JP2023032466A - Method for producing conductive polymer-containing liquid, and method for producing conductive laminate - Google Patents

Abstract

To provide a method for producing a conductive polymer-containing liquid containing a conductivity complex having excellent dispersion stability to an organic solvent such as isopropyl alcohol without using a hydroxy pyridine compound, and a method for producing a conductive laminate.SOLUTION: A method for producing a conductive polymer-containing liquid includes a reaction precipitation step for adding, to an alcohol solution containing a quaternary ammonium compound, a conductive polymer aqueous dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, and reacting some anion groups of the polyanion with the quaternary ammonium compound, so that a reaction product deposits; and a preparation step for dispersing the reaction product in a disperse solvent to prepare a conductive polymer-containing liquid.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing a conductive polymer-containing liquid containing a π-conjugated conductive polymer, and a method for producing a conductive laminate.

A conductive polymer dispersion containing a conductive composite in which a π-conjugated conductive polymer is doped with a polyanion is sometimes used as a paint or a component thereof for forming a conductive layer. For example, poly(3,4-ethylenedioxythiophene), which is a π-conjugated conductive polymer, is difficult to disperse in water. Increased dispersibility in water.
When a conductive polymer dispersion is applied to a plastic substrate to form a conductive layer, the conductive polymer dispersion is required to have high wettability to the substrate. For this purpose, in order to disperse the conductive composite in an organic solvent such as alcohol instead of an aqueous dispersion medium, a technique has been disclosed in which an amine compound is reacted with the conductive composite to make it hydrophobic (for example, Patent Documents 1).

JP 2021-095459 A

However, in the method disclosed in Patent Document 1, there is a restriction that a hydroxypyridine compound must be used as an essential component in addition to the amine compound to be bound to the conductive composite.

The present invention provides a method for producing a conductive polymer-containing liquid containing a conductive composite having excellent dispersion stability in an organic solvent such as isopropyl alcohol without using a hydroxypyridine compound, and a method for producing a conductive laminate. offer.

[1] An aqueous conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion is added to an alcohol solution containing a quaternary ammonium compound to obtain an anion of a part of the polyanion. a reaction precipitation step of reacting the group with the quaternary ammonium compound to precipitate a reaction product; and a preparation step of dispersing the reaction product in a dispersion solvent to obtain a conductive polymer-containing liquid. A method for producing a conductive polymer-containing liquid.
[2] After the reaction precipitation step, a recovery step of recovering the reaction product, a cleaning step of cleaning the recovered reaction product with a cleaning liquid, and subjecting the cleaned reaction product to the preparation step to perform the The method for producing a conductive polymer-containing liquid according to [1], further comprising obtaining a conductive polymer-containing liquid.
[3] a sedimentation step of precipitating the reaction product in the alcohol solution after the reaction precipitation step and removing the supernatant to obtain a slurry containing the reaction product; and the slurry obtained in the precipitation step. After adding a washing liquid to and stirring, the reaction product is precipitated in the washing liquid, the supernatant is removed, and a washing step of obtaining a slurry containing the reaction product, and the slurry obtained in the washing step contains The method for producing a conductive polymer-containing liquid according to [1], further comprising: obtaining the conductive polymer-containing liquid by subjecting the reaction product to the preparation step.
[4] The method for producing a conductive polymer-containing liquid according to any one of [1] to [3], wherein the dispersion solvent contains isopropyl alcohol.
[5] The method for producing a conductive polymer-containing liquid according to [4], wherein the content of isopropyl alcohol with respect to the total mass of the conductive polymer-containing liquid is 84% by mass or more.
[6] Any one of [1] to [5], wherein the total mass of the conductive polymer aqueous dispersion added to 100 to 300 parts by mass of the alcohol solution containing the quaternary ammonium compound is 100 parts by mass. A method for producing a conductive polymer-containing liquid according to the item.
[7] The method for producing a conductive polymer-containing liquid according to any one of [1] to [6], wherein the quaternary ammonium compound contains a tetraalkylammonium halide.
[8] The conductive polymer-containing liquid according to any one of [1] to [7], including further adding a conductivity enhancer to the conductive polymer-containing liquid in the preparation step. Production method.
[9] Any one of [1] to [8], wherein the π-conjugated conductive polymer contains poly(3,4-ethylenedioxythiophene), or the polyanion contains polystyrenesulfonic acid. A method for producing a conductive polymer-containing liquid according to the item.
[10] A step of obtaining a conductive polymer-containing liquid by the production method according to any one of [1] to [9], and coating at least a part of a substrate with the conductive polymer-containing liquid. A method for manufacturing a conductive laminate, comprising:

According to the method for producing a conductive polymer-containing liquid of the present invention, it is possible to easily produce a conductive polymer-containing liquid having excellent dispersion stability (in other words, storage stability) of the conductive composite.
According to the method for producing the conductive laminate of the present invention, the conductive polymer-containing liquid to be used has excellent dispersion stability and excellent wettability to the substrate, so that the conductive laminate can be easily produced.

The present invention is considered to contribute to SDGs Goal 12 “Responsible consumption and production”.

