JP7291555B2 - Conductive polymer-containing liquid, conductive film, and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a conductive polymer-containing liquid, a conductive film, and a method for producing the same.

A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system forms a conductive composite when doped with a polyanion having an anion group, and has dispersibility in water. Manufacture of a conductive film having a conductive layer by applying a conductive polymer-containing liquid containing a conductive composite (also referred to as a conductive polymer dispersion) to a film substrate or the like. can be done. However, a conductive layer containing a conductive composite has a problem that its conductivity decreases over time due to exposure to the atmosphere. As a method of reducing this problem, a method of incorporating an antioxidant into the conductive layer has been disclosed (Patent Document 1).

Japanese Patent No. 5509462

In addition, the conductive layer is required to improve light resistance not only to atmospheric exposure but also to light such as ultraviolet rays, but the method of adding an antioxidant described in Patent Document 1 does not necessarily provide sufficient light resistance. do not have.

The present invention provides a conductive film with excellent light resistance, a production method for easily producing the same, and a conductive polymer-containing liquid used in the production method.

[1] A conductive polymer-containing liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, and one or more nitrogen-containing cyclic compounds represented by the following chemical formula (A).
[2] In the following chemical formula (A), R ¹ is a hydrogen atom, an oxyl group, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and one of the hydrogen atoms of the alkyl group above may be substituted with a hydroxyl group, R ² to R ¹¹ are each independently an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and one of the hydrogen atoms of the alkyl group The conductive polymer-containing liquid according to [1], wherein one or more may be substituted with hydroxyl groups.
[3] The nitrogen-containing cyclic compound is 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1-methylpiperidine, piperidine, 4-hydroxypiperidine, 4-hydroxy-1-methylpiperidine, 1 selected from 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine The conductive polymer-containing liquid according to [1] or [2], containing at least one species.
[4] The molar ratio between the nitrogen-containing cyclic compound content G1 and the monomer unit content G2 of the polyanion is G2=1 and G1≧0.25, [1] to [ 3], the conductive polymer-containing liquid according to any one of items.
[5] The conductive polymer-containing liquid according to any one of [1] to [4], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[6] The conductive polymer-containing liquid according to any one of [1] to [5], wherein the polyanion is polystyrenesulfonic acid.
[7] The conductive polymer-containing liquid according to any one of [1] to [6], further containing one or more phenolic antioxidants.
[8] The conductive polymer-containing liquid according to [7], wherein the phenolic antioxidant contains one or more selected from gallic acid, methyl gallic acid, ethyl gallic acid and propyl gallic acid.
[9] The conductive polymer-containing liquid according to any one of [1] to [8], further containing a binder component.
[10] The conductive polymer-containing liquid according to any one of [9], wherein the binder component contains a curable monomer or oligomer having at least one of an epoxy group and an oxetane group.
[11] The conductive polymer-containing liquid according to [9], wherein the binder component contains an acrylic resin or a polyester resin.
[12] The conductive polymer-containing liquid according to any one of [1] to [11], further containing at least one of water and an alcoholic solvent.
[13] The conductive polymer-containing liquid according to any one of [1] to [12], further comprising a high-boiling solvent having a boiling point of 150°C or higher at 1 atmosphere.
[14] Conductive, comprising applying the conductive polymer-containing liquid according to any one of [1] to [13] to at least one surface of a film substrate to form a coating film. Film production method.
[15] A conductive composite containing a π-conjugated conductive polymer and a polyanion and one or more nitrogen-containing cyclic compounds represented by the following chemical formula (A) are applied to at least one surface of a film substrate. A conductive film provided with a conductive layer comprising:

［式（Ａ）中、Ｒ^１～Ｒ^１１は、それぞれ独立に、水素原子又は任意の置換基を表す。］

[In Formula (A), R ¹ to R ¹¹ each independently represent a hydrogen atom or an arbitrary substituent. ]

According to the conductive polymer-containing liquid of the present invention and the method for producing a conductive film using the same, a conductive film having a conductive layer with excellent light resistance can be easily produced.

≪Liquid containing conductive polymer≫
The conductive polymer-containing liquid of the first aspect of the present invention is a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a nitrogen-containing cyclic compound represented by the chemical formula (A) described later. and above. Moreover, a solvent such as water or an organic solvent may be included depending on the purpose such as diluting to a viscosity suitable for coating.
In the conductive polymer-containing liquid of the present invention, the conductive composite may be in a dispersed state or in a dissolved state.

[Conductive composite]
The conductive composite in this aspect 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.

(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 from the viewpoint of 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 weight 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 gel permeation chromatography and calculated in terms of polystyrene.

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. and more preferably in the range of 100 parts by mass or more and 500 parts by mass or less. 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 π-conjugated conductive polymer can be sufficiently contained, and sufficient conductivity can be ensured.

