JP2021038328A - Conductive polymer dispersion, conductive laminate, and method of producing the same - Google Patents

Abstract

To provide a conductive polymer dispersion capable of forming a conductive layer excellent in light fastness even if not containing a diol compound in a high concentration, a conductive laminate having a conductive layer composed of a hardened layer of the conductive polymer dispersion, and a method of producing the same.SOLUTION: The conductive polymer dispersion includes a conductive complex including a π-conjugated conductive polymer, and polyanion; a specific hydroxypyridine compound(s); and a dispersion medium. The hydroxypyridine compound(s) preferably includes one or more selected from the group consisting of, for example, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dihydroxypyridine, 2,3-dihydroxypyridine, 2,6-dimethyl-4-hydroxypyridine, 2,4-dihydroxy-6-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxyisonicotinic acid, 2-hydroxynicotinic acid, 6-hydroxynicotinic acid, and 3-hydroxy-2-pyridinecarboxylic acid.SELECTED DRAWING: None

Description

The present invention relates to a conductive polymer dispersion, a conductive laminate, and a method for producing the same.

As a coating material for forming the conductive layer, a conductive polymer dispersion containing a conductive composite in which poly (3,4-ethylenedioxythiophene) is doped with polystyrene sulfonic acid may be used.
Patent Document 1 discloses that a conductive layer formed of a conductive polymer dispersion containing a diol compound in a proportion of 85 to 100% by mass is excellent in light resistance.

Japanese Unexamined Patent Publication No. 2019-116537

However, since the conductive polymer dispersion described in Patent Document 1 contains a diol compound at a high concentration, it has a high viscosity, and there is a problem that it is difficult to apply it to a substrate by spin coating.

The present invention comprises a conductive polymer dispersion liquid capable of forming a conductive layer having excellent light resistance without containing a high concentration of a diol compound, and a conductive layer composed of a cured layer of the conductive polymer dispersion liquid. Provided are a conductive laminate provided and a method for producing the same.

[1] A conductive polymer dispersion liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a hydroxypyridine compound represented by the following formula (1), and a dispersion medium.
[2] The hydroxypyridine compound is 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dihydroxypyridine, 2,3-dihydroxypyridine, 2,6-dimethyl-4-hydroxypyridine, 2 , 4-Dihydroxy-6-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxyisonicotinic acid, 2-hydroxynicotinic acid, 6-hydroxynicotinic acid, and 3-hydroxy-2-pyridinecarboxylic acid The conductive polymer dispersion according to [1], which comprises at least one selected from the group.
[3] The conductive polymer dispersion according to [1] or [2], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the polyanion is polystyrene sulfonic acid.
[5] The conductive polymer dispersion liquid according to any one of [1] to [4], which further contains a binder component.
[6] The conductive polymer dispersion according to [5], wherein the binder component contains at least one selected from the group consisting of a thermoplastic resin, a curable monomer, a curable oligomer, and silica.
[7] A conductive layer formed on at least one surface of the substrate and composed of a cured layer of the conductive polymer dispersion liquid according to any one of [1] to [6]. A conductive laminate.
[8] A method for producing a conductive laminate, which comprises coating at least one surface of a base material with the conductive polymer dispersion liquid according to any one of [1] to [6].

［式（１）中、Ｒ^１は水酸基であり、Ｒ^２はカルボキシル基または炭素数１〜４のアルキル基であり、ｍは１〜３の整数であり、ｎは０〜２の整数である。］

[In the formula (1), R ¹ is a hydroxyl group, R ² is a carboxyl group or an alkyl group having 1 to 4 carbon atoms, m is an integer of 1 to 3, and n is an integer of 0 to 2. .. ]

According to the conductive polymer dispersion liquid of the present invention, it is possible to form a conductive layer having excellent light resistance even if it does not contain a high concentration of a diol compound. This conductive layer is excellent in durability because the decrease in conductivity due to exposure to a high temperature and high humidity environment is suppressed. Further, when the conductive layer contains an antioxidant which is an optional component, the bleed-out of the antioxidant due to exposure to a high temperature and high humidity environment is suppressed, and high transparency can be maintained. Similarly, bleeding out of the hydroxypyridine compound represented by the formula (1) described later due to exposure to a high temperature and high humidity environment hardly occurs, and high transparency can be maintained.
Since the conductive laminate of the present invention has a conductive layer having excellent light resistance, durability, and transparency, it is also suitable for applications such as displays and optical members.
In the method for producing a conductive laminate of the present invention, a conductive polymer dispersion can be applied by a general-purpose coating method such as a bar coater or spin coating, and a conductive layer having a film thickness suitable for the application can be applied. Can be easily formed.