In the present specification and claims, the lower limit and upper limit of the numerical range indicated by "-" shall be included in the numerical range.

<<Method for producing liquid containing conductive polymer>>
In the first aspect of the present invention, an aqueous conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion is added to an alcohol solution (reaction solution) containing a quaternary ammonium compound. a reactive deposition step of reacting a part of the anionic groups of the polyanion with the quaternary ammonium compound to deposit a reaction product; A method for producing a conductive polymer-containing liquid, comprising a preparation step of obtaining

[Reactive precipitation step]
In this step, an aqueous conductive polymer dispersion is added to an alcohol solution (reaction solution) containing a quaternary ammonium compound to form a reaction product of the conductive composite and the quaternary ammonium compound in the reaction solution. It is a process of precipitating inside.

Examples of the quaternary ammonium compound contained in the reaction solution and reacted with the conductive composite include those capable of forming the substituent (C) described below.

When the conductive polymer aqueous dispersion is added to the reaction solution, the quaternary ammonium compound reacts with some anionic groups of the polyanions of the conductive composite. As a result, a substituent (C) described later is formed, the conductive composite becomes hydrophobic, and the dispersion stability in organic solvents such as isopropyl alcohol is improved, and stable dispersion in the reaction solution is achieved. It becomes difficult and precipitates out as a precipitate.

The alcohol contained in the reaction solution may be of one type or two or more types.
Specific examples include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, t-butanol, allyl alcohol and the like.

The content of the quaternary ammonium compound in the reaction solution is preferably 10 parts by mass or more and 5000 parts by mass or less, and 100 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the total mass of the conductive composite to be added. is more preferable, and 150 parts by mass or more and 500 parts by mass or less is even more preferable.
When it is at least the lower limit of the above range, the reaction efficiency between the conductive composite and the quaternary ammonium compound is enhanced, and the reaction product can be easily obtained.
If it is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in conductivity of the conductive composite due to contamination with an unreacted quaternary ammonium compound.

The aqueous conductive polymer dispersion is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium. Examples of the π-conjugated conductive polymer and polyanion include those described later.
The aqueous dispersion medium is water or a mixture of water and a water-soluble organic solvent. A water-soluble organic solvent is one that dissolves 1 g or more in 100 g of water (20° C.). Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The number of water-soluble organic solvents contained in the aqueous dispersion medium may be one, or two or more.
The water content relative to the total mass of the aqueous dispersion medium is preferably more than 50% by mass, more preferably 60% by mass or more, still more preferably 80% by mass or more, and may be 100% by mass. A high water content increases the dispersibility of the conductive composite, which in turn increases the reaction efficiency with the quaternary ammonium compound. Furthermore, the reaction product is easily precipitated in the reaction solution.

The conductive polymer aqueous dispersion can be obtained, for example, by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous polyanion solution. A commercially available conductive polymer aqueous dispersion may also be used.
A known catalyst may be applied to the chemical oxidation polymerization. For example, catalysts and oxidants can be used. Examples of catalysts include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

The content of the π-conjugated conductive polymer and the polyanion is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 2% by mass or less with respect to the total mass of the aqueous conductive polymer dispersion. is more preferable, and 0.8% by mass or more and 1.5% by mass or less is even more preferable.
Within the above preferred range, the dispersibility of the conductive composite increases, and the reaction efficiency with the quaternary ammonium compound increases.

The total mass of the conductive polymer aqueous dispersion added to 100 to 300 parts by mass of the alcohol solution (reaction solution) containing the quaternary ammonium compound is preferably 20 to 200 parts by mass, more preferably 100 parts by mass. Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

The volume ratio (V1/V2) of the volume V2 of the conductive polymer aqueous dispersion to be added to the volume V1 of the reaction solution is preferably 0.3 to 3.0, more preferably 0.5 to 2.5. 0.8 to 2.0 is more preferred.
Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

The method of adding the conductive polymer aqueous dispersion to the reaction solution is not particularly limited, and the desired amount may be added at once in several seconds, or may be added dropwise slowly. From the viewpoint of obtaining a conductive composite with a small particle size and increasing the conductivity, the method of dropping slowly is preferred.
The speed at which the conductive polymer aqueous dispersion is dropped into the reaction solution is preferably 1 minute to 3 hours, more preferably 10 minutes to 2 hours, from the start of dropping to the end of dropping, assuming that a constant amount of water is continuously dropped. . It is preferable to gently stir the reaction solution during the dropping.
Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

The amount of the conductive polymer aqueous dispersion added dropwise to the reaction solution is preferably 0.1 to 100 ml/min, more preferably 1 to 10 ml/min. It is preferable to gently stir the reaction solution during the dropping.
Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

When the conductive polymer dispersion is added to the reaction solution and gently stirred, the reaction product is precipitated within several minutes to several hours. The completion of the reaction can be confirmed by visually observing the completion of precipitation of the reaction product.

The temperature of the reaction solution is not particularly limited, and may be, for example, 5 to 40°C.

The production method of this embodiment may further include a recovery step, a sedimentation step, and a washing step described below after the reactive precipitation step and before the preparation step.