In the polyanions in the conductive composite, not all anionic groups are doped into the π-conjugated conductive polymer, and there are surplus anionic groups that do not participate in doping. The surplus anionic group is a hydrophilic group, and the dispersibility of the conductive composite in which the anionic group is not modified is high in an aqueous dispersion medium and low in an organic solvent.

(Content of conductive composite)
From the viewpoint of improving dispersibility, the content of the conductive composite relative to the total mass of the conductive polymer-containing liquid is preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 5% by mass. % or less, and more preferably 0.2 mass % or more and 2 mass % or less.

[Nitrogen-containing cyclic compound]
The conductive polymer-containing liquid of this embodiment contains a nitrogen-containing cyclic compound represented by the following chemical formula (A) (hereinafter referred to as a nitrogen-containing cyclic compound (A)). By including the nitrogen-containing cyclic compound (A), light resistance can be imparted to the conductive layer.

Each of R ¹ to R ¹¹ in the chemical formula (A) is independently a hydrogen atom or an arbitrary substituent.
Examples of optional substituents include alkyl groups having 1 to 14 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), alkoxy groups having 1 to 14 carbon atoms (eg, methoxy group, ethoxy group, etc.). , propoxy group, butoxy group, etc.), hydroxyl group, amino group, carboxy group and the like. The hydrogen atoms of these substituents are further substituted by other substituents (e.g., (meth)acryloyloxy group, carboxyl group, hydroxyl group, epoxy group, amino group, trialkoxysilyl group, halogen (e.g., fluorine atom, chlorine atom). , bromine atom), etc.).

From the viewpoint of enhancing the effect of including the nitrogen-containing cyclic compound (A), in the chemical formula (A), R ¹ is a hydrogen atom, an oxyl group (i.e., a group obtained by removing a proton from a hydroxyl group, an oxy radical group), or a hydroxyl group. , an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, one or more hydrogen atoms of the alkyl group may be substituted with a hydroxyl group, and R ² to R ¹¹ are each independently It is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and one or more hydrogen atoms of the alkyl group may be substituted with a hydroxyl group.
Further, R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, or an oxyl group, and R ² to R ¹¹ each independently has 1 to 1 carbon atoms. 3 alkyl groups or hydroxyl groups are more preferred.
Furthermore, R ¹ is a hydrogen atom, an alkyl group having 1 carbon atoms or an oxyl group, R ² to R ³ and R ¹⁰ to R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R More preferably, R ⁴ to R ⁵ and R ⁸ to R ⁹ are hydrogen atoms, one of R ⁶ to R ⁷ is hydrogen and the other is hydrogen or hydroxyl.

Suitable nitrogen-containing cyclic compounds (A) as described above include, for example, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1-methylpiperidine, piperidine, 4-hydroxypiperidine, 4- Hydroxy-1-methylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethyl piperidine and the like.

The nitrogen-containing cyclic compound (A) contained in the conductive polymer-containing liquid of this embodiment may be of one type or two or more types.
The molar ratio between the content G1 of the nitrogen-containing cyclic compound (A) contained in this embodiment and the content G2 of the monomer units of the polyanion is preferably G1≧0.25 with respect to G2=1, and G1 ≧0.5 is more preferred, G1≧0.75 is even more preferred, and G1≧1.0 is particularly preferred. As the G1 content ratio increases, the light resistance tends to improve.
The upper limit of the content G1 is not particularly limited, and from the viewpoint of increasing the content ratio of the conductive composite in the formed conductive layer as much as possible and obtaining good conductivity, for example, G1 ≤ 10 is preferable, and G1 ≤ 5 is more preferable, and G1≦3 is even more preferable.

The total content of the nitrogen-containing cyclic compound (A) contained in this aspect is preferably 1 part by mass or more and 1000 parts by mass or less, and 10 parts by mass or more and 500 parts by mass with respect to 100 parts by mass of the conductive composite. It is more preferably not more than 50 parts by mass, and more preferably 50 parts by mass or more and 300 parts by mass or less. If the content of the nitrogen-containing cyclic compound (A) is at least the lower limit, the light resistance of the conductive layer can be further improved. On the other hand, when the content of the nitrogen-containing cyclic compound (A) is equal to or less than the above upper limit, it is possible to suppress a decrease in conductivity due to a decrease in the content of the conductive composite.

[Dispersion medium]
The conductive polymer-containing liquid preferably further contains at least one of water and an organic solvent. Here, the dispersion medium is a compound other than the nitrogen-containing cyclic compound (A).
Since water or an organic solvent can dissolve the nitrogen-containing cyclic compound (A) and disperse or dissolve the conductive composite, it can be called a dispersion medium or a solvent. In the present specification, the term "dispersion" may be used without distinguishing between dispersing and dissolving, and the term "dispersion medium" may be used without distinguishing between a dispersion medium and a solvent.
When the conductive polymer-containing liquid of this embodiment contains a dispersion medium, the dispersibility of the conductive composite can be improved, which is preferable.

