniline), poly (t-butoxyaniline),
Examples thereof include poly (hydroxy-substituted aniline), poly (nitro-substituted aniline), poly (fluoroaniline), poly (chloroaniline), and poly (halogen-substituted aniline) such as poly (bromoaniline). Each of these aniline polymers may be used alone, or two or more of them may be mixed at an arbitrary ratio.

The above aniline-based polymer is generally obtained in a state in which an anion contained in a solvent at the time of polymerization is doped, so that in order to be solubilized in the solvent, a deacidification treatment or a reduction treatment is performed. Must be subjected to dedoping treatment. Although there is no particular limitation on the undoping method, a method of treating with ammonia water or an aqueous sodium hydroxide solution or treating with hydrazine or the like is used.

The aniline-based polymer film (m) can be a aniline-based polymer composite film by adding a polymer compound to the aniline-based polymer. This allows the hardness of the film,
Abrasion resistance and adhesion to a substrate are further improved.

The ratio of the aniline-based polymer to the high-molecular compound is expressed in terms of weight ratio: aniline-based polymer: high-molecular compound = 1
It is good to select appropriately from 0: 0 to 1: 9, preferably from 10: 0 to 6: 4. Here, when the proportion of the polymer compound is high, the conductivity tends to decrease.

As the polymer compound, for example, polyethylene, polyvinyl chloride, polypropylene, polystyrene,
Polyester, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyamide, polyimide,
Polyaramid, polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, and the like are used.

The soluble aniline-based conductive polymers (a) used as the doping agent are preferably those represented by the following structural formula (2) or those having a repeating unit having a partial structure of 70% or more.

That is, (a) is

Embedded image (In the formula, A is a sulfone group, a carboxyl group, or one group selected from alkali metal salts, ammonium salts, and substituted ammonium salts thereof, and B is hydrogen, a methyl group, an ethyl group, an n-propyl group, iso-propyl group,
n-butyl group, iso-butyl group, sec-butyl group,
alkyl groups such as t-butyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group,
From an alkoxy group such as a t-butoxy group, a heptoxy group, a hexoxy group, an octoxy group, a nanooxy group, a decanoloxy group, an undecanoloxy group, a dodecanoloxy group, a hydroxy group, a nitro group, and a fluoro group, a chloro group, and a halogen group such as a bromo group. Shows one selected group. x is 0
Represents an arbitrary number of 1 to 1; n represents a degree of polymerization;
0) a polymer having an acidic group-substituted aniline having an acidic group such as a sulfone group and / or a carboxyl group represented by the formula (1) or an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof as a repeating unit of 70% or more. Having a weight average molecular weight of 190
Those having a solid state of 0 or more at room temperature are preferable.

Examples of the alkali metal salt include lithium, sodium, potassium and the like.

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

As the aliphatic ammoniums, the following formula (4)

Embedded image (Wherein R _{24 to} R ₂₇ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH, and CH ₂ 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,
Ethyl butyl ammonium, tetramethyl ammonium, tetramethylol ammonium, tetraethyl ammonium, tetra n-butyl ammonium, tetrase
Examples thereof include c-butylammonium and tetra-t-butylammonium. Among them, R ₂₄ ~R ₂₇
Most preferably, one of them is hydrogen and the other three are alkyl groups having 1 to 4 carbon atoms. Then, when two of R _{24 to} R ₂₇ 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 ammoniums include pyridinium, α-picolinium, β-picolinium, γ-
Examples include picolinium, quinolinium, isoquinolinium, pyrrolium, and derivatives having these skeletons.

As the soluble aniline-based conductive polymers (a), those obtained by various synthetic methods such as chemical and electrochemical methods can be used. For example, the present inventors have proposed (Japanese Patent Application No. 05-353698). No., Japanese Patent Application No. 06
General formula (3)

Embedded image (Wherein, R _{19 to} R ₂₃ are each selected from hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, an acidic group, a hydroxyl group, a nitro group, and a halogen. At least one of which represents an acidic group, wherein the acidic group represents a sulfone group or a carboxyl group); A soluble aniline-based conductive polymer obtained by polymerizing at least one compound (a) among salts with an oxidizing agent in a solution containing a basic compound (b) is preferably used.

The method comprises the steps of: (a) at least one compound selected from the group consisting of an acid-substituted aniline having an acidic group such as a sulfone group and / or a carboxyl group as a monomer, and alkali metal salts, ammonium salts and substituted ammonium salts thereof;
Is especially polymerized using a oxidizing agent in a solution containing a basic compound (b), the reactivity is particularly improved, and the conventional aniline having a sulfone group and / or a carboxyl group can be chemically oxidized by itself. Contrary to the common belief that polymerization is difficult, polymerization is possible. Moreover, the resulting soluble aniline-based conductive polymer has an acidic group for all of the benzene nuclei, so that it has a high conductivity and an alkaline, neutral (particularly simply water), acidic aqueous solution having all pH values. And excellent solubility in organic solvents such as alcohols.

The compound (A) such as an acid-substituted aniline represented by the general formula (3) has a polymer in which an acidic group is bonded to the amino group at the o-position or the m-position. It has excellent solubility and other properties, and is highly effective as a dopant.

The most representative examples of the aniline substituted with an acidic group are aniline substituted with a sulfone group or aniline substituted with a carboxyl group. Preferably, it is a sulfone-substituted aniline.