[Recovery process]
This step is a step of separating and recovering the reaction precipitate deposited in the reaction precipitation step from the reaction solution.
Examples of recovery methods include filtration.
The amount of water in the recovered reaction product (precipitate) is preferably as low as possible, and most preferably no water at all.
Methods for reducing the water content include, for example, a method of washing away the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[Sedimentation process]
This step is a step of allowing the reaction precipitate deposited in the reaction precipitation step to settle in the reaction solution (in the alcohol solution), removing the supernatant, and obtaining a slurry containing the reaction precipitate.
Precipitation of reaction deposits can be carried out by allowing the reaction solution after the reaction to stand still. The method for removing the supernatant after sedimentation is not particularly limited, and examples thereof include decantation and suction.

[Washing process]
A washing step is preferably added after the recovering step or the sedimentation step.
The washing step is a step of washing the reaction product with a washing liquid.
Examples of the method for washing the reaction product recovered in the recovery step include a method of pouring a cleaning liquid over the reaction product and a method of gently stirring the reaction product in the cleaning liquid. After stirring, the reaction product can be recovered from the washing liquid in the same manner as the recovery step.
As the washing step performed after the sedimentation step, a method of adding a washing liquid to the slurry and stirring the slurry can be used. After stirring, the reaction product is allowed to settle in the washing solution in the same manner as in the precipitation step, and the supernatant is removed to obtain a slurry containing the reaction product.
By the washing process described above, residual water, unreacted quaternary ammonium compound, and impurities contained in the conductive polymer aqueous dispersion can be removed.
The above cleaning process is not limited to being performed once, and may be performed multiple times.

The cleaning liquid is preferably one that can clean while minimizing the dissolution of precipitates. Therefore, as the cleaning liquid, an alcohol-based solvent other than isopropyl alcohol is preferable. One type of organic solvent may be contained in the cleaning liquid, or two or more types may be used.

[Preparation process]
This step is a step of dispersing the reaction product obtained in the preceding step in a dispersing solvent to obtain a conductive polymer-containing liquid.

The dispersion solvent in this step contains one or more organic solvents, and contains isopropyl alcohol because the reaction product (the conductive composite reacted with the quaternary ammonium compound) has excellent dispersion stability. is preferred.
The content of isopropyl alcohol with respect to the total mass of the conductive polymer-containing liquid obtained in this step is preferably 84% by mass or more, more preferably 86% by mass or more, still more preferably 88% by mass or more, and particularly 90% by mass or more. Preferably, 92% by mass or more is most preferable. The upper limit of the content of isopropyl alcohol is, for example, 99.9% by mass or less, leaving room for containing the reaction product. Within the above preferred range, the dispersion stability of the reaction product is improved, and the wettability to the substrate is also excellent.

The conductive polymer-containing liquid obtained in this step may contain a small amount of water.
The water content relative to the total mass of the conductive polymer-containing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the water content is low, the dispersion stability of the conductive composite is improved and the wettability to the substrate is also excellent.

An organic solvent other than isopropyl alcohol may be added to the conductive polymer-containing liquid obtained in this step.
Examples of the organic solvent include hydrocarbon-based solvents, ketone-based solvents, alcohol-based solvents, ether-based solvents, and nitrogen atom-containing compound-based solvents.
Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
Ketone solvents include, for example, diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of alcohol solvents include methanol, ethanol, 1-propanol, n-butanol, t-butanol, and allyl alcohol.
Examples of ether-based solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, and the like.
Examples of nitrogen atom-containing compound solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
Among the above solvents, alcohol-based solvents having high compatibility with isopropyl alcohol are preferred, and ethanol or 1-propanol is more preferred.

It is preferable to subject the conductive polymer-containing liquid obtained by adding a dispersing solvent such as isopropyl alcohol to the reaction product to a dispersion treatment by stirring. The method of stirring is not particularly limited, and may be stirring with a weak shearing force such as a stirrer, or may be stirred using a dispersing machine (such as a homogenizer) with a high shearing force, or a high-pressure homogenizer with a high shearing force. It is preferable to stir using.

The content of the reaction product with respect to the total mass of the conductive polymer-containing liquid dispersed by the high-pressure homogenizer is, for example, preferably 0.01% by mass or more and 5% by mass or less, and 0.05% by mass or more and 2% by mass or less. It is more preferably 0.1% by mass or more and 1% by mass or less.
When the concentration is within the above range, the dispersion stability of the reaction product can be sufficiently enhanced.

(high conductivity agent)
A conductivity enhancer may be further added to the conductive polymer-containing liquid obtained in this step.
Here, π-conjugated conductive polymers, polyanions, organic solvents, and quaternary ammonium compounds are not classified as highly conductive agents.
Conductive agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxyl groups, compounds having one or more hydroxyl groups and one or more carboxyl groups, compounds having an amide group, and imide groups. at least one compound selected from the group consisting of a compound having a A compound is preferred. Among them, it has good solubility in isopropyl alcohol and easily obtains the effect of increasing conductivity. Certain compounds are more preferred. Here, the unsaturated bond includes not only the unsaturated bond between adjacent carbon atoms but also the unsaturated bond between adjacent atoms other than carbon atoms.
The conductive polymer-containing liquid of the present embodiment may contain one type of conductivity enhancer, or two or more types thereof.