(Organic solvent)
The organic solvent in this embodiment may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a solubility of 1 g or more in 100 g of water at 20°C, and the water-insoluble organic solvent is an organic solvent having a solubility of less than 1 g in 100 g of water at 20°C.
A water-soluble organic solvent is preferable from the viewpoint of improving the dispersibility of the conductive composite.

Examples of water-soluble organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, and nitrogen atom-containing solvents.
Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, Ethylene glycol, propylene glycol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether and the like can be mentioned.
Examples of ether solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, diethylene glycol diethyl ether 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 nitrogen atom-containing solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like. Here, the nitrogen atom-containing solvent is a compound different from the nitrogen-containing cyclic compound (A).

One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
As the water-soluble organic solvent, an alcohol-based solvent or a ketone-based solvent is preferable, since the conductive polymer-containing liquid can be coated onto the film substrate well.

From the viewpoint that the coating film of the conductive polymer-containing liquid applied to the film substrate dries relatively slowly and the formation of a uniform conductive layer is facilitated, the dispersion medium is It preferably contains a high-boiling solvent having a boiling point of 150° C. or higher.

Specific examples of high boiling point solvents and their boiling points at 1 atmosphere are shown below. Boiling points are rounded off to the nearest whole number.
Examples of high-boiling alcohol solvents include ethylene glycol (boiling point 198°C), propylene glycol (boiling point 188°C), 1,3-propanediol (boiling point 214°C), and 1,4-butanediol (boiling point 230°C). and other polyhydric alcohols.
Examples of high-boiling ether solvents include propylene glycol dimethyl ether (boiling point 175° C.) and diethylene glycol diethyl ether (boiling point 188° C.).
Examples of high-boiling ketone-based solvents include methyl amyl ketone (boiling point 151° C.) and diacetone alcohol (boiling point 168° C.).
Examples of high-boiling nitrogen atom-containing solvents include N-methylpyrrolidone (boiling point 202° C.), dimethylacetamide (boiling point 165° C.), N,N-dimethylformamide (boiling point 153° C.) and the like.
Examples of high-boiling sulfur atom-containing solvents include dimethyl sulfoxide (boiling point: 189° C.).

Among the high boiling point solvents exemplified above, dimethyl sulfoxide (boiling point 189° C.), N,N-dimethylformamide (boiling point 153° C.), Ethylene glycol (boiling point 198°C), propylene glycol (boiling point 188°C), 1,3-propanediol (boiling point 214°C), or 1,4-butanediol (boiling point 230°C) is preferred, and propylene glycol is more preferred.

The content of the high-boiling solvent is preferably 10 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 conductive composite. It is more preferable that the content is 2500 parts by mass or more. If the content of the high-boiling-point solvent is at least the lower limit, the above effect due to the addition of the high-boiling-point solvent is sufficiently exhibited. A decrease in conductivity can be prevented.

(Aqueous dispersion medium)
From the viewpoint of improving the dispersibility of the conductive composite in this aspect, it is preferable to include an aqueous dispersion medium.
The aqueous dispersion medium is water or a mixture of water and a water-soluble organic solvent. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
The water content relative to the total mass of the aqueous dispersion medium is more than 50% by mass, preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

(binder component)
The conductive polymer-containing liquid may contain a binder component. The binder component is a nitrogen-containing cyclic compound (A), a resin other than the π-conjugated conductive polymer and the polyanion, or a precursor thereof, and is a thermoplastic resin or a curable monomer that cures when the conductive layer is formed. or an oligomer. The thermoplastic resin becomes the binder resin as it is, and the resin formed by curing the curable monomer or oligomer becomes the binder resin.
A binder component may be used individually by 1 type, and may use 2 or more types together.

Specific examples of binder resins derived from binder components include epoxy resins, acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, polyether resins, melamine resins, and silicones.

The curable monomers or oligomers may be thermosetting monomers or oligomers or photocurable monomers or oligomers. Here, an oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of curable monomers include acrylic monomers (acrylic compounds), epoxy monomers, and organosiloxanes. Examples of curable oligomers include acrylic oligomers (acrylic compounds), epoxy oligomers, and silicone oligomers (curable silicone).
When an acrylic monomer or acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When curable monomers or oligomers are included, it is preferable to further include a curing catalyst. For example, if it contains a thermosetting monomer or oligomer, it preferably contains a thermal polymerization initiator that generates radicals by heating, and if it contains a photocurable monomer or oligomer, it generates radicals by light irradiation. It preferably contains a photopolymerization initiator that causes the

When a curable monomer or oligomer is included as a binder component, the monomer or oligomer preferably has at least one functional group of an epoxy group and an oxetane group from the viewpoint of enhancing the curability of the binder component. Epoxy resins are formed by curing monomers or oligomers (prepolymers) having epoxy or oxetane groups.