≪Conductive polymer dispersion liquid≫
The first aspect of the present invention is a highly conductive composite containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a hydroxypyridine compound represented by the formula (1) described later, and a dispersion medium. It is a molecular dispersion liquid.

[Conductive composite]
The conductive composite contained in the conductive polymer dispersion of this embodiment contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite is doped with a π-conjugated conductive polymer to form a conductive composite having conductivity.
In the poly anion, only a part of the anion groups are doped in the π-conjugated conductive polymer, and the poly anion has a surplus anion group that is not involved in the doping. Since the excess anion group is a hydrophilic group, the conductive composite has water dispersibility.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer may be an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, or a polyacetylene-based conductive polymer has high conductivity. Examples thereof include molecules, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene vinylene-based conductive polymers, and copolymers thereof. 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 (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-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers 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-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable because it is excellent in conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer contained in the conductive complex may be of one type or two or more types.

(Polyanion)
A polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic 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 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, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid. The polyanion is a single monomer. It may be a homopolymer obtained by polymerizing the above, or it may be a copolymer obtained by polymerizing two or more kinds of monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight measured by gel permeation chromatography and determined in terms of polystyrene.

The content ratio 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. It is more preferable that the amount is 100 parts by mass or more and 500 parts by mass or less. When the content ratio of the polyanion is at least the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

The content of the conductive composite contained in the conductive polymer dispersion of this embodiment is preferably 0.01% by mass or more and 5% by mass or less with respect to the total mass of the conductive polymer dispersion. It is preferably 05% by mass or more and 3% by mass or less, and more preferably 0.1% by mass or more and 2% by mass or less.
When it is at least the lower limit of the above range, the conductivity of the conductive layer formed by applying the conductive polymer dispersion can be further improved.
When it is not more than the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer dispersion can be enhanced and a uniform conductive layer can be formed.

[Hydroxypyridine compound]
One or more kinds of hydroxypyridine compounds contained in the conductive polymer dispersion of this embodiment are compounds represented by the following formula (1) (hereinafter, may be referred to as "hydroxypyridine compound (1)"). Is.

In the above formula (1), R ¹ is a hydroxyl group, R ² is a carboxyl group or an alkyl group having 1 to 4 carbon atoms, m is an integer of 1 to 3, and n is an integer of 0 to 2. ..
From the viewpoint of further enhancing the effect of the present invention, the formula (1) preferably has the following configuration.
The alkyl group may be linear or branched.
The alkyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2, and even more preferably 1.
The ^{m representing the number of functional groups of R 1} is preferably 1 or 2, and more preferably 1.
When n representing the number of functional groups of ^{R 2 is 0, m is preferably 1.}
When n representing the number of functional groups of ^{R 2 is 1, R 2} is preferably a carboxyl group, and m is preferably 1.
When n representing the number of functional groups of ^{R 2 is 2, at least one of the two R 2} is preferably a methyl group, and m is preferably 1.

Preferable specific examples of the hydroxypyridine compound (1) are 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dihydroxypyridine, 2,3-dihydroxypyridine, 2,6-dimethyl-4-. Hydroxypyridine, 2,4-dihydroxy-6-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxyisonicotinic acid, 2-hydroxynicotinic acid, 6-hydroxynicotinic acid, and 3-hydroxy-2-pyridine Carous acid can be mentioned. The conductive polymer dispersion liquid of this embodiment preferably contains at least one selected from this group.
Among the above-exemplified examples, 4-hydroxypyridine is particularly preferable because the durability of the formed conductive layer is particularly easy to improve.

In the conductive polymer dispersion liquid of this embodiment, the content of the hydroxypyridine compound (1) with respect to 100 parts by mass (parts by weight) of the conductive composite is preferably 1 part by mass or more and 1000 parts by mass or less, and 10 parts by mass or more. It is more preferably 500 parts by mass or less, and further preferably 20 parts by mass or more and 200 parts by mass or less. Within the above-mentioned preferable range, the durability and light resistance of the conductive layer can be further improved.