Specific examples of suitable high-conductivity agents include at least one selected from propylene glycol, dimethylsulfoxide, hydroxyethylacrylamide, N,N-dimethylacrylamide, 2,3-butenediol, and 2,3-butynediol. mentioned.

The content of the conductive agent with respect to the total mass of the conductive polymer-containing liquid is preferably 1% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 10% by mass or less, and 3% by mass or more and 7% by mass or less. is more preferred.
When the amount is at least the lower limit of the above range, the effect of improving conductivity by adding the high conductivity agent is sufficiently exhibited, and when the amount is at most the upper limit of the above range, the dispersion stability of the conductive composite is further improved.

(Other additives)
Other known additives may be added to the conductive polymer-containing liquid obtained in this step.
Additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers and the like can be used.
Examples of surfactants include nonionic, anionic, and cationic surfactants, with nonionic surfactants being preferred from the standpoint of storage stability. A polymeric surfactant such as polyvinylpyrrolidone may also be added.
Examples of inorganic conductive agents include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Antifoaming agents include silicone resins, polydimethylsiloxane, silicone oils and the like.
Examples of coupling agents include silane coupling agents having a vinyl group or an amino group.
Antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars and the like.
UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. is mentioned.
When the conductive polymer-containing liquid contains the above additive, the content ratio is appropriately determined according to the type of additive. It can be in the range of 5 parts by mass or less.

≪Liquid containing conductive polymer≫
The conductive polymer-containing liquid obtained by the manufacturing method of the first aspect of the present invention preferably has the following aspects. First, the conductive polymer-containing liquid preferably contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and isopropyl alcohol (isopropanol).
The polyanion is modified by reaction of some anionic groups of the polyanion with a quaternary ammonium compound.
The content of the isopropyl alcohol with respect to the total mass of the conductive polymer-containing liquid is preferably 84% by mass or more.
In the conductive polymer-containing liquid, the conductive composite may be in a dispersed state or in a dissolved state. In this specification, the dispersed state and the dissolved state are not distinguished from each other unless otherwise specified, and are simply referred to as the dispersed state.

[Conductive composite]
The conductive composite contained in the conductive polymer-containing liquid contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite forms a conductive composite having conductivity by doping the π-conjugated conductive polymer.
In the polyanion, only some of the anionic groups are doped into the π-conjugated conductive polymer, and there are surplus anionic groups that do not participate in the doping. Since the surplus anionic groups are hydrophilic groups, the conductive composite in which the surplus anionic groups are not modified has water dispersibility.

(π-conjugated conductive polymer)
The π-conjugated conductive polymer may be any organic polymer having a π-conjugated main chain. molecules, polyphenylene-based conductive polymers, polyphenylene-vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, copolymers thereof, and the like. Polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable from the viewpoint of stability in air, and polythiophene-based conductive polymers are more preferable from the viewpoint of transparency.

Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), and poly(3-hexylthiophene). , poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly (3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene) , poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene) , poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3 ,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene) , poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly( 3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3- methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxy butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butyl pyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3 -carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole) , poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), poly(3-methyl-4-hexyloxypyrrole).
Polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid).
Among these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred because of its excellent conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

(polyanion)
A polyanion is a polymer having two or more monomer units having an anionic group in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, Polymers having carboxy groups such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, etc. A polyanion is a single monomer. may be a homopolymer obtained by polymerizing or a copolymer obtained by polymerizing two or more monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
One of the polyanions may be used alone, or two or more thereof may be used in combination.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The mass-average molecular weight is a mass-based average molecular weight determined by pullulan conversion using gel filtration chromatography.

Assuming that the total number of anionic groups in the polyanion is 100 mol %, the excess anionic group is preferably 30 mol % or more and 90 mol % or less, more preferably 45 mol % or more and 75 mol % or less.

The polyanion that constitutes the conductive composite of the present invention is modified by reacting surplus anionic groups of the polyanion that do not participate in doping (hereinafter also referred to as "partial anionic groups") with a quaternary ammonium compound. ing. That is, the polyanion of the present invention has substituents (C) formed by reaction of the quaternary ammonium compound with some of the anionic groups.

(Substituent C)
Substituent (C) is presumed to be a group represented by the following formula (C).

-N ⁺ R ¹¹ R ¹² R ¹³ R ¹⁴ (C)
[In Formula (C), R ¹¹ to R ¹⁴ are each independently a hydrocarbon group which may have a substituent. ]

In the substituent (C), the leftmost bond represents that the negative charge of the anion group and the positive charge of the quaternary ammonium cation are bonded. Examples of negatively charged anionic groups include anionic groups in which active protons are bonded to oxygen atoms, such as “—SO ₃ ⁻ ”.