When the dispersion medium of the conductive polymer-containing liquid is an aqueous dispersion medium, the binder resin to be contained is preferably a water-dispersible resin, more preferably a water-dispersible emulsion resin. Water-dispersible resins are emulsion resins or water-soluble resins.

Specific examples of water-dispersible emulsion resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, melamine resins, etc., which are emulsified with an emulsifier. Among them, a polyester emulsion is preferable because the strength of the coating film obtained by coating the conductive polymer-containing liquid on the film substrate increases, and the adhesion of the coating film to the film substrate increases.

Specific examples of water-soluble resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, and melamine resins having an acid group such as a carboxy group or a sulfo group, or a salt thereof. Here, the water-soluble resin preferably dissolves in 100 g of distilled water at 25° C. in an amount of 1 g or more, preferably 5 g or more, more preferably 10 g or more.

Acid groups such as carboxy groups and sulfo groups possessed by the water-dispersible resin may form salts with cations such as sodium ions and potassium ions.

The content ratio of the binder component in the conductive polymer-containing liquid is preferably 10 parts by mass or more and 10000 parts by mass or less, and 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive composite. is more preferred. When the content of the binder component is at least the above lower limit, it is possible to improve the film formability and film strength when the conductive polymer-containing liquid is applied to the film substrate. If the content of the binder component is equal to or less than the above upper limit, it is possible to suppress a decrease in conductivity due to a decrease in the content of the conductive composite.

(high conductivity agent)
The conductive polymer-containing liquid may contain a conductivity enhancing agent in order to further improve the conductivity.
Conductive agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having two or more carboxyl groups, one or more hydroxy groups and one or more carboxyl groups. , compounds having an amide group, compounds having an imide group, lactam compounds, and compounds having a glycidyl group.
However, the conductivity enhancing agent is a compound other than the π-conjugated conductive polymer, polyanion, dispersion medium, nitrogen-containing cyclic compound (A), and binder component described above.
Among the highly conductive agents, glycol, which is a linear compound having two hydroxy groups, is preferred, and propylene glycol is more preferred, because of its high effect of improving conductivity.
The conductive polymer-containing liquid may contain one or more conductive agents.

The content of the high conductivity agent is preferably 10 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 conductive composite. It is more preferable that the amount is from 1 part to 2500 parts by mass. If the content of the high-conductivity agent is at least the above lower limit, the effect of improving conductivity by adding the high-conductivity agent is sufficiently exhibited, and if it is at or below the above upper limit, the concentration of the π-conjugated conductive polymer is reduced. It is possible to prevent the decrease in conductivity caused by the decrease.

[Other additives]
The conductive polymer-containing liquid may contain other additives.
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.
However, the additive is other than the above-mentioned π-conjugated conductive polymer, polyanion, dispersion medium, nitrogen-containing cyclic compound (A), binder component, and high-conductivity agent.
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 an epoxy group, 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 additive, the content ratio is appropriately determined according to the type of the additive. It can be in the range of 5 parts by mass or less.

(Antioxidant)
In order to prevent oxidative deterioration of the conductive layer formed from the conductive polymer-containing liquid of this embodiment, the conductive polymer-containing liquid may contain an antioxidant.
Among the examples of antioxidants described above, phenol-based antioxidants are preferred because they provide a high level of antioxidation to the conductive layer. Among the phenolic antioxidants, at least one of gallic acid (gallic acid) and esters of gallic acid is preferred. Gallic acid and gallic acid esters exhibit high antioxidant performance and also have the effect of improving electrical conductivity.
Esters of gallic acid include, for example, methyl gallate, ethyl gallate, and propyl gallate.

In the conductive polymer-containing liquid of this aspect, the content of the antioxidant is preferably 10 parts by mass or more and 10000 parts by mass or less, and 20 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive composite. is more preferable. If the content of the antioxidant is at least the lower limit value, the antioxidant property of the conductive layer formed from the conductive polymer-containing liquid is higher, and if it is at most the upper limit value, the conductive polymer-containing liquid It is possible to prevent a decrease in the conductivity of the conductive layer formed from.

<<Method for producing liquid containing conductive polymer>>
The conductive polymer-containing liquid of the present invention can be easily produced, for example, by any one of the following methods (a) to (b).
(a) A method comprising adding a nitrogen-containing cyclic compound (A) to a conductive polymer aqueous dispersion containing a π-conjugated conductive polymer, a polyanion, and at least water among water and an organic solvent.
(b) Drying a conductive composite containing a π-conjugated conductive polymer and a polyanion and a conductive polymer aqueous dispersion containing at least water among water and an organic solvent to obtain a dried conductive composite. and a step of adding at least the nitrogen-containing cyclic compound (A) among the nitrogen-containing cyclic compound (A) and the dispersion medium to the dried product.