The most typical sulfone-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 anilines substituted with a sulfone group include methylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid, n-propylaminobenzenesulfonic acid, iso-propylaminobenzenesulfonic acid, and n-propylaminobenzenesulfonic acid.
Alkyl-substituted aminobenzenesulfonic acids such as -butylaminobenzenesulfonic acid, iso-butylaminobenzenesulfonic acid, sec-butylaminobenzenesulfonic acid, t-butylaminobenzenesulfonic acid, methoxyaminobenzenesulfonic acid, ethoxyaminobenzenesulfonic acid Acid, n-propoxyaminobenzenesulfonic acid, iso-propoxyaminobenzenesulfonic acid, n
-Butoxyaminobenzenesulfonic acid, sec-butoxyaminobenzenesulfonic acid, iso-butoxyaminobenzenesulfonic acid, t-butoxyaminobenzenesulfonic acid, heptoxyaminobenzenesulfonic acid, hexoxyaminobenzenesulfonic acid, octoxyaminobenzene Alkoxy-substituted aminobenzenesulfonic acids such as sulfonic acid, nanoxyaminobenzenesulfonic acid, decanoxyaminobenzenesulfonic acid, undecanoxyaminobenzenesulfonic acid, and dodecanooxyaminobenzenesulfonic acid; Examples include hydroxy-substituted aminobenzenesulfonic acids, nitro-substituted aminobenzenesulfonic acids, halogen-substituted aminobenzenesulfonic acids such as fluoroaminobenzenesulfonic acid, chloroaminobenzenesulfonic acid, and bromoaminobenzenesulfonic acid. Preferably, an alkyl group-substituted aminobenzenesulfonic acid and an alkoxy-substituted aminobenzenesulfonic acid are used. These sulphone-substituted anilines may be used alone or in a mixture of isomers at an arbitrary ratio.

The most typical 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-substituted anilines include methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid,
Alkyl-substituted aminobenzenecarboxylic acids such as n-butylaminobenzenecarboxylic acid, iso-butylaminobenzenecarboxylic acid, sec-butylaminobenzenecarboxylic acid, t-butylaminobenzenecarboxylic acid, methoxyaminobenzenecarboxylic acid, ethoxyaminobenzene Carboxylic acid, n-propoxyaminobenzenecarboxylic acid, iso-propoxyaminobenzenecarboxylic acid,
n-butoxyaminobenzenecarboxylic acid, sec-butoxyaminobenzenecarboxylic acid, iso-butoxyaminobenzenecarboxylic acid, t-butoxyaminobenzenecarboxylic acid, heptoxyaminobenzenecarboxylic acid, hexoxyaminobenzenecarboxylic acid, octoxyamino Alkoxy-substituted aminobenzenecarboxylic acids such as benzenecarboxylic acid, nanoxyaminobenzenecarboxylic acid, decanoxyaminobenzenecarboxylic acid, undecanoxyaminobenzenecarboxylic acid, dodecanooxyaminobenzenecarboxylic acid, and hydroxy-substituted aminobenzenecarboxylic acid Acids, nitro-substituted aminobenzenecarboxylic acids,
Examples thereof include halogen-substituted aminobenzenecarboxylic acids such as fluoroaminobenzenecarboxylic acid, chloroaminobenzenecarboxylic acid, and bromoaminobenzenecarboxylic acid. Preferably, an alkyl group-substituted aminobenzenecarboxylic acid and an alkoxy-substituted aminobenzenecarboxylic acid are used. These carboxyl group-substituted anilines may be used alone, or may be used by mixing isomers at an arbitrary ratio.

More specifically, specific examples of the acidic group-substituted aniline represented by the general formula (3) include a sulfone group-substituted alkylaniline, a carboxyl group-substituted alkylaniline, a sulfone group-substituted alkoxyaniline, a carboxyl group-substituted alkoxyaniline, and a sulfone group-substituted aniline. Hydroxyaniline, carboxyl-substituted hydroxyaniline, sulfone-substituted nitroaniline, carboxyl-substituted nitroaniline, sulfone-substituted fluoroaniline, carboxyl-substituted fluoroaniline, sulfone-substituted chloroaniline, carboxyl-substituted chloroaniline, sulfone-substituted bromoaniline And carboxyl-substituted alkylanilines. Specific examples of the positions and combinations of these substituents are shown in Table 1.

[0031]

[Table 1] Here, A: represents one group selected from a sulfone group or a carboxyl group, an alkali metal salt, an ammonium salt, and a substituted ammonium salt thereof; B: a methyl group, an ethyl group, an n-propyl group, an iso-propyl group , N-butyl group, iso-butyl group, sec-
Alkyl groups such as butyl group and t-butyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-
Halogen groups such as alkoxy groups such as butoxy group, t-butoxy group, heptoxy group, hexoxy group, octoxy group, nanoxy group, decanoloxy group, undecanoloxy group and dodecanoloxy, nitro group, fluoro group, chloro group, and bromo group. And H represents hydrogen.

The above-mentioned acidic group-substituted aniline may further comprise at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines (d)
And can be used as a copolymer with the compound (a).

The N-alkylaniline includes N-alkylaniline.
Methylaniline, N-ethylaniline, Nn-propylaniline, N-iso-propylaniline, N-butylaniline 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 can be used alone or in combination.

The ratio of the compound (a) such as the acidic group-substituted aniline of the general formula (3) to the compound (d) is (a) :( d) = 10: 0 to 7: 3 in equivalent ratio. Preferably 1
It is used in the range of 0: 0 to 8: 2. That is, the introduction ratio of the compound (a) such as an acid-substituted aniline is 70% or more, preferably 80% or more. Here, when the ratio of the compound (d) is high, the solubility in the doping solvent is reduced, the doping rate is reduced, and the conductivity of the aniline-based conductive polymer film tends to be reduced.

Next, as the basic compound (b) used for synthesizing the soluble aniline-based conductive polymers (a) used as the dopant of the present invention, the compound (a) such as the above-mentioned acid-substituted aniline is used. Any compound may be used as long as it forms a salt with ammonia, ammonia,
Aliphatic amines, cyclic saturated amines, cyclic unsaturated amines, inorganic bases and the like are preferably used. More preferably, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and the like can be mentioned.

