JP6576003B2 - Method for producing conductive polymer dispersion and method for producing conductive film - Google Patents

Description

  The present invention relates to a method for producing a conductive polymer dispersion containing a π-conjugated conductive polymer and a method for producing a conductive film including a conductive layer containing a π-conjugated conductive polymer.

As a paint for forming the conductive layer, a conductive polymer aqueous dispersion in which poly (3,4-ethylenedioxythiophene) is doped with polystyrene sulfonic acid may be used.
Usually, the film substrate to which the conductive layer is applied is made of a hydrophobic plastic film. Therefore, when the dispersion medium contained in the conductive polymer dispersion is water, the adhesion with the film substrate tends to be low. Further, when the dispersion medium is water, the drying time becomes longer, and thus the productivity of forming the conductive layer tends to be lowered.
Therefore, an organic solvent may be added to the conductive polymer dispersion to increase the content of the organic solvent to improve the adhesion with the film substrate (Patent Document 1). As the organic solvent, alcohol such as isopropanol may be used because it is easy to dry and has a small environmental load.

JP 2008-115215 A

However, in a conductive polymer dispersion using alcohol as a dispersion medium, the conductivity of the conductive layer formed by applying the conductive polymer dispersion increases as the storage time after preparation increases. There was a decline.
An object of this invention is to provide the manufacturing method of the conductive polymer dispersion liquid which can form a conductive layer with high electroconductivity easily even if storage time is long.
Moreover, an object of this invention is to provide the manufacturing method of the electroconductive film which can manufacture an electroconductive film with high electroconductivity easily.

The present invention has the following aspects.
[1] Conductive polymer dispersion having an addition step of adding a secondary alcohol obtained by reducing a ketone compound to a preliminary dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion Liquid manufacturing method.
[2] The method for producing a conductive polymer dispersion according to [1], wherein the ketone compound is acetone and the secondary alcohol is isopropanol.
[3] The method for producing a conductive polymer dispersion according to [1], wherein the ketone compound is methyl ethyl ketone and the secondary alcohol is 2-butanol.
[4] The method for producing a conductive polymer dispersion according to any one of [1] to [3], wherein the preliminary dispersion contains water as a dispersion medium.
[5] The method for producing a conductive polymer dispersion according to any one of [1] to [4], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). .
[6] The method for producing a conductive polymer dispersion according to any one of [1] to [5], wherein the polyanion is polystyrene sulfonic acid.
[7] The method for producing a conductive polymer dispersion according to any one of [1] to [6], wherein in the addition step, a primary alcohol is added to the preliminary dispersion.
[8] The method for producing a conductive polymer dispersion according to any one of [1] to [7], wherein the primary alcohol is methanol.
[9] The method for producing a conductive polymer dispersion according to any one of [1] to [8], wherein in the addition step, a binder resin is further added to the preliminary dispersion.
[10] The method for producing a conductive polymer dispersion according to [9], wherein the binder resin is a water-dispersible emulsion resin.
[11] The method for producing a conductive polymer dispersion according to [10], wherein the water-dispersible emulsion resin is a polyester emulsion.
[12] The method for producing a conductive polymer dispersion according to any one of [1] to [11], wherein in the addition step, a highly conductive agent is further added to the preliminary dispersion.
[13] Coating in which the conductive polymer dispersion produced by the method for producing a conductive polymer dispersion according to any one of [1] to [12] is applied to at least one surface of the film substrate. The manufacturing method of the electroconductive film which has a construction process and the drying process which dries the apply | coated conductive polymer dispersion liquid.
[14] The method for producing a conductive film according to [13], wherein the film substrate is a polyethylene terephthalate film.

According to the method for producing a conductive polymer dispersion of the present invention, a conductive layer having high conductivity can be easily formed even if the storage time is long.
According to the method for producing a conductive film of the present invention, a conductive film having high conductivity can be easily produced.

<Conductive polymer dispersion>
The conductive polymer dispersion in one embodiment of the present invention contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a secondary alcohol.
The conductive polymer dispersion may contain a primary alcohol, a binder resin, a high conductivity agent, and other additives as necessary.