The conductive polymer aqueous dispersion used as the materials (a) to (b) is a conductive polymer-containing liquid in which a conductive composite is dispersed in an aqueous dispersion medium. The conductive polymer aqueous dispersion can be obtained, for example, by adding a monomer constituting the π-conjugated conductive polymer to an aqueous polyanion dispersion and subjecting the mixture to oxidative polymerization. A commercially available conductive polymer aqueous dispersion may also be used.

Freeze-drying or spray-drying is preferable as the method for drying the conductive polymer aqueous dispersion in (b). A dry product obtained by freeze-drying or spray-drying has a large surface area and is easily dispersed in a dispersion medium.

The conductive polymer-containing liquid obtained by adding the nitrogen-containing cyclic compound (A) is stirred using a high-pressure homogenizer while applying a high shearing force, and the conductive composite is sufficiently dispersed. preferably applied.

<Method for producing conductive film>
The method for producing a conductive film according to the second aspect of the present invention includes forming a coating film by applying the conductive polymer-containing liquid according to the first aspect to at least one surface of a film substrate.

(Film substrate)
Examples of film substrates include plastic films.
Examples of film substrate resins constituting plastic films include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio nate and the like. Among these film substrate resins, polyethylene terephthalate is preferable because it is inexpensive and has excellent mechanical strength.

Resins for film substrates 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 adhesion 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 thickness of a member in this specification is a value obtained by measuring the thickness at arbitrary 10 points and averaging the measured values.

A known polarizing film can also be used as the film substrate.
As a polarizing film, for example, one having a pair of transparent films and a polarizing layer disposed therebetween is known.
Examples of the transparent resin that constitutes the transparent film include triacetyl cellulose, polyethylene terephthalate, polycarbonate, polycycloolefin, polystyrene, polyvinyl alcohol, and acrylic resin.
The thickness of the transparent film can be, for example, 10 μm or more and 500 μm or less.
As the polarizing layer, for example, a hydrophilic film to which a dichroic substance is adhered is uniaxially stretched to orient the dichroic substance. Hydrophilic films include, for example, polyvinyl alcohol films and partially saponified ethylene/vinyl acetate copolymer films. Dichroic substances include, for example, iodine and dichroic dyes.
The thickness of the polarizing layer can be, for example, 10 μm or more and 500 μm or less.

When the conductive film is used for optical purposes, the film substrate is preferably transparent. Specifically, the total light transmittance of the film substrate is preferably 65% or more, more preferably 70% or more, and even more preferably 80% or more. The total light transmittance is a value measured according to JIS K7136.

Methods for coating (applying) the conductive polymer-containing liquid to the film substrate include, for example, gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, rod coaters, Apply methods using coaters such as air doctor coaters, knife coaters, blade coaters, cast coaters, and screen coaters; methods using atomizers such as air spray, airless spray, and rotor dampening; and immersion methods such as dipping. can be done.
Commercially available bar coaters are numbered according to coating thickness, and the larger the number, the thicker the coating.
The amount of the conductive polymer-containing liquid applied to the film substrate is not particularly limited, but in consideration of conductivity and film strength, the solid content is in the range of 0.01 g/m ² or more and 10.0 g/m ² or less. is preferably

By drying and removing the dispersion medium arbitrarily contained in the applied coating film composed of the conductive polymer-containing liquid, and when the coating film contains the curable binder component described above, by curing it. , a conductive film having the desired conductive layer formed thereon can be obtained.
Heat drying, vacuum drying, etc. are mentioned as a method of drying the coated conductive polymer containing liquid. As heat drying, for example, a normal method such as hot air heating or infrared heating can be used. 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.

When the binder component contained in the conductive polymer-containing liquid is thermosetting, it is preferable to heat-cure the coating film by applying heat drying when drying the coating film.
When the binder component contained in the conductive polymer-containing liquid is active energy ray-curable, it is preferable to irradiate the active energy ray after drying the coating film.
Examples of active energy rays include 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 are examples of ultraviolet light sources.
The illuminance in ultraviolet irradiation is preferably 100 mW/cm ² or more. When the illuminance is 100 mW/cm ² or more, sufficient polymerization and curing can be achieved. A guideline for the upper limit of the illuminance is, for example, 1000 mW/cm ² or less.
The cumulative amount of UV irradiation is preferably 50 mJ/cm ² or more. When the cumulative amount of light is 50 mJ/cm ² or more, sufficient polymerization and curing can be achieved. As a guideline for the upper limit of the integrated amount of light, for example, 1000 mJ/cm ² or less can be mentioned.
The above illuminance and integrated light intensity are measured using, for example, Topcon UVR-T1 (industrial UV checker, photodetector; UD-T36, measurement wavelength range: 300 nm or more and 390 nm or less, peak sensitivity wavelength: about 355 nm). be able to.