R ¹¹ to R ¹⁴ in chemical formula (C) are hydrocarbon groups which may have a substituent. R ¹¹ to R ¹⁴ in chemical formula (C) are substituents derived from a quaternary ammonium compound.
The hydrocarbon group in the chemical formula (C) is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. groups.
Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl groups.
A phenyl group, a hydroxyl group, etc. are mentioned as a substituent of an aliphatic hydrocarbon group.
A phenyl group, a naphthyl group, etc. are mentioned as an aromatic-hydrocarbon group.
Substituents for the aromatic hydrocarbon group include alkyl groups having 1 to 5 carbon atoms, hydroxyl groups and the like.

The quaternary ammonium compound preferably has a substituent having 3 or more carbon atoms on the nitrogen atom, and has a substituent of 5 or more, because the dispersibility in the organic solvent increases and the conductivity improves. It is more preferable to have a substituent having 7 or more carbon atoms on the nitrogen atom. The upper limit of the carbon number of each substituent on the nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in solvents, for example, it is preferably 40 or less, more preferably 30 or less, and further 20 or less. preferable.
The total number of carbon atoms of R ¹¹ to R ¹⁴ in the quaternary ammonium compound is preferably 8-44, more preferably 12-40, even more preferably 16-36.
The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

Preferably, the quaternary ammonium compound is water insoluble. Here, "water-insoluble" means that the solubility in 100 g of water at 20°C is less than 1 g.
Since the water-insoluble quaternary ammonium compound has high reactivity with polyanions, it is possible to easily form the target substituent (C).

Preferably, the quaternary ammonium compound is a tetraalkylammonium halide. This is because the polyanion is highly reactive and the reaction product is difficult to dissolve in an aqueous dispersion medium and easily precipitates. The halogen ion of the counter anion is preferably a bromide ion or a chloride ion, more preferably a bromide ion.

Specific examples of quaternary ammonium compounds include tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetra-n-octylammonium salts, tetra-n-decylammonium salts, and tetraphenylammonium salts. , tetrabenzylammonium salts, tetranaphthylammonium salts, and other quaternary ammonium salts.
Counter anions of ammonium cations include, for example, halogen ions such as bromide ions and chloride ions, and hydroxy ions.

The content of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. is more preferable, and 100 parts by mass or more and 500 parts by mass or less is even more preferable. If the polyanion content is at least the above lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the polyanion content is equal to or less than the above upper limit, the amount of anionic groups that do not participate in doping is appropriately suppressed, and the anionic groups can be easily converted to hydrophobicity when the quaternary ammonium compound is reacted.

The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid is, for example, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, 0.2% by mass or more and 1% by mass or less is more preferable. Within the above preferred range, the dispersion stability of the conductive composite is further improved.

<Particle size>
The dispersion stability of the produced conductive polymer-containing liquid can be evaluated by the particle size of the conductive composite in the liquid. Comparing the particle size Q0 immediately after production and the particle size Q1 after storage, the closer the ratio represented by Q1/Q0 to 1, the better the dispersion stability. Particles of the electrically conductive composite gradually aggregate after production, and when aggregated to the extent that they are visible, they settle to form a precipitate. Such a conductive polymer-containing liquid containing an aggregated conductive composite is difficult to apply, and even if it can be applied, uneven distribution of the conductive composite contained in the coating film occurs, resulting in The conductivity of the conductive layer becomes poor.

The particle size of the conductive composite is preferably 10 nm or more and 500 nm or less at 25° C. when the concentration of the conductive composite is adjusted to 0.1 to 0.5% by mass with respect to the total mass of the conductive polymer-containing liquid. 50 nm or more and 450 nm or less is more preferable, and 100 nm or more and 400 nm or less is even more preferable. Within these preferred ranges, the dispersion stability of the conductive composite is further improved.
The particle size is obtained as a value obtained by measuring the cumulant average particle size by a dynamic light scattering method.

<<Method for manufacturing conductive laminate>>
A second aspect of the present invention comprises a step of obtaining a conductive polymer-containing liquid by the production method of the first aspect, and coating the conductive polymer-containing liquid on at least one surface of a substrate. A method for manufacturing a conductive laminate.
By the production method of this aspect, a conductive laminate is obtained which includes a base material and a conductive layer formed on at least one surface of the base material and formed of a cured product of the conductive polymer-containing liquid of the first mode. be done.

[Conductive layer]
The average thickness of the conductive layer provided on at least one surface of the substrate is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and 30 nm or more and 30 μm or less. is more preferred.
If the average thickness of the conductive layer is at least the lower limit, high conductivity can be exhibited, and if the average thickness is at most the upper limit, the adhesion of the conductive layer to the substrate is further improved.

The conductive layer included in the conductive laminate contains a conductive composite containing a π-conjugated conductive polymer and a polyanion.
When the conductive polymer-containing liquid applied to the substrate contains a binder component, the conductive layer contains the binder component or a cured product obtained by curing the binder component.

[Base material]
The base material constituting the conductive laminate may be a base material made of an insulating material or a base material made of a conductive material. The shape of the substrate is not particularly limited, and examples thereof include shapes mainly composed of planes such as films and substrates.
Examples of insulating materials include glass, synthetic resins, and ceramics.
Examples of conductive materials include metals, conductive metal oxides, and carbon.