As the fatty amines, the following formula (5)

Embedded image _{(Wherein, R} 28 _{~ 30,} respectively, an alkyl group having 1 to 4 carbon atoms, a _{C H} 2 OH and C _H 2 _CH 2 independently selected groups from the group consisting of OH) compound represented by the ,
Or the general formula (6)

Embedded image (Wherein, R ₃₁ to R ₃₄ each represent hydrogen, carbon number 1 to 4
Alkyl group, and a hydro-key side compound represented by a is) C H 2 _OH and C H 2 _CH 2 independently selected groups from the group consisting of _OH of.

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

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 and lithium hydroxide are preferably used. Aliphatic amines, cyclic saturated amines, cyclic unsaturated amines The conductivity tends to be inferior to that of.

The concentration of these basic compounds (b) is 0.1
It is used in an amount of at least mol / l, preferably 0.1 to 10.0 mol / l, more preferably 0.2 to 8.0 mol / l. At this time, if the amount is 0.1 mol / liter or less, the yield of the obtained polymer decreases, and
When it is 0.0 mol / liter or more, the conductivity tends to decrease. The basic compound (b) can be used by mixing at an arbitrary ratio.

The weight ratio of the compound (a) such as the above-mentioned acidic group-substituted aniline to the basic compound (b) is (a):
(B) = 1: 100-100: 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. Conversely, when the ratio is high, the ratio of forming a salt of an acidic group and a basic compound in the obtained polymer increases, and the conductivity tends to decrease. 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:
0.5 to 1:15 can be used. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. Conversely, when the ratio is high, the ratio of the salt formed between the acidic group and the basic compound in the obtained polymer increases, and the conductivity tends to decrease.

The polymerization or copolymerization is carried out by oxidative polymerization with an oxidizing agent in a solution containing these basic compounds. Solvents include water, alcohols such as methanol, ethanol and isopropyl alcohol, nitriles such as acetonitrile, ketones such as methyl isobutyl ketone and methyl ethyl ketone, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. And various organic solvents such as ethers such as tetrahydrofuran, or a mixture of water with these organic solvents.

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, but peroxodisulfuric acid, ammonium peroxodisulfate, peroxodisulfuric acids such as sodium peroxodisulfate and potassium peroxodisulfate, hydrogen peroxide, and the like are preferably used, and are preferably used in 1 mole of the monomer. 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 is preferably carried out in a temperature range of -15 to 70 ° C, more preferably -5 to 70 ° C.
A range of 60 ° C. applies. Here, when the temperature is lower than −15 ° C. or higher than 70 ° C., the conductivity tends to decrease.

In the soluble aniline-based conductive polymers (a) produced by the above method, hydrogen in the sulfone group or carboxyl group in A in the general formula (2) is hydrogen,
It is a group independently selected from the group consisting of alkali metals, ammonium and substituted ammonium, that is, these groups can be obtained not only alone but also in a mixed state.

Specifically, when polymerized in the presence of sodium hydroxide, most of the hydrogen in the sulfone group or carboxyl group in the isolated polymer has been replaced with sodium.

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

When a basic compound is used as a mixture, the mixture is obtained in a mixed state. Specifically, when polymerized in the presence of sodium hydroxide and ammonia, hydrogen at the sulfone or carboxyl groups in the isolated polymer is obtained in the presence of both sodium and ammonium. Similarly, 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 obtained in a state where both sodium and ammonium are present.

The polymer in which a part of the acidic group forms a salt can be converted into a polymer in which the salt is replaced by hydrogen when treated in an acidic solution. Hydrochloric acid as an acidic solution,
Examples thereof include sulfuric acid, p-toluenesulfonic acid, and nitric acid. However, it is difficult to obtain a product completely substituted with hydrogen even if the acid substitution is sufficiently performed.

However, since the polymer obtained by the production method of the present method precipitates out of the polymerization solvent, the rate of salt formation is low, so that it is not necessary to treat the polymer in an acidic solution. Polymer can be produced.

The soluble aniline-based conductive polymers (a) containing 70% or more of sulfone groups and / or carboxyl groups with respect to all aromatic rings thus obtained have a polymerization degree of 3 to 5000, preferably 5 to 5. 5,000 and a molecular weight of about 1900-3240000, preferably 3200-3240000. This polymer can be used without further sulphonation operation without any water, a base such as ammonia and an alkylamine or a 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 the like. It can be dissolved in a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or a mixture thereof.

The aniline-based conductive polymer film according to the present invention is a undoped aniline-based polymer film represented by the above-mentioned general formula wherein the soluble aniline-based conductive polymer (a) as described above is used as a dopan. m).

A second aspect of the present invention is to form a dedoped or undoped aniline-based polymer film (m) represented by the above general formula on at least one surface of a substrate. Thereafter, a polymer having 70% or more of an acidic group-substituted aniline having a sulfone group and / or a carboxyl group, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof as a repeating unit, and having a weight average molecular weight of 1900 or more The soluble aniline-based conductive polymers (a), which are solids at room temperature,
And a method for producing an aniline-based conductive polymer film, which comprises doping with a composition comprising a solvent and a solvent (b), and then allowing the composition to stand at room temperature or heating.

As a method for forming the aniline-based polymer film (m) on the substrate, a undoped aniline-based polymer-containing solution is processed on the surface of the substrate by a method used for a general coating material. 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,
Application methods such as screen coating, spray methods such as spray coating, and dipping methods such as dip are used.