≪Conductive film≫
A third aspect of the present invention includes a conductive composite containing a π-conjugated conductive polymer and a polyanion and at least one nitrogen-containing cyclic compound (A) on at least one surface of a film substrate. A conductive film provided with a conductive layer.
The conductive film of this aspect can be produced by the production method of the second aspect.
The explanation of the film substrate of the conductive film of this aspect is the same as the explanation of the film substrate of the second aspect.

(Conductive layer)
The average thickness of the conductive layer provided on at least one surface of the film substrate is preferably 10 nm or more and 50000 nm or less, more preferably 50 nm or more and 25000 nm or less, and 100 nm or more and 10000 nm or less. More preferred.
If the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and if the average thickness is at most the upper limit value, a uniform conductive layer can be easily formed.

The conductive layer of the conductive film of the present embodiment has a resistance of 1×10 ¹ Ω/□ or more and 1×10 ⁷ Ω/□ or less after a light resistance test to be described later, as a measure of good conductivity and light resistance. It preferably has a surface resistance value of 1×10 ¹ Ω/□ or more and 1×10 ⁶ Ω/□ or less, more preferably 1×10 ¹ Ω/□ or more and 1×10 ⁵ Ω/□ or more. It is more preferable to have a surface resistance value of □ or less.

<Effect>
The conductive layer of the conductive film of the third aspect of the present invention contains the nitrogen-containing cyclic compound (A), and the decrease in conductivity due to exposure to light is suppressed.
The mechanism by which the nitrogen-containing cyclic compound (A) contributes to the light resistance has not yet been elucidated.
In general, it is said that when a polymer absorbs light such as ultraviolet rays, some carbon atoms become radicals and react with oxygen molecules in the atmosphere, resulting in auto-oxidation. The nitrogen-containing cyclic compound (A) has extremely low absorption of ultraviolet light, unlike aromatic nitrogen-containing compounds. For this reason, when the conductive layer according to the present invention is exposed to light and the atmosphere, "instead of the conductive composite absorbing light and auto-oxidizing, the nitrogen-containing cyclic compound (A) absorbs light. Therefore, it is thought that the mechanism of "suppressing autoxidation of the conductive composite" does not work.
Generally, the nitrogen atom in the nitrogen-containing cyclic compound (A) is more basic than the nitrogen atom in the nitrogen-containing aromatic compound. It is possible that this basicity contributes to light resistance, but triethylamine, which is strongly basic, does not contribute to light resistance (see Comparative Examples below). Since the nitrogen atom of the nitrogen-containing cyclic compound (A) is in the ring structure, it may more stereochemically contribute to the reaction that contributes to light resistance than the nitrogen atom of triethylamine.

Since the nitrogen-containing cyclic compound (A) and the conductive composite are stably dispersed in the conductive polymer-containing liquid of the first aspect of the present invention, it is suitable for the method for producing a conductive film of the second aspect. ing.
Since the method for producing a conductive film according to the second aspect of the present invention uses the conductive polymer-containing liquid according to the first aspect, the conductive film according to the third aspect can be easily produced.

(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 adding dropwise for 20 minutes, the solution was stirred for 12 hours. 1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting solution containing sodium polystyrene sulfonate, and about 1000 ml of solvent was removed from the solution containing polystyrene sulfonate 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. As a result of measuring the weight average molecular weight, the molecular weight was 300,000. The weight average molecular weight was measured using an HPLC (High Performance Liquid Chromatography) system with a GPC (gel permeation chromatography) column, using pullulan manufactured by Showa Denko KK as a standard substance.

(Production Example 2) Production of PEDOT-PSS aqueous dispersion Solution of 14.2 g of 3,4-ethylenedioxythiophene and 44.0 g of polystyrene sulfonic acid obtained in Production Example 1 dissolved in 2000 ml of deionized water were mixed at 20°C. The resulting mixed solution was kept at 20° C., and with 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, and the mixture was stirred for 3 hours. The mixture was stirred and reacted. 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 sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, about 2000 ml of the solvent is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to the residual liquid. , about 2000 ml of solvent 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 a blue PEDOT-PSS aqueous dispersion with a solid content concentration of 1.2% by mass and PEDOT:PSS=1:3 (mass ratio).

(Production Example 3) Preliminary Preparation 1
To 34.53 g (solid content 0.414 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 0.5% of Aron Oxetane 121 (manufactured by Toagosei Co., Ltd.), which is a thermosetting resin having an epoxy group and an oxetane group, was added. 34 g, 2.4 g of propylene glycol, 46 g of ethanol, and 16.73 g of ion-exchanged water were added to obtain a preliminary dispersion liquid X containing a conductive composite.