(Film substrate)
When a film substrate is used as the substrate, the conductive laminate becomes a conductive film.
Examples of the film substrate include a plastic film made of a synthetic resin. Examples of the synthetic resin include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyacrylate. , polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, and the like.
From the viewpoint of enhancing the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably the same type of resin as the binder resin, and polyester resin such as polyethylene terephthalate is particularly preferable.

The synthetic resin for the film substrate may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
The film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc., in order to further improve the adhesiveness of the conductive layer formed from the conductive polymer-containing liquid.

The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is at least the lower limit, the film is less likely to break, and when it is at most the upper limit, sufficient flexibility as a film can be ensured.
The average thickness of the film substrate is the value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

(Glass substrate)
Examples of glass substrates include alkali-free glass substrates, soda-lime glass substrates, borosilicate glass substrates, quartz glass substrates, and the like. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease, so among the above glass substrates, non-alkali glass is preferable. Here, the alkali-free glass is a glass composition in which the content of alkali components is 0.1% by mass or less with respect to the total mass of the glass composition.

The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is at least the lower limit, it will be difficult to break, and if it is at most the upper limit, it can contribute to thinning of the conductive laminate.
The average thickness of the glass substrate is the value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

Examples of methods for coating (applying) the conductive polymer-containing liquid onto any surface of the substrate include gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, and fountain coaters. , methods using coaters such as rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters and screen coaters, methods using atomizers such as air spray, airless spray, and rotor dampening, immersion methods such as dipping, etc. can be applied.

The amount of the conductive polymer-containing liquid to be applied to the substrate is not particularly limited, but the solid content is 0.01 g/m ² or more in consideration of uniform coating, conductivity and film strength. It is preferably in the range of 10.0 g/m ² or less.

Conductivity in which a conductive layer (conductive film) is formed by drying a coating film made of a conductive polymer-containing liquid applied on a substrate and removing the dispersion medium, thereby curing the coating film. A laminate can be obtained.
Heat drying, vacuum drying, etc. are mentioned as a method of drying a coating film. As heat drying, for example, a method such as hot air heating or infrared heating can be employed.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, but is usually in the range of 50°C or higher and 150°C or lower. Here, the heating temperature is the set temperature of the drying device. A suitable drying time within the above heating temperature range is preferably 1 minute or more and 30 minutes or less, more preferably 5 minutes or more and 15 minutes or less.

When the conductive polymer-containing liquid contains an active energy ray-curable binder component, an active energy ray irradiation step of irradiating the dried conductive polymer coating film with an active energy ray is performed after the drying step. You may have more. If the active energy ray irradiation step is included, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
When having an active energy ray irradiation step, the active energy ray used includes ultraviolet rays, electron beams, visible rays, and the like. Ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, and the like can be used as the ultraviolet light source.

(Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of an ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was added while stirring at 80°C. After 20 minutes of addition, the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting sodium styrenesulfonate-containing solution, and about 1000 ml of the solvent in the polystyrenesulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This washing operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Production Example 2) Synthesis of Conductive Polymer Dispersion Containing π-Conjugated Conductive Polymer and Polyanion 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid were dissolved in 2000 ml of ion-exchanged water. was mixed at 20°C.
The mixed solution thus obtained was kept at 20° C., and while stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were slowly added, The mixture was stirred for 3 hours to react.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three times.
Next, 200 ml of 10 mass % diluted sulfuric acid and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by ultrafiltration. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated five times to obtain an aqueous dispersion of poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) doped with polystyrenesulfonic acid having a concentration of 1.2% by mass. The PSS content in PEDOT-PSS was 75% by mass.

(Production Example 3) Reaction A with quaternary ammonium salt
To the organic layer (organic solution) in which 2.4 g of tetrabutylammonium bromide was dissolved in 100 g of methanol, 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2 was added in one second and stirred for 30 minutes. As a result, a reaction product of tetrabutylammonium bromide and the conductive composite was deposited. This precipitate was collected by filtration, added with 100 g of methanol, stirred for 30 minutes while lightly suspending the precipitate, and then collected by filtration again. This washing operation was repeated once more. As a result, 1.1 g of the conductive composite having the aforementioned substituent (C) was obtained.

(Production Example 4) Reaction B with quaternary ammonium salt
1.1 g of a conductive composite having the substituent (C) was obtained in the same manner as in Production Example 3, except that 2.4 g of tetrabutylammonium bromide was changed to 2.4 g of tetraoctylammonium bromide.

(Production Example 5) Reaction C with quaternary ammonium salt
1.1 g of a conductive composite having the substituent (C) was obtained in the same manner as in Production Example 3, except that 2.4 g of tetrabutylammonium bromide was changed to 2.4 g of tetradecylammonium bromide.

(Production Example 6) Reaction D with quaternary ammonium salt
1.1 g of a conductive composite having the aforementioned substituent (C) was obtained in the same manner as in Production Example 3, except that 100 g of the PEDOT-PSS aqueous dispersion was added dropwise over 30 minutes. .

(Production Example 7) Reaction E with quaternary ammonium salt
1.1 g of a conductive composite having the substituent (C) was obtained in the same manner as in Production Example 4, except that 100 g of the PEDOT-PSS aqueous dispersion was added dropwise over 30 minutes. .