As the substrate on which the aniline-based polymer-containing solution is applied, polymer compounds, wood, paper, ceramics, and films or glass plates thereof are used.
For example, as the polymer compound and the film, polyethylene, polyvinyl chloride, polypropylene, polystyrene,
Polyester, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyamide, polyimide,
Examples include polyaramid, polyphenylene sulfide, polyetheretherketone, polyphenyleneether, polyethernitrile, polyamideimide, polyethersulfone, polysulfone, polyetherimide, polybutyleneterephthalate, and films thereof. In order to form an aniline-based polymer film on at least one surface of these polymer films, the film surface is preferably subjected to a corona surface treatment or a plasma treatment for the purpose of improving the adhesion of the polymer film.

The aniline-based polymer-containing solution may be prepared by adding the undoped aniline-based polymer alone or the aniline-based polymer and a polymer compound to a solvent and dissolving the solution at room temperature or by heating and stirring. Or by mixing. The solvent is not particularly limited as long as it is a solvent in which the undoped aniline-based polymer and the polymer compound are soluble, but alcohols such as methanol, ethanol, and isopropanol; nitriles such as acetonitrile; methyl isobutyl ketone; methyl ethyl ketone; Various organic solvents such as ketones, polar solvents such as N, N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and ethers such as tetrahydrofuran, or a mixture of water and these organic solvents. Can be mentioned. Preferably, N, N-
Polar solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide are used, and N, N-dimethylformamide or N-methyl-2-pyrrolidone is more preferably used.

In the method of the present invention, the doping treatment
The soluble aniline-based conductive polymer (a) and the solvent (b) or the soluble aniline-based conductive polymer (a) and the solvent (b) further contain at least one kind selected from amines and quaternary ammonium salts. A deoxidized or reduced undoped aniline-based polymer film formed on at least one surface of the substrate is immersed in a composition comprising a nitrogen compound (c) and / or a surfactant (d). To process. Thereafter, excess soluble aniline-based conductive polymers (a) are washed away with a solvent and dried. It should be noted that two or more soluble aniline-based conductive polymers can be used without any problem.

The solvent (b) used in the present invention includes:
The solvent is not particularly limited as long as it is a solvent in which the soluble aniline-based conductive polymers (a) are soluble, but water, an acidic solvent, and an organic solvent are used, and 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 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 such as methyl propylene glycol and ethyl propylene glycol. Glycols, amides such as dimethylformamide and dimethylacetamide, pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone, ethyl lactate, methyl lactate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate, α-hydroxyiso Examples include hydroxyesters such as ethyl butyrate and methyl α-methoxyisobutyrate, and alcohols, propylene glycols, amides and pyrrolidones are preferred. Irare, alcohols are more preferably used. By using the above organic solvent or a solvent containing an organic solvent, the wettability of the solvent (b) with respect to the aniline-based polymer film can be improved, and the doping ratio tends to increase and the conductivity tends to improve. The ratio used as a mixed system with water is water: organic solvent =
1: 100 to 100: 1 is preferred.

Further, by adding an acidic compound to the solvent (b), a doping effect from the acidic compound is added, and the conductivity can be improved. Examples of the acidic compound include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as p-toluenesulfonic acid, acetic acid, and methanesulfonic acid. The ratio of the weight ratio of the solvent (b) to be added is as follows: solvent: acid compound = 70: 30 to 100: 0.01
Is preferred. Each of the above-mentioned solvents may be used as a mixture of one or more kinds at an arbitrary ratio.

The proportion of the soluble aniline-based conductive polymer (a) and the solvent (b) is 10
The amount is 0.01 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 20 parts by weight based on 0 parts by weight. If the proportion of component (a) is less than 0.01 parts by weight, the conductivity will be poor. On the other hand, if it exceeds 30 parts by weight, the viscosity of the doping solution will increase, making it difficult to dope, and the conductivity will reach a peak. Does not increase.

Further, by adding at least one nitrogen-containing compound (c) selected from amines and quaternary ammonium salts to the solvent (b), the pH of the composition can be adjusted arbitrarily. And corrosiveness to the substrate and the like can be prevented.

The soluble aniline-based conductive polymer (a) used as a dopant in the present method can be easily converted into a dopant by subjecting it to a normal temperature or heat treatment after doping even if it contains a nitrogen-containing compound. The aniline-based conductive polymer film obtained by scattering from the inside shows high conductivity.

The nitrogen-containing compound (c) used in the present invention
Is a compound represented by the formula (7) or (8). Formula (7) shows the structural formula of the amines used.

[0064]

Embedded image (Wherein, R _{35 to} R ₃₇ are each independently hydrogen, carbon 1
To 4 alkyl groups, CH ₂ OH, CH ₂ CH ₂ OH, C
(Representing ONH ₂ or NH ₂ ) Further, the structural formula of the quaternary ammonium salt used is shown in formula (8).

[0065]

Embedded image ( Wherein , R _{38 to} R ₄₁ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH) CH ₂ CH ₂ O
X represents OH ⁻ , 1 / H, CONH ₂ or NH ₂ ;
2. SO ₄ ²⁻ , NO ₃ ⁻ , 1 / 2CO ₃ ²⁻ , HCO
^{_{3 -, 1/2 · (}} COO) 2 2-, or R'COO
^- (Wherein, R 'represents an alkyl group having 1 to 3 carbon atoms)

The conductivity of the nitrogen-containing compound (c) can be further improved 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 it is preferable that amines / ammonium salts = 1/10 to 10/0.

The proportion of the nitrogen-containing compound (c) added to the solvent (b) is 0 to 100 parts by weight of the solvent (b).
-30 parts by weight, preferably 0-20 parts by weight. 30
If the amount is more than 10 parts by weight, the solution exhibits strong basicity, the doping rate decreases, and the conductivity of the aniline-based conductive polymer becomes poor. The pH of the solution can be arbitrarily adjusted by the concentration, type and mixing ratio of the nitrogen-containing compound.
It can be used in the range of 1 to 12.