(Production Example 4) Preliminary Preparation 2
To 34.53 g (solid content 0.414 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.4 g of propylene glycol, 46 g of ethanol, and 17.07 g of ion-exchanged water were added to obtain a conductive composite. A predispersion Y containing

(Production Example 5) Preliminary Preparation 3
To 34.53 g (solid content 0.414 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 0.5% of Aron Oxetane 121 (manufactured by Toagosei Co., Ltd.), which is a thermosetting resin having an epoxy group and an oxetane group, was added. 34 g, 46 g of ethanol, and 19.13 g of ion-exchanged water were added to obtain a preliminary dispersion Z containing a conductive composite.

[Example 1]
0.072 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (4HpMP) was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4HpMP is 1:0.25.

[Example 2]
0.144 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4HpMP is 1:0.5.

[Example 3]
0.217 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4HpMP is 1:0.75.

[Example 4]
0.289 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4HpMP is 1:1.

[Example 5]
0.126 g of 1-methylpiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:1-methylpiperidine is 1:0.75.

[Example 6]
0.108 g of piperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The PSS:piperidine molar ratio is 1:0.75.

[Example 7]
0.128 g of 4-hydroxypiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4-hydroxypiperidine is 1:0.75.

[Example 8]
0.146 g of 4-hydroxy-1-methylpiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4-hydroxy-1-methylpiperidine is 1:0.75.

[Example 9]
0.291 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is 1:1. In addition, Example 9 is a comparative example.

[Example 10]
0.171 g of 4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine was added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4-hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine is 1:0.5.

[Example 11]
0.289 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine and 0.144 g of gallic acid were added to 100 g of preliminary dispersion liquid X to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4HpMP is 1:1.

[Comparative Example 1]
Without adding the nitrogen-containing cyclic compound (A), the preliminary dispersion liquid X was used as a mixed dispersion liquid for the production of the conductive film.

[Comparative Example 2]
0.144 g of gallic acid was added to 100 g of preliminary dispersion liquid X to obtain a mixed dispersion liquid. The molar ratio of PSS:gallic acid is 1:0.5.

[Comparative Example 3]
0.043 g of triethylamine (TEA) was added to 100 g of preliminary dispersion liquid X to obtain a mixed dispersion liquid. The molar ratio of PSS:TEA is 1:0.25.

[Comparative Example 4]
0.086 g of triethylamine was added to 100 g of preliminary dispersion liquid X to obtain a mixed dispersion liquid. The molar ratio of PSS:TEA is 1:0.5.

[Comparative Example 5]
0.128 g of triethylamine was added to 100 g of preliminary dispersion liquid X to obtain a mixed dispersion liquid. The molar ratio of PSS:TEA is 1:0.75.

[Comparative Example 6]
0.171 g of triethylamine was added to 100 g of preliminary dispersion liquid X to obtain a mixed dispersion liquid. The molar ratio of PSS:TEA is 1:1.

[Example 12]
0.289 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine was added to 100 g of the preliminary dispersion liquid Y that did not contain the thermosetting resin arone oxetane 121, and a conductive polymer-containing liquid was obtained. got The molar ratio of PSS:4HpMP is 1:1.

[Comparative Example 7]
The preliminary dispersion liquid Y was used as a mixed dispersion liquid for the production of the conductive film without adding the nitrogen-containing cyclic compound (A).

[Example 13]
0.289 g of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine was added to 100 g of preliminary dispersion Z containing no propylene glycol to obtain a conductive polymer-containing liquid. The molar ratio of PSS:4HpMP is 1:1.

[Comparative Example 8]
Without adding the nitrogen-containing cyclic compound (A), the preliminary dispersion Z was used as a mixed dispersion for the production of the conductive film.

<Production of conductive film>
Bar coater no. 20, the conductive polymer-containing liquid obtained in each example and the mixed dispersion obtained in each comparative example were coated on one side of a PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4300). and dried at 120° C. for 2 minutes to obtain a conductive film having a conductive layer formed thereon.

<Light resistance test>
For the produced conductive film, first, the initial surface resistance value R0 immediately after production was measured.
Next, using a xenon arc weather meter Ci4000, ultraviolet light was applied to the conductive layer of the conductive film under the following conditions: radiation wavelength: 340 nm, irradiance: 0.86 W/m ² , radiation time: 100 hours, temperature inside the tank: 55°C. was irradiated. After that, the surface resistance value R1 of the conductive film was measured. A low resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Anatelic Co., Ltd.) was used to measure the surface resistance value. Each measurement result is shown in Tables 1 to 3.
The smaller the surface resistance value (unit: Ω/□ (ohms per square)) in the measurement results, the higher the conductivity. Also, the smaller the surface resistance ratio (magnification of change) represented by R1/R0, the better the light resistance.