[Dispersion medium]
Examples of the dispersion medium contained in the conductive polymer dispersion liquid of this embodiment include water, an organic solvent, and a mixed liquid of water and an organic solvent.
Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents and the like.
Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, and propylene glycol monomethyl. Monohydric alcohols such as ether and ethylene glycol monomethyl ether; dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. Can be mentioned.
Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether and the like.
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.
Examples of solvents not classified above include dimethyl sulfoxide.
One type of organic solvent may be used alone, or two or more types may be used in combination.
Among the organic solvents, one or more selected from alcohol solvents and dimethyl sulfoxide are preferable because the dispersibility of the conductive composite can be further enhanced.
From the viewpoint of further enhancing the dispersibility of the conductive composite, the alcohol solvent and dimethyl sulfoxide are preferably contained in combination with water.
Dimethyl sulfoxide is preferably contained in combination with one or more alcohol solvents.

Since the conductive composite has high dispersibility in water, the dispersion medium of the conductive polymer dispersion liquid of this embodiment is preferably an aqueous dispersion medium containing water.
The content ratio of water to the total dispersion medium contained in the conductive polymer dispersion liquid of this embodiment is, for example, preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and 40% by mass or more. 65% by mass or less is more preferable. Further, it is preferable that 100 to 250 parts by mass of water is contained with respect to 1 part by mass of the conductive composite contained in the conductive polymer dispersion liquid of this embodiment.
As the dispersion medium other than water, the above-mentioned organic solvent is preferable. It should be noted that, among the high conductivity agents described later, the mass of the one corresponding to the example of the organic solvent is included in the mass of the total dispersion medium.

[Binder component]
The binder component is a compound other than the π-conjugated conductive polymer, the polyanion, and the hydroxypyridine compound (1), and is a group consisting of a thermoplastic resin, a curable monomer that cures when the conductive layer is formed, a curable oligomer, and silica. At least one selected from. The thermoplastic resin becomes a binder as it is, and the cured product formed by curing becomes a binder (binding material) for the curable monomer, the curable oligomer, and silica.
Specific examples of the binder derived from the binder component include acrylic resin, polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, silicone, a condensate of alkoxysilane, and a condensate of silicate.
In the present specification, a silane compound is a general term for a condensate of alkoxysilane and a condensate of silicate.
The binder component contained in the conductive polymer dispersion liquid of this embodiment may be one kind or two or more kinds.

When the binder component is a thermoplastic resin, the binder resin is preferably a water-dispersible resin that can be dispersed in a conductive polymer dispersion. The water-dispersible resin is an emulsion resin or a water-soluble resin.
Specific examples of the emulsion resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, melamine resin and the like, which have been emulsified with an emulsifier.
Specific examples of the water-soluble resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, and melamine resin, which have an acid group such as a carboxy group or a sulfo group or a salt thereof.
The water-soluble resin is dissolved in distilled water at 25 ° C. in an amount of 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more.

When the base material to which the conductive polymer dispersion liquid of this embodiment is applied is made of a polyester resin, it is preferable that the binder component contains at least one selected from the above-mentioned water-dispersible polyester resin.

The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, the oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of the curable monomer include an acrylic monomer, an epoxy monomer, an organosiloxane, an alkoxysilane, and a silicate.
Examples of the curable oligomer include an acrylic oligomer, an epoxy oligomer, and a silicone oligomer (curable silicone).

When an acrylic monomer or an acrylic oligomer is contained as a binder component, it can be easily cured by heating or light irradiation. When an organosiloxane or a silicone oligomer is contained as a binder component, releasability can be imparted to the conductive layer. Further, when alkoxysilane, silicate, or silica is contained as a binder component, a silanol structure is formed by heating, and further condensing and easily curing can impart hardness to the conductive layer.

As used herein, the alkoxysilane is a compound having one silicon atom in the molecule and having one or more alkoxy groups bonded to the silicon atom.
Since the alkoxysilane contained in this embodiment is easily hydrolyzed, it preferably has a methoxy group or an ethoxy group, and more preferably has a methoxy group.
The alkoxysilane may have, for example, an epoxy group, an allyl group, a vinyl group, a glycidyl group, or the like as a functional group other than the alkoxy group.
Specific preferred alkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltri. Examples thereof include ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like.

The preferable content of alkoxysilane in the conductive polymer dispersion of this embodiment is preferably 10 parts by mass or more and 10000 parts by mass or less, and 50 parts by mass or more and 5000 parts by mass with respect to 100 parts by mass (weight parts) of the conductive composite. It is more preferably 100 parts by mass or more and 2000 parts by mass or less.
When the content of the silicate is at least the lower limit value, the hardness of the conductive layer formed from the conductive polymer dispersion can be sufficiently increased, and when it is at least the upper limit, the conductivity from the conductive polymer dispersion is used. It is possible to prevent a decrease in the conductivity of the formed conductive layer.