The doping solution of the present invention has a good doping effect even when only the components of the soluble aniline-based conductive polymers (a) and the solvent (b) or the components (a), (b) and the nitrogen-containing compound (c) are used. However, when the surfactant (d) is added to these doping solvents, the wettability of the undoped aniline-based polymer film is further improved, and the conductivity is also improved because the doping rate is increased. Is shown.

Examples of the surfactant include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylcarboxylic acid, alkylnaphthalenesulfonic acid, α-olefinsulfonic acid, dialkylsulfosuccinic acid, α-sulfonated fatty acid, and N-methyl-N-oleyltaurine. , Petroleum sulfonic acid, alkyl sulfate, sulfated oil, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, naphthalene Anionic surfactants such as sulfonic acid formaldehyde condensates and salts thereof, primary to tertiary fatty amines, quaternary ammonium, tetraalkylammonium, trialkylbenzylammonium alcohol Quilpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N-dialkylmorpholinium, polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide Cationic surfactants such as quaternary ammonium and salts thereof, N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine, N, N-dialkyl-N,
N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-1-
Amphoteric surfactants such as betaines such as hydroxyethylimidazolinium betaine, and aminocarboxylic acids such as N, N-dialkylaminoalkylene carboxylate;
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene Nonionic such as polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylated castor oil, fatty acid diethanolamide, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester, trialkylamine oxide, etc. Surfactants and fluoroalkylcarboxylic acids, perfluoroalkylcarboxylic acids, perfluoroalkylbenzenes Acid, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used. Here, the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. Among these surfactants, nonionic surfactants and anionic surfactants are particularly preferably used, and among them, surfactants having an anionic group such as a sulfone group or a carboxyl group in the molecule are more preferably used. . In addition, even if it uses two or more surfactants, there is no problem.

The proportion of the surfactant to be used is 10% in the solvent (b).
0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 0 parts by weight. When the proportion of the surfactant exceeds 10 parts by weight, dispersibility and wettability decrease, and conductivity also tends to decrease.

The treatment after the formation of the aniline-based conductive polymer film on the substrate can be carried out by leaving it at room temperature, but the amount of the components (b) and (c) remaining after the heat treatment Is further reduced, so that the conductivity is further improved (the resistance value is reduced).
The amount of the component (c) remaining in the aniline-based conductive polymer film depends on the intended use.
The amount is preferably 2 parts by weight or less, more preferably 1 part by weight or less based on 00 parts by weight. Further, it is better that the component (b) is not substantially present. As the heat treatment, heating at 250 ° C. or less, preferably 40 to 200 ° C. is preferable. 25
If the temperature is higher than 0 ° C., the conductivity may decrease due to the deterioration of the soluble aniline-based conductive polymers (a).

Thus, an aniline-based conductive polymer film having as a dopant a soluble aniline-based conductive polymer containing 70% or more of an acidic group with respect to all aromatic rings,
While exhibiting high conductivity, it has chemically and physically excellent properties such as heat resistance and weather resistance.

[0073]

Embodiments will be described below with reference to embodiments. In addition, IR spectrum is model 1600 manufactured by PerkinElmer.
The measurement was performed using the apparatus described in (1). For the measurement of the molecular weight distribution and the molecular weight, GPC measurement (in terms of polystyrene) was performed using a GPC column for N, N-dimethylformamide.
The column has 3 columns for N, N-dimethylformamide.
Types were used in conjunction. The eluent contains 0.01 mol /
A solution of liter triethylamine and 0.1 mol / liter lithium bromide in N, N-dimethylformamide was used. For the conductivity, a four-terminal method was used for measuring the conductivity, and a two-terminal method was used for measuring the surface resistance. Was used.

<Synthesis of Soluble Aniline-Based Conductive Polymer> Example 1 100 mmol of o-aminobenzenesulfonic acid was added at 25 ° C.
And dissolve in 4 mol / l ammonia aqueous solution with stirring.
An aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours.
g was obtained. This had a volume resistance of 12.0 Ωcm. As a result of measuring the molecular weight distribution and the molecular weight, the number average molecular weight was 150,000, the weight average molecular weight was 190,000, Z
Average molecular weight 210,000, dispersity MW / MN 1.5,
MZ / MW was 1.3. The polymer was added little by little to 10 ml of water, 0.1 mol / l sulfuric acid aqueous solution or 0.1 mol / l ammonia water. When the polymer no longer dissolved, the mixture was filtered and the dissolved amount was determined. The solubility of the obtained conductive polymer was 230 mg / ml of water and 0.1 mol / l of an aqueous sulfuric acid solution 225 mg / ml and 0.1 mol / l of aqueous ammonia and 200 mg / ml.

Example 2 100 mmol of 2-aminoanisole-4-sulfonic acid
Is dissolved in a 4 mol / l aqueous ammonia solution at 25 ° C. with stirring to obtain 100 mmol of ammonium peroxodisulfate.
Was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed, and dried to obtain 15 g of a polymer powder. This has a volume resistance of 9.0Ωc.
m. As a result of measuring and measuring the molecular weight distribution and the molecular weight, the number average molecular weight was 200,000 and the weight average molecular weight was 330,0.
00, Z average molecular weight 383,000, dispersity MW / MN
1.63, MZ / MW 1.16. The polymer was added little by little to 10 ml of water, 0.1 mol / l sulfuric acid aqueous solution or 0.1 mol / l ammonia water, and the mixture was dissolved.
The solubility of the conductive polymer synthesized in Example 1 was 210 mg / ml of water, 0.1 mol / l of a sulfuric acid aqueous solution, 205 mg / ml, and 0.1 mol / l of aqueous ammonia, 190 mg / ml.