(Production Example 8) Reaction F with quaternary ammonium salt
1.1 g of a conductive composite having the aforementioned substituent (C) was obtained in the same manner as in Production Example 5, except that 100 g of the PEDOT-PSS aqueous dispersion was added dropwise over 30 minutes. .

(Production Example 9) Reaction G with quaternary ammonium salt
In the same manner as in Production Example 3, except that 100 g of methanol was changed to 100 g of ethanol, and 100 g of PEDOT-PSS aqueous dispersion was added dropwise in 30 minutes, 1.1 g of a conductive composite having a substituent (C) described above. got

(Production Example 10) Reaction H with quaternary ammonium salt
In the same manner as in Production Example 3, except that 100 g of methanol was changed to 100 g of isopropyl alcohol, and 100 g of the PEDOT-PSS aqueous dispersion was added dropwise in 30 minutes, a conductive composite 1 having the substituent (C) described above was prepared. 1 g was obtained.

(Production Example 11) Reaction I with quaternary ammonium salt
1.1 g of a conductive composite having the substituent (C) was obtained in the same manner as in Production Example 3, except that 100 g of methanol was changed to 50 g of methanol and 50 g of isopropyl alcohol.

[Example 1]
1.1 g of the conductive composite obtained in Production Example 3 and 274 g of isopropyl alcohol were added and treated with a high-pressure homogenizer to obtain an initial conductive polymer-containing liquid. Table 1 shows the results of measuring the particle size (cumulant average particle size) Q0 of the conductive composite contained in this conductive polymer-containing liquid by a dynamic light scattering method. Subsequently, the conductive polymer-containing liquid was applied to a PET film (Lumirror T60 manufactured by Toray Industries, Inc.) using a bar coater #8, and dried at 120° C. for 2 minutes to obtain a conductive film. Table 1 shows the results of measuring the surface resistivity R0 of this conductive film.
In addition, the initial conductive polymer-containing liquid was left to stand at 40° C. for 10 days, and then the conductive polymer-containing liquid was obtained. Table 1 shows the results of measurement by the light scattering method.

[Example 2]
To the organic layer (organic solution) in which 2.4 g of tetrabutylammonium bromide was dissolved in 100 g of methanol, 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2 was added in one second and stirred for 30 minutes. As a result, a reaction product of tetrabutylammonium bromide and the conductive composite was deposited. Subsequently, after standing for 30 minutes to settle the reaction product (precipitate), 100 g of the supernatant liquid is decanted and removed, and 100 g of isopropyl alcohol is added to lightly suspend the precipitate. After stirring for 30 minutes, precipitate again. The material was allowed to settle and 100 g of supernatant liquid was decanted off. This washing operation (solvent exchange operation) was repeated three times. As a result, 1.1 g of the conductive composite having the aforementioned substituent (C) and 102.4 g of a conductive polymer-containing liquid containing isopropyl alcohol (concentration of 90% by mass or more) were obtained.
Except for using this as the initial conductive polymer-containing liquid, a conductive polymer-containing liquid after storage was obtained in the same manner as in Example 1, the particle size Q0 and the particle size Q1 were measured, and the conductive film was obtained. It was produced and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 3]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 4. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 4]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 5. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 5]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 6. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 6]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 7. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 7]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 8. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 8]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 9. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 9]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 10. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Example 10]
A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 1.1 g of the conductive composite obtained in Production Example 3 was changed to 1.1 g of the conductive composite obtained in Production Example 11. , the particle size Q0 and the particle size Q1 were measured, a conductive film was produced, and the surface resistivity R0 was measured. Table 1 shows the results.

[Comparative Example 1]
2.4 g of tetrabutylammonium bromide was dissolved in 100 g of a mixture of 50 g of acetone and 50 g of toluene to form an organic layer (organic solution). Stirred for 30 minutes. As a result, a reaction product of tetrabutylammonium bromide and the conductive composite was deposited. This precipitate was collected by filtration, 100 g of the above mixture was added, and the mixture was stirred for 30 minutes while lightly suspending the precipitate. This washing operation was repeated once more. As a result, 1.1 g of the conductive composite having the aforementioned substituent (C) was obtained.
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that 1.1 g of the conductive composite obtained here was used, the particle size Q0 and the particle size Q1 were measured, and a conductive film was produced. Surface resistivity R0 was measured. Table 1 shows the results. Visual observation of the conductive polymer-containing liquid after storage (after standing still at 4° C. for 10 days) revealed that the conductive composite aggregated and sedimented.

[Comparative Example 2]
An organic solution was obtained by dissolving 2.4 g of tetrabutylammonium bromide in 100 g of a mixture of 50 g of acetone and 50 g of toluene. This organic solution was added at once to 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2 in 1 second and stirred for 30 minutes. As a result,
Tetrabutylammonium bromide precipitated, and the reaction was insufficient, so a deposit of the conductive composite could not be obtained.