  The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as the main chain is an organic polymer composed of π-conjugated system. For example, polypyrrole-based conductive polymer, polythiophene-based polymer Conductive polymer, polyacetylene conductive polymer, polyphenylene conductive polymer, polyphenylene vinylene conductive polymer, polyaniline conductive polymer, polyacene conductive polymer, polythiophene vinylene conductive polymer, and These copolymers are exemplified. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer 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 ( -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-dioctyl) Oxythiophene), poly (3,4-didecyloxythiophene), poly (3, -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-carboxybutylthiophene) is mentioned.
Examples of the polypyrrole conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and 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-hexyl) Oxy pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid).
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer may be used alone or in combination of two or more.

The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfone. Polymers having a sulfonic acid group such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid , Polymers having a carboxylic acid group such as polymethacrylcarboxylic acid, poly (2-acrylamido-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable because conductivity can be further increased.
The said polyanion may be used individually by 1 type, and may use 2 or more types together.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less.
The mass average molecular weight in the present specification is a value obtained by measuring with gel permeation chromatography and obtaining the standard substance as polystyrene.

  The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass to 1000 parts by mass with respect to 100 parts by mass of the π-conjugated conductive polymer, and 10 parts by mass to 700 parts by mass. It is more preferable that it is the range of 100 mass parts or more and 500 mass parts or less. If the polyanion content is less than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be weak, the conductivity may be insufficient, and the conductivity in the conductive polymer dispersion may be insufficient. The dispersibility of the sex complex decreases. On the other hand, when the content of the polyanion exceeds the upper limit, the content of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

The polyanion is coordinated and doped to the π-conjugated conductive polymer to form a conductive composite.
However, in the polyanion in this embodiment, not all anion groups are doped into the π-conjugated conductive polymer, but have excess anion groups that do not contribute to doping.

The secondary alcohol in this embodiment is obtained by reducing a ketone compound, and is a dispersion medium for the conductive complex. As a ketone compound, since the affinity with the water of the obtained secondary alcohol is high, C3-C6 is preferable. As a reduction method, since it is general-purpose, a hydrogen reduction method in which hydrogen is reacted in the presence of a hydrogenation catalyst is preferable.
Specific examples of the secondary alcohol include, for example, isopropanol obtained by hydrogen reduction of acetone, 2-butanol obtained by hydrogen reduction of methyl ethyl ketone, 3-pentanol obtained by hydrogen reduction of diethyl ketone, and methyl propyl ketone. 2-pentanol obtained by hydrogen reduction, cyclohexanol obtained by hydrogen reduction of cyclohexanone, and the like. Among these, isopropanol obtained by hydrogen reduction of acetone and 2-butanol obtained by hydrogen reduction of methyl ethyl ketone are preferable because of high affinity with water and higher dispersibility of the conductive complex.
Secondary alcohol may be used individually by 1 type, and may use 2 or more types together.

  The content ratio of the secondary alcohol in the dispersion medium is preferably 10% by mass or more, and more preferably 20% by mass or more. The secondary alcohol may be 100% by mass of the dispersion medium. If the content rate of the said secondary alcohol is more than the said lower limit, the electroconductivity fall at the time of storing a conductive polymer dispersion for a long time can be suppressed more.

In this embodiment, a dispersion medium other than the secondary alcohol may be included. Examples of the other dispersion medium include water and organic solvents other than the secondary alcohol. The other dispersion medium preferably contains water because the dispersibility of the conductive composite becomes high.
Another dispersion medium may be used individually by 1 type, and may use 2 or more types together.

Examples of other organic solvents include alcohol solvents, ketone solvents, ester solvents, and aromatic hydrocarbon solvents.
Examples of alcohol solvents include primary alcohols. Examples of the primary alcohol include methanol, ethanol, n-butanol, and allyl alcohol.
Examples of the ketone solvent include 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 the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and the like.
Among other organic solvents, alcohol-based solvents are preferable, primary alcohols are more preferable, and methanol is more preferable because the conductive composite is highly dispersible and inexpensive.