Example 3 3-Methyl-6-aminobenzenesulfonic acid 100 mm
was dissolved in a 4 mol / l aqueous solution of trimethylamine with stirring at 4 ° C., and ammonium peroxodisulfate 100
An aqueous solution of mmol was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 6 hours, and the reaction product was separated by filtration, washed, and dried.
10 g of a polymer powder was obtained. This polymer was stirred for 1 hour in an acetone solution of 1 mol / liter PTS, washed by filtration and then washed.
After drying, 18 g of a polymer powder free of sulfone groups was obtained. This had a volume resistance of 12.5 Ωcm.

Example 4 2-carboxaniline (anthranilic acid) 100 m
mol was dissolved in a 4 mol / l quinoline aqueous solution at 4 ° C. with stirring, and ammonium peroxodisulfate was added in an amount of 100 mmol.
l of aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed, and dried to obtain 11 g of a polymer powder. The volume resistance of this is 45Ωc
m.

<Synthesis of undoped aniline polymer> Example 5 100 mmol of aniline was dissolved in a 1 mol / l aqueous sulfuric acid solution at 4 ° C. with stirring, and a 1 mol / l aqueous sulfuric acid solution of 100 mmol ammonium peroxodisulfate was added dropwise. . After the addition, the mixture was further stirred at 25 ° C. for 12 hours,
8. Doped aniline-based polymer (polyaniline) powder
5 g were obtained. Next, this dope type aniline polymer was stirred and mixed in a 0.5 mol / l aqueous ammonia solution for 2 hours, washed by filtration, dried and obtained, to obtain 7.2 g of a undoped aniline polymer.

Example 6 100 mmol of 3-methylaniline was dissolved in a 1 mol / l aqueous sulfuric acid solution at 4 ° C. with stirring, and a 1 mol / l aqueous sulfuric acid solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours to obtain 10.5 g of a doped aniline-based polymer (poly (methylaniline)) powder. Next, this dope type aniline polymer was stirred and mixed in a 0.5 mol / liter aqueous ammonia solution for 2 hours, filtered, washed and dried to obtain 8.5 g of a undoped aniline polymer.

Example 7 100 mmol of 3-methoxyaniline was added at 4 ° C.
The mixture was stirred and dissolved in 1 liter of a sulfuric acid aqueous solution, and a 1 mol / l aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours to obtain 11.2 g of a doped aniline polymer (poly (methoxyaniline)) powder. Next, this dope type aniline polymer was stirred and mixed in a 0.5 mol / liter aqueous ammonia solution for 2 hours, washed by filtration, dried and obtained, thereby obtaining 9.1 g of a undoped aniline polymer.

<Production of an aniline-based conductive polymer film> Example 8 3 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 2) were stirred and dissolved in 100 parts by weight of water at room temperature, and a doping solution was prepared. A composition was prepared. The pH of the doping solution composition was 2.5. Next, 2 parts by weight of an aniline-based polymer (polyaniline synthesized in Example 5) was dissolved by stirring at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, and the solution was applied on a glass substrate by a spin coating method, and then applied at 120 ° C. To form an aniline-based polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω.
/ □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour, and then washed with water.
The resultant was dried at ℃ to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 2.0 × 10 ⁷ Ω / □. Next, the conductive polymer film was subjected to a heat treatment at 250 ° C. for 2 hours, and the surface resistance was measured.
0 ⁷ Ω / □ and is, also, after standing for 1 week at 120 ° C., was measured surface resistance again, 2.0 × 10 ^{7 Ω} / □ and is the change in conductivity is not recognized and stable at high temperatures It was confirmed that the film was an aniline-based conductive polymer film.

Example 9 5 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 1) and 0.05 parts by weight of dodecylbenzenesulfonic acid were stirred and dissolved in 100 parts by weight of water at room temperature.
A doping solution composition was prepared. The pH of the doping solution composition was 1.5. Next, 2 parts by weight of an aniline-based polymer (polyaniline synthesized in Example 5) was stirred and dissolved at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, and applied on a glass substrate by spin coating.
It was dried at 120 ° C. to form an aniline-based polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □.
The values were above. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 1.0 × 10 ⁷ Ω / □.
Then, after the the conductive polymer film was heated for 2 hours at 250 ° C., was measured surface resistance, 1.0 × 10 ⁷
When the surface resistance was measured again after being left at 120 ° C. for one week, it was found to be 1.0 × 10 ⁷ Ω / □, and no change in conductivity was observed. It was confirmed that the film was a conductive polymer film.

Example 10 5 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 1) and 1.5 parts by weight of ammonia were added to water 1
The mixture was stirred and dissolved in 00 parts by weight at room temperature to prepare a doping solution composition. The pH of the doping solution composition is 7.3.
Met. Next, 2 parts by weight of an aniline-based polymer (polyaniline synthesized in Example 5) was dissolved by stirring at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, and the solution was applied on a glass substrate by a spin coating method, and then applied at 120 ° C. And let it dry
An aniline polymer film was formed. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film is
It was 3.0 × 10 ⁷ Ω / □. Next, the conductive polymer film was subjected to heat treatment at 250 ° C. for 2 hours, and the surface resistance was measured. As a result, it was 2.8 × 10 ⁷ Ω / □.
After being left at 120 ° C. for one week, the surface resistance was measured again. As a result, it was 2.8 × 10 ⁷ Ω / □, no change in conductivity was observed, and the aniline-based conductive polymer film was stable at high temperatures. Was confirmed.