As used herein, a silicate is a compound having two or more silicon atoms in one molecule, in which at least one set of silicon atoms is ether-bonded via one oxygen atom. The number of silicon atoms contained in one molecule of the silicate is preferably 4 or more, preferably 6 or more, because the hardness of the conductive layer formed from the conductive polymer dispersion liquid of this embodiment becomes higher. It is more preferable that there are eight or more, and it is further preferable that there are eight or more. Further, from the viewpoint of enhancing the solubility of the silicate in the conductive polymer dispersion liquid of this embodiment, the number of silicon atoms contained in one molecule of the silicate is preferably 40 or less, more preferably 30 or less.
_{The content of 2} units of SiO of the silicate is preferably 15% by mass or more and 70% by mass or less, and more preferably 25% by mass or more and 50% by mass or less with respect to the total mass of the silicate. _{When the content of 2} units of SiO in the silicate is at least the lower limit value, the hardness of the conductive layer formed from the conductive polymer dispersion liquid of this embodiment becomes higher, and when it is at least the upper limit value, the conductive layer is said. It is possible to prevent a decrease in conductivity.
_{Here, the content of 2} units of SiO in the silicate _{is the ratio of the mass of 2} units of SiO (-O-Si-O- units) contained in the silicate to 100% by mass of the molecular weight of the silicate, and is obtained by element analysis. Can be measured.

The silicate is preferably a compound represented by the following chemical formula (X).
(X) ... R ³ O-[(R ⁴ O-) (R ⁵ O-) Si-O-] _s- R ⁶

In formula (X), R ³ , R ⁴ , R ⁵ , and R ⁶ are independently linear or branched alkyl groups having 1 to 4 carbon atoms, and s is an integer of 2 to 100. Is.
The alkyl group having 1 to 4 carbon atoms may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group.
s is preferably 2 to 50, more preferably 3 to 25, and even more preferably 4 to 10.

It is more preferable that the silicate is at least one of the compound represented by the following chemical formula (x1) and the compound represented by the following chemical formula (x2).
_{(X1) ... Si m O m} -1 (OCH 3) 2m + 2
(X2) ... Si _{n On -1} (OCH ₂ CH ₃ ) _{2n + 2}
In the above formulas (x1) and (x2), m is 2 or more and 100 or less, and n is 2 or more and 100 or less.
In the above equations (x1) and (x2), Si and O are bonded, and Si and O are not adjacent to each other.

The preferable content of the silicate in the conductive polymer dispersion is appropriately selected according to the content of _{2 units of SiO of the silicate. When the content of 2} units of SiO of the silicate is in the above-mentioned preferable range, the content of the silicate is preferably 1 part by mass or more and 100,000 parts by mass or less with respect to 100 parts by mass of the conductive composite. It is more preferably 10,000 parts by mass or less, and further preferably 100 parts by mass or more and 2000 parts by mass or less.
When the content of the silicate is at least the lower limit value, the hardness of the conductive layer formed from the conductive polymer dispersion can be sufficiently increased, and when it is at least the upper limit, the conductivity from the conductive polymer dispersion is used. It is possible to prevent a decrease in the conductivity of the formed conductive layer.

When the base material to which the conductive polymer dispersion liquid of this embodiment is applied is made of glass, the binder component preferably contains one or more selected from the above-mentioned alkoxysilanes or silicates.

When a curable monomer or oligomer is used, a curing catalyst may be added. In the case of thermosetting monomers or oligomers, thermal polymerization initiators that generate radicals upon heating are preferred. In the case of a photocurable monomer or oligomer, a photopolymerization initiator that generates radicals by light irradiation is preferable. When an organosiloxane or a silicone oligomer is used, it is preferable to use a platinum catalyst for curing.

As the silica, colloidal silica is preferable from the viewpoint of dispersibility, and organic solvent-dispersible colloidal silica (hereinafter, also referred to as “organosilica sol”) is more preferable. Commercially available organosilica sol products include methanol silica sol, MA-ST-M, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, EG-ST-ZL, DMAC-ST, DMAC-ST-ZL, NPC-ST-30, PGM-ST, MEK-ST, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-SD, PMA-ST, EAC-ST, NBAC-ST, XBA-ST, TOR-ST, MEK-AC-2101, MEK-AC-4101 (trade name, manufactured by Nissan Chemical Industries, Ltd.); OSCAL-1