The binder resin is a resin other than the π-conjugated conductive polymer and the polyanion, and is a resin that increases the coating film strength.
Specific examples of the binder resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, and the like.
The binder resin is preferably a water-dispersible resin that can be dispersed in a conductive polymer dispersion, and more preferably a water-dispersible emulsion resin.
Specific examples of the water-dispersible emulsion resin include acrylic resins, polyester resins, polyurethane resins, polyimide resins, melamine resins, and the like that are made into an emulsion.
Among the water-dispersible emulsion resins, a polyester emulsion is preferable because the strength of the coating film can be further increased and is easily available. In particular, when the conductive polymer dispersion is applied to a polyester film substrate, the adhesion of the coating film is increased, and therefore, among the water-dispersible resins, a polyester emulsion is preferable.
The water-dispersible resin may be an acrylic resin, a polyester resin, a polyurethane resin, a polyimide resin, a melamine resin, or a water-soluble resin such as one having an acid group such as a carboxy group or a sulfo group or a salt thereof. Good. In the present specification, water-soluble means that 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more is dissolved in 25 ° C. distilled water.
The said binder resin may be used individually by 1 type, and may use 2 or more types together.

  The content ratio of the binder resin is preferably 100 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the solid content of the conductive composite. More preferably, they are 100 mass parts or more and 1000 mass parts or less. If the content rate of binder resin is more than the said lower limit, film forming property and coating-film intensity | strength can be improved. However, when the content ratio of the binder resin exceeds the upper limit value, the content ratio of the conductive composite decreases, and thus the conductivity may decrease.

The conductive polymer dispersion may contain a highly conductive agent in order to further improve the conductivity.
Specifically, the highly conductive agent includes a saccharide, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having two or more carboxy groups, one or more hydroxy groups, and one It is at least one compound selected from the group consisting of a compound having the above carboxy group, a compound having an amide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group. The said highly conductive agent may be used individually by 1 type, and may use 2 or more types together.
Specific examples of these compounds are described in, for example, JP 2010-87401 A. However, the highly conductive agent is a compound other than the π-conjugated conductive polymer, the polyanion, the dispersion medium, and the binder resin.
Among the highly conductive agents, glycol which is a linear compound having two hydroxy groups is preferable, and propylene glycol is more preferable because the effect of improving conductivity is high.

  The content ratio of the highly conductive agent is preferably 1 to 1000 times, more preferably 2 to 100 times the total mass of the conductive composite. If the content ratio of the high conductive agent is equal to or higher than the lower limit value, the effect of improving the conductivity due to the addition of the high conductive agent is sufficiently exhibited. It is possible to prevent a decrease in conductivity due to the above.

The conductive polymer dispersion may contain a known additive.
The additive is not particularly limited as long as it has the effect of the present invention, and for example, a surfactant, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used. However, an additive consists of compounds other than the said polyanion, the said dispersion medium, the said binder resin, and the said highly conductive agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Moreover, you may add polymer type surfactants, such as polyvinyl alcohol and polyvinylpyrrolidone.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving a metal salt in water.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and saccharides.
Examples of 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 dispersion contains the additive, the content ratio is appropriately determined according to the type of the additive, but is generally 0. 10 parts by mass relative to 100 parts by mass of the solid content of the conductive composite. It is in the range of not less than 001 parts by mass and not more than 5 parts by mass.

<Method for producing conductive polymer dispersion>
The method for producing a conductive polymer dispersion of one embodiment of the present invention includes an addition step of adding a secondary alcohol obtained by reducing a ketone compound to a preliminary dispersion containing a conductive composite.
The preliminary dispersion contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium for dispersing the conductive complex.
In the addition step, a dispersion medium may be further added to the preliminary dispersion, or a binder component may be added.

A conductive polymer dispersion containing a secondary alcohol obtained by reducing a ketone compound can easily form a conductive layer having high conductivity even if the storage time is long.
Normally, secondary alcohols are produced by hydration of alkenes. However, conductive polymer dispersions containing secondary alcohols obtained by hydration of alkenes are more conductive as the storage time increases. It is easy to deteriorate. The reason for this is not clear, but the secondary alcohol obtained by hydration of the alkene contains impurities that degrade the π-conjugated conductive polymer or polyanion, and the secondary alcohol obtained by reducing the ketone compound Seems to be free of such impurities.

<Method for producing conductive film>
The method for producing a conductive film of one embodiment of the present invention includes a coating step of coating the conductive polymer dispersion on at least one surface of a film substrate to form a coated film, and a coated conductive film. A drying step of drying the functional polymer dispersion.
The conductive film obtained by this manufacturing method includes a film substrate and a conductive layer formed on at least one surface of the film substrate, and the conductive layer includes a π-conjugated conductive polymer and a polyanion. Contains a conductive composite.
The average thickness of the conductive layer is preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and further preferably 30 nm or more and 500 nm or less. If the average thickness of the conductive layer is equal to or higher than the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is equal to or lower than the upper limit, the conductive layer can be easily formed.