Example 11 5 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 1) and 1 part by weight of triethylamine were stirred and dissolved in 100 parts by weight of water at room temperature to prepare a doping solution composition. Next, 2 parts by weight of the aniline-based polymer (polyaniline synthesized in Example 5) was added to N-methyl-2-
The solution was stirred and dissolved in 100 parts by weight of pyrrolidone at room temperature, applied on a glass substrate by spin coating, and dried at 120 ° C. to form an aniline-based polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □ or more.
The aniline-based polymer film was immersed in the doping solution for 1 hour, dried at 120 ° C., and washed with water.
The resultant was dried at ℃ to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 8.0 × 10 ⁶ Ω / □. Next, the conductive polymer film was subjected to a heat treatment at 250 ° C. for 2 hours, and the surface resistance was measured.
0 ⁷ Ω / □ and is, also, after standing for 1 week at 120 ° C., was measured surface resistance again, 8.3 × 10 ^{7 Ω} / □ and is the change in conductivity is not recognized and stable at high temperatures It was confirmed that the film was an aniline-based conductive polymer film.

Example 12 3 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 3) was stirred and dissolved in 100 parts by weight of water at room temperature to prepare a doping solution composition. Next, 2 parts by weight of an aniline-based polymer (poly (methylaniline) synthesized in Example 6) and 0.5 part by weight of polyethylene terephthalate “Vylon 200” (manufactured by Toyobo Co., Ltd.) were added to N-methyl-2-pyrrolidone. 100 parts by weight were stirred and dissolved at room temperature, and applied on a glass substrate by a spin coating method.
It was dried at 0 ° C. to form an aniline-based polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 5.5 × 10 ⁷ Ω / □. Next, the conductive polymer film was subjected to a heat treatment at 250 ° C. for 2 hours, and the surface resistance was measured. The result was 5.3 × 10 ⁷ Ω / □.
The surface resistance was measured again after being left at 120 ° C. for one week, and found to be 5.9 × 10 ⁷ Ω / □, no change in conductivity was observed. It was confirmed to be a molecular film.

Example 13 5 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 4) was stirred and dissolved at room temperature in 100 parts by weight of water / isopropyl alcohol (7/3) to prepare a doping solution composition. Prepared. Next, an aniline-based polymer (poly (methoxyaniline) synthesized in Example 7) 2
A part by weight was stirred and dissolved at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, applied on a glass substrate by a spin coating method, and dried at 120 ° C. to form an aniline polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³
The value was Ω / □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour and then washed with water.
It was dried at 0 ° C. to form an aniline-based conductive polymer film.
The surface resistance of the obtained film was 4.8 × 10 ⁷ Ω / □. Next, the conductive polymer film was subjected to a heat treatment at 250 ° C. for 2 hours, and the surface resistance was measured.
10 ⁷ Ω / □, and after standing at 120 ° C. for 1 week,
When the surface resistance was measured again, it was 5.0 × 10 ⁷ Ω / □.
No change in conductivity was observed, and it was confirmed that the aniline-based conductive polymer film was stable at high temperatures.

Example 14 5 parts by weight of a soluble aniline-based conductive polymer (the polymer synthesized in Example 2), 2 parts by weight of triethanolamine and 0.1 part by weight of dodecylbenzenesulfonic acid were added to 100 parts of water.
The solution was stirred and dissolved at room temperature in parts by weight to prepare a doping solution composition. Next, 2 parts by weight of an aniline-based polymer (polyaniline synthesized in Example 5) was dissolved by stirring at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, and the solution was applied on a glass substrate by a spin coating method, and then applied at 120 ° C. To form an aniline-based polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 1.
It was 6 × 10 ⁷ Ω / □. Next, the conductive polymer film was heated at 250 ° C. for 2 hours, and the surface resistance was measured to be 1.4 × 10 ⁷ Ω / □.
After leaving at 0 ° C for one week, the surface resistance was measured again.
1.1 × 10 ⁷ Ω / □, no change in conductivity was observed, and it was confirmed that the aniline-based conductive polymer film was stable at high temperatures.

Comparative Example 1 3 parts by weight of p-toluenesulfonic acid was dissolved in 100 parts by weight of water at room temperature with stirring to prepare a doping solution composition. Next, 2 parts by weight of an aniline-based polymer (polyaniline synthesized in Example 5) was added to N-methyl-2-pyrrolidone 100
The aniline-based polymer film was formed by dissolving in parts by weight at room temperature while stirring and dissolving it, applying it on a glass substrate by spin coating, and drying it at 120 ° C. The surface resistance of the obtained film was 1.
The value was 0 × 10 ¹³ Ω / □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 6.2 × 10 ⁹
Ω / □. Next, the above conductive polymer film was
After heat treatment at 2 ° C. for 2 hours, the surface resistance was measured and found to be 1.0 × 10 ¹³ Ω / □ or more.
After one week, the surface resistance was measured again.
It was 0 × 10 ¹³ Ω / □ or more, and the conductivity was remarkably reduced, and it was confirmed that the film was unstable at high temperatures.

Comparative Example 2 3 parts by weight of sulfuric acid was stirred and dissolved in 100 parts by weight of water at room temperature to prepare a doping solution composition. Next, 2 parts by weight of an aniline-based polymer (polyaniline synthesized in Example 5) was stirred and dissolved at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, and applied on a glass substrate by spin coating.
It was dried at 120 ° C. to form an aniline-based polymer film. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □.
The values were above. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film was 4.7 × 10 ⁹ Ω / □.
Then, after the the conductive polymer film was heated for 2 hours at 250 ° C., was measured surface resistance, 1.0 × 10 ¹³
Ω / □ or more, and after being left at 120 ° C. for 1 week, the surface resistance was measured again. As a result, it was 1.0 × 10 ¹³ Ω / □ or more. It was confirmed that.