The chemical formulas of the compounds used in each example are shown below.

From the results in Tables 1 to 3, it is clear that the conductive layer containing the nitrogen-containing cyclic compound (A) exhibits excellent light resistance and good electrical conductivity.
The results in Table 1 are a comparison when containing a binder component and a high boiling point solvent. By including a binder component, the adhesiveness of the conductive layer to the base material can be improved, and the film strength can be improved, which is preferable.
In addition, the inclusion of a high boiling point solvent is preferable because the surface resistance value of the conductive layer can be greatly reduced.
From the results of Examples 1 to 4, when the content of the nitrogen-containing cyclic compound (A) is 0.25 mol or more with respect to 1 mol of the monomer unit of PSS, sufficient light resistance is exhibited, and 1 mol The closer it gets, the more the light resistance improves, and there is a tendency that the improvement rate of the light resistance gradually peaks out.
The results in Table 2 are the results when no binder component is contained. Even without containing a binder component, the addition of the nitrogen-containing cyclic compound (A) has the effect of improving the light resistance of the conductive layer.
The results in Table 3 are the results when no high conductivity agent is contained. By adding the nitrogen-containing cyclic compound (A), the effect of improving the light resistance of the conductive layer is observed.

From the results of Comparative Examples 1, 7, and 8, in order to reduce the resistance and improve the adhesion of the conductive layer, a high boiling point solvent (propylene glycol) and a binder component (epoxy group and oxetane group-containing thermal curable resin), it is understood that the light resistance is remarkably deteriorated. However, as shown in Examples 1 to 13, by adding the nitrogen-containing cyclic compound (A), it is possible to markedly reduce the deterioration of the light resistance described above.
From the above, it is clear that the conductive polymer-containing liquid of the present invention containing the nitrogen-containing cyclic compound (A) can form a conductive layer with excellent light resistance even when it contains a high boiling point solvent and a binder component. .

Claims (15)

A conductive polymer-containing liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, and one or more nitrogen-containing cyclic compounds represented by the following chemical formula (A).

[In the formula (A), R ¹ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and one or more of the hydrogen atoms of the alkyl group is substituted with a hydroxyl group; and each of R ² to R ¹¹ independently represents a hydrogen atom or any substituent. ] In the chemical formula (A), the optional substituent is an alkyl group having 1 to 14 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, a hydroxyl group, an amino group, or a carboxy group, and hydrogen possessed by these substituents 2. The conductive polymer-containing liquid according to claim 1, wherein atoms may be substituted with other substituents. The nitrogen-containing cyclic compound is 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1-methylpiperidine, piperidine, 4-hydroxypiperidine, 4-hydroxy-1-methylpiperidine , and 4- 3. The conductive polymer-containing liquid according to claim 1, comprising at least one selected from hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine. 4. The molar ratio between the nitrogen-containing cyclic compound content G1 and the monomer unit content G2 of the polyanion is G1≧0.25 with respect to G2=1. The conductive polymer-containing liquid according to item 1. The conductive polymer-containing liquid according to any one of claims 1 to 4, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The conductive polymer-containing liquid according to any one of claims 1 to 5, wherein the polyanion is polystyrenesulfonic acid. The conductive polymer-containing liquid according to any one of claims 1 to 6, further comprising one or more phenolic antioxidants. 8. The conductive polymer-containing liquid according to claim 7, wherein said phenolic antioxidant contains one or more selected from gallic acid, methyl gallic acid, ethyl gallic acid and propyl gallic acid. The conductive polymer-containing liquid according to any one of claims 1 to 8, further comprising a binder component. 10. The conductive polymer-containing liquid according to claim 9, wherein said binder component contains a curable monomer or oligomer having at least one of an epoxy group and an oxetane group. 10. The conductive polymer-containing liquid according to claim 9, wherein the binder component contains acrylic resin or polyester resin. The conductive polymer-containing liquid according to any one of claims 1 to 11, further comprising at least one of water and an alcoholic solvent. The conductive polymer-containing liquid according to any one of claims 1 to 12, further comprising a high-boiling solvent having a boiling point of 150°C or higher at 1 atmosphere. A method for producing a conductive film, comprising applying the conductive polymer-containing liquid according to any one of claims 1 to 13 to at least one surface of a film substrate to form a coating film. A conductive layer containing a conductive composite containing a π-conjugated conductive polymer and a polyanion and at least one nitrogen-containing cyclic compound represented by the following chemical formula (A) on at least one surface of a film substrate. A conductive film provided with.

[In the formula (A), R ¹ is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and one or more of the hydrogen atoms of the alkyl group is substituted with a hydroxyl group; and each of R ² to R ¹¹ independently represents a hydrogen atom or any substituent. ]