A plastic film is mentioned as a film base material used in the coating process of this aspect.
Examples of the resin for the film base material constituting the plastic film include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate. , Polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio And the like. Among these resins for film base materials, polyethylene terephthalate is preferable because it is inexpensive and has excellent mechanical strength.
The film base resin may be amorphous or crystalline.
Further, the film substrate may be unstretched or stretched.
In addition, the film substrate may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or flame treatment in order to improve the adhesion of the conductive layer formed from the conductive polymer dispersion.

As an average thickness of a film base material, it is preferable that it is 10-500 micrometers, and it is more preferable that it is 20-200 micrometers. If the average thickness of the film substrate is equal to or greater than the lower limit value, it is difficult to break, and if it is equal to or less than the upper limit value, sufficient flexibility as a film can be ensured.
The thickness in the present specification is a value obtained by measuring the thickness at any 10 locations and averaging the measured values.

Examples of the method for applying the conductive polymer dispersion include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an air doctor coater, a knife coater, A coating method using a coater such as a blade coater, cast coater or screen coater, a spraying method using a sprayer such as air spray, airless spray or rotor dampening, a dipping method or the like can be applied.
Of these, a bar coater may be used because it can be applied easily. In the bar coater, the coating thickness varies depending on the type, and in the commercially available bar coater, a number is assigned to each type, and the larger the number, the thicker the coating can be made.
The amount of the conductive polymer dispersion applied to the film substrate is not particularly limited, but the solid content is preferably in the range of 0.1 g / m ^{2 to} 2.0 g / m ² .

Examples of the drying method in the drying step include heat drying and vacuum drying. As heat drying, for example, a normal 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 to 150 ° C. Here, the heating temperature is a set temperature of the drying apparatus.

  In the method for producing a conductive film, since the conductive layer is formed using the conductive polymer dispersion, a conductive film having high conductivity can be easily produced.

(Production Example 1)
In 18 ml of ion-exchanged water, 206 g of sodium styrenesulfonate was dissolved, and while stirring at 80 ° C., 6.18 g of ammonium persulfate oxidizer solution previously dissolved in 10 ml of water was added dropwise for 20 minutes. Stir for hours.
To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and 1000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was used as the remaining liquid. And about 2000 ml of solution was removed using ultrafiltration. The above ultrafiltration operation was repeated three times.
Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of solution was removed using an ultrafiltration method. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless polystyrene sulfonic acid solid.

(Production Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C.
While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of solution was removed by ultrafiltration. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, about 2000 ml of solution is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to this solution. About 2000 ml of solution was removed by external filtration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.2% by mass polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion (PEDOT-PSS aqueous dispersion).

Example 1
20 g of water, 50 g of methanol, and 20 g of isopropanol obtained by reducing acetone were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Example 2)
20 g of water, 30 g of methanol, and 40 g of isopropanol obtained by reducing acetone were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Example 3)
40 g of water, 100 g of methanol, and 50 g of isopropanol obtained by reducing acetone were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

Example 4
40 g of water, 60 g of methanol, and 90 g of isopropanol obtained by reducing acetone were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Example 5)
To 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 20 g of water, 40 g of methanol, 20 g of isopropanol obtained by reducing acetone, and binder components (Plus Coat RZ-105 manufactured by Kyoyo Chemical Co., Ltd., water) 10 g of a dispersion polyester and an aqueous solution having a solid concentration of 25% by mass were added to obtain a conductive polymer dispersion.

(Example 6)
To 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 20 g of water, 50 g of methanol, 20 g of isopropanol obtained by reducing acetone, and 5 g of propylene glycol are added to form a conductive polymer dispersion. Obtained.

(Example 7)
20 g of water, 50 g of methanol, and 20 g of 2-butanol obtained by reducing methyl ethyl ketone were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Comparative Example 1)
20 g of water, 50 g of methanol, and 20 g of isopropanol obtained by hydrating propylene were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Comparative Example 2)
20 g of water, 30 g of methanol, and 40 g of isopropanol obtained by hydrating propylene were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Comparative Example 3)
40 g of water, 100 g of methanol, and 50 g of isopropanol obtained by hydrating propylene were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Comparative Example 4)
40 g of water, 60 g of methanol, and 90 g of isopropanol obtained by hydrating propylene were added to 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

(Comparative Example 5)
To 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 20 g of water, 40 g of methanol, 20 g of isopropanol obtained by hydrating propylene, and binder components (Plus Coat RZ-105 manufactured by Kyoyo Chemical Co., Ltd., 10 g of an aqueous dispersion polyester and an aqueous solution having a solid content concentration of 25% by mass were added to obtain a conductive polymer dispersion.

(Comparative Example 6)
To 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 20 g of water, 50 g of methanol, 20 g of isopropanol obtained by hydrating acetone, and 5 g of propylene glycol are added to form a conductive polymer dispersion. Got.

(Comparative Example 7)
To 10 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 20 g of water, 50 g of methanol, and 20 g of 2-butanol obtained by hydrating 1-butene were added to obtain a conductive polymer dispersion. Obtained.

<Evaluation>
The conductive polymer dispersion liquid of each example immediately after obtained was No. 4 was applied to a polyethylene terephthalate film using a bar coater to form a coating film. The coating film was heat-dried at a drying temperature of 120 ° C. and a drying time of 1 minute, and the dispersion medium was removed to obtain a conductive film. The surface resistance value (initial surface resistance value) of the conductive film was measured using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.) under an applied voltage of 10V. The measurement results are shown in Table 1.
In addition, after the conductive polymer dispersion of each example was stored at 25 ° C. for 24 hours, 4 was applied to a polyethylene terephthalate film using a bar coater to form a coating film. The coating film was heat-dried at a drying temperature of 120 ° C. and a drying time of 1 minute, and the dispersion medium was removed to obtain a conductive film. The surface resistance value (surface resistance value after storage for 24 hours) of the conductive film was measured using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co., Ltd.) under an applied voltage of 10V. The measurement results are shown in Table 1.

According to the conductive polymer dispersion of each example containing a secondary alcohol obtained by reducing a ketone compound, a highly conductive conductive layer could be formed even when the storage time was long.
On the other hand, in the conductive polymer dispersion of each comparative example containing a secondary alcohol obtained by hydrating a ketone compound, the conductivity of the resulting conductive layer may be lowered when the storage time is long. .

Claims (14)

  Production of conductive polymer dispersion having addition step of adding secondary alcohol obtained by reducing ketone compound to preliminary dispersion containing conductive complex containing π-conjugated conductive polymer and polyanion Method.   The method for producing a conductive polymer dispersion according to claim 1, wherein the ketone compound is acetone and the secondary alcohol is isopropanol.   The method for producing a conductive polymer dispersion according to claim 1, wherein the ketone compound is methyl ethyl ketone and the secondary alcohol is 2-butanol.   The method for producing a conductive polymer dispersion according to any one of claims 1 to 3, wherein the preliminary dispersion contains water as a dispersion medium.   The method for producing a conductive polymer dispersion according to claim 1, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).   The method for producing a conductive polymer dispersion according to claim 1, wherein the polyanion is polystyrene sulfonic acid.   The method for producing a conductive polymer dispersion according to any one of claims 1 to 6, wherein in the addition step, a primary alcohol is added to the preliminary dispersion.   The manufacturing method of the conductive polymer dispersion liquid as described in any one of Claims 1-7 whose said primary alcohol is methanol.   In the said addition process, binder resin is further added to the said preliminary dispersion liquid, The manufacturing method of the conductive polymer dispersion liquid as described in any one of Claims 1-8.   The method for producing a conductive polymer dispersion according to claim 9, wherein the binder resin is a water-dispersible emulsion resin.   The method for producing a conductive polymer dispersion according to claim 10, wherein the water-dispersible emulsion resin is a polyester emulsion.   The method for producing a conductive polymer dispersion according to any one of claims 1 to 11, wherein in the addition step, a highly conductive agent is further added to the preliminary dispersion.   A coating step of coating the conductive polymer dispersion produced by the method for producing a conductive polymer dispersion according to any one of claims 1 to 12 on at least one surface of the film substrate; And a drying step of drying the coated conductive polymer dispersion.   The manufacturing method of the electroconductive film of Claim 13 whose said film base material is a polyethylene terephthalate film.