Comparative Example 3 3 parts by weight of sulfuric acid and 1 part by weight of ammonia were dissolved in 100 parts by weight of water with stirring at room temperature to prepare a doping solution composition.
Next, 2 parts by weight of an aniline-based polymer (poly (methylaniline) synthesized in Example 6) was stirred and dissolved at room temperature in 100 parts by weight of N-methyl-2-pyrrolidone, and applied to a glass substrate by spin coating. And dried at 120 ° C.
An aniline polymer film was formed. The surface resistance of the obtained film was 1.0 × 10 ¹³ Ω / □ or more. The aniline-based polymer film was immersed in the doping solution for 1 hour, washed with water, and dried at 120 ° C. to form an aniline-based conductive polymer film. The surface resistance of the obtained film is
1.0 × 10 ¹³ Ω / □ or more. Next, the conductive polymer film was subjected to a heat treatment at 250 ° C. for 2 hours, and the surface resistance was measured. As a result, it was 1.0 × 10 ¹³ Ω / □ or more. When measuring the surface resistivity, 1.0 × 10 ¹³ Ω / □ or more in and conductivity is significantly decreased, was confirmed to be unstable at high temperatures.

[0091]

According to the present invention, as a dopant for an aniline-based polymer film, an acid group-substituted aniline having a sulfone group and / or a carboxyl group is used as a repeating unit.
%, A chemically and physically stable aniline-based conductive polymer film having high conductivity and excellent heat resistance and weather resistance can be provided.

[Brief description of the drawings]

FIG. 1 shows an IR spectrum of the aniline-based conductive polymer film produced in Example 8 by an ATR method.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08J 5/18 C08L 79/00-79/08

Claims (9)

(57) [Claims] 1. A compound of the general formula (1) (Wherein, R _{1 to} R ₁₈ are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a nitro group, an amino group, and a halogen atom. X represents an arbitrary number from 0 to 1, n represents a degree of polymerization, and 2 to 50.
Aniline-based polymer film 00 undoped state that deacidified or reduction treatment represented by the number a is) of (m), sulfo
Group- containing aniline having an acidic group of a carboxyl group and / or a carboxyl group, a polymer having 70% or more as a repeating unit of an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof, and having a weight average molecular weight of 1900 or more An aniline-based conductive polymer film, wherein the soluble aniline-based conductive polymer (a) which is a solid at room temperature is added as a dopant. 2. The aniline-based conductive polymer film according to claim 1, wherein the aniline-based polymer film (m) is a composite film containing a polymer compound. 3. The soluble aniline-based conductive polymer (a) is represented by the general formula (2): (In the formula, A is a sulfone group, a carboxyl group, or one group selected from alkali metal salts, ammonium salts, and substituted ammonium salts thereof, and B is hydrogen, a methyl group, an ethyl group, an n-propyl group, iso-propyl group,
n-butyl group, iso-butyl group, sec-butyl group,
alkyl groups such as t-butyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group,
t-butoxy group, heptoxy group, hexoxy group, octoxy group, nanoxy group, decoxy group, undecanoxy group, alkoxy group such as dodecanoxy group, hydroxy group, nitro group, and fluoro group, chloro group, bromo group
And represents one group selected from halogen groups . x is 0-1
Any indicates the number of, n represents indicates the degree of polymerization, a sulfone group and / or carboxy represented by a is) Number of 3-5000
A polymer having an acid group-substituted aniline having an acid group of a xyl group, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof in a proportion of 70% or more as a repeating unit and having a weight average molecular weight of 1900 or more at room temperature. The aniline-based conductive polymer film according to claim 1 or 2. 4. The method according to claim 1, wherein the soluble aniline-based conductive polymer (a) has a sulfone group and / or a carboxyl group.
An acidic group-substituted aniline having an acidic group , an alkali metal salt thereof, an ammonium salt, or a substituted ammonium salt thereof, obtained by polymerizing at least one compound (a) with a oxidizing agent in a solution containing a basic compound (b). The aniline-based conductive polymer film according to claim 1, which is a soluble conductive polymer obtained. 5. The compound (a) represented by the general formula (3): (Wherein, R _{19 to} R ₂₃ are each selected from hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 12 carbon atoms, an acidic group, a hydroxyl group, a nitro group, and a halogen. At least one of which represents an acidic group, wherein the acidic group represents a sulfone group or a carboxyl group), an aniline substituted with an acidic group represented by the following formula: The aniline-based conductive polymer film according to claim 4, which is at least one compound among ammonium salts. 6. The method according to claim 1, wherein at least one surface of the substrate has the general formula (1) (Wherein, R _{1 to} R ₁₈ are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a nitro group, an amino group, and a halogen atom. X represents an arbitrary number from 0 to 1, n represents a degree of polymerization, and 2 to 50.
After the formation of the undoped or reduced aniline-based polymer film (m) represented by the following formula:
An acid-substituted aniline having an acid group of a sulfone group and / or a carboxyl group, a polymer having at least 70% of an alkali metal salt, an ammonium salt and / or a substituted ammonium salt as a repeating unit, and having a weight average molecular weight of 1900 or more A soluble aniline-based conductive polymer (a) which is a solid at room temperature and a solvent (b)
A method for producing an aniline-based conductive polymer film, comprising doping with a composition comprising: 7. The composition according to claim 6, wherein the composition contains at least one nitrogen-containing compound (c) and / or a surfactant (d) selected from amines and quaternary ammonium salts. A method for producing an aniline-based conductive polymer film. 8. The aniline-based polymer film (m) is a composite film containing a polymer compound.
A method for producing the aniline-based conductive polymer film according to the above. 9. The aniline-based conductive polymer according to claim 6, wherein the heat treatment is performed in a temperature range of 40 to 250 ° C. to remove the solvent (b) and the nitrogen-containing compound (c). Manufacturing method of membrane.