[Comparative Example 3]
An organic solution was obtained by dissolving 2.4 g of tetrabutylammonium bromide in 100 g of methanol. This organic solution was added at once to 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2 in 1 second and stirred for 30 minutes. As a result, tetrabutylammonium bromide was deposited, and the reaction was insufficient, so a deposit of the conductive composite could not be obtained.

[Comparative Example 4]
An organic solution was obtained by dissolving 2.4 g of tetrabutylammonium bromide in 100 g of methanol. This organic solution was added dropwise over 30 minutes to 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2, followed by stirring for 30 minutes. As a result, tetrabutylammonium bromide was deposited, and the reaction was insufficient, so a deposit of the conductive composite could not be obtained.

[Method for measuring particle size]
Using the conductive polymer-containing liquid prepared in each example as a sample (25 ° C), using a zeta potential / particle size / molecular weight measurement system (ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.), the photon correlation is determined by the dynamic light scattering method. The average particle diameter d (hydrodynamic diameter) and the polydispersity index were obtained by the cumulant method from the autocorrelation function obtained by the method, and the values were defined as the particle size.

[Measurement of surface resistivity]
For the conductive film produced in each example, the surface resistivity of the conductive layer was measured using a resistivity meter (Hiresta manufactured by Nitto Seiko Analyticc Co., Ltd.) under the condition of an applied voltage of 10V.

In the conductive polymer-containing liquid of each example according to the present invention, the conductive composite is reacted with the quaternary ammonium compound, so that the conductive composite is sufficient for the dispersion solvent containing isopropanol. , and had excellent dispersion stability. As a result, an increase in the particle size of the conductive composite was suppressed during standing. Moreover, the conductivity of the conductive layer formed by coating was also good.
During the reaction, when the aqueous dispersion containing the conductive composite is slowly added dropwise to the organic solution containing the quaternary ammonium compound to react (Examples 5 to 10), when the reaction is performed by adding at once (implementation Compared to Examples 1 to 4), a conductive composite with a relatively small particle size was obtained, and the conductivity was also excellent. From these results, it is clear that the dropping method described above is preferable in the reaction.
In Comparative Example 1, since the organic solvent constituting the reaction solution was not alcohol, a conductive composite with excellent dispersion stability could not be obtained.
In Comparative Example 2, an organic solvent solution other than alcohol containing a quaternary ammonium compound was added to the conductive polymer aqueous dispersion, so that the quaternary ammonium compound and the conductive composite were sufficiently reacted. I couldn't.
In Comparative Examples 3 and 4, since the organic solution containing the quaternary ammonium compound was added to the aqueous dispersion containing the conductive composite, the reaction was insufficient and the desired precipitate was not obtained.

Claims (10)

An aqueous conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion is added to an alcohol solution containing a quaternary ammonium compound to obtain a partial anionic group of the polyanion and the A reactive precipitation step of reacting with a quaternary ammonium compound to precipitate a reaction product;
and a preparation step of dispersing the reaction product in a dispersion solvent to obtain a conductive polymer-containing liquid. a recovery step of recovering the reaction product after the reactive precipitation step;
a cleaning step of cleaning the recovered reaction product with a cleaning liquid;
2. The method for producing a conductive polymer-containing liquid according to claim 1, further comprising subjecting the washed reaction product to the preparation step to obtain the conductive polymer-containing liquid. After the reaction precipitation step, the reaction product is precipitated in the alcohol solution, the supernatant is removed, and a slurry containing the reaction product is obtained;
A washing step of obtaining a slurry containing the reaction product by adding a washing liquid to the slurry obtained in the sedimentation step and agitating the slurry, then allowing the reaction product to settle in the washing liquid and removing the supernatant;
2. The conductive polymer-containing liquid according to claim 1, further comprising subjecting the reaction product contained in the slurry obtained in the washing step to the preparation step to obtain the conductive polymer-containing liquid. manufacturing method. The method for producing a conductive polymer-containing liquid according to any one of claims 1 to 3, wherein the dispersion solvent contains isopropyl alcohol. 5. The method for producing a conductive polymer-containing liquid according to claim 4, wherein the content of isopropyl alcohol with respect to the total mass of said conductive polymer-containing liquid is 84% by mass or more. The conductive material according to any one of claims 1 to 5, wherein the total mass of the conductive polymer aqueous dispersion added to 100 to 300 parts by mass of the alcohol solution containing the quaternary ammonium compound is 100 parts by mass. A method for producing a liquid containing a high molecular weight polymer. The method for producing a conductive polymer-containing liquid according to any one of claims 1 to 6, wherein the quaternary ammonium compound contains a tetraalkylammonium halide. 8. The method for producing a conductive polymer-containing liquid according to any one of claims 1 to 7, further comprising adding a conductivity enhancing agent to said conductive polymer-containing liquid in said preparation step. The conductive polymer according to any one of claims 1 to 8, wherein the π-conjugated conductive polymer contains poly(3,4-ethylenedioxythiophene), or the polyanion contains polystyrenesulfonic acid. A method for producing a liquid containing a high molecular weight polymer. A step of obtaining a conductive polymer-containing liquid by the production method according to any one of claims 1 to 9;
A method for producing a conductive laminate, comprising the step of applying the conductive polymer-containing liquid to at least part of a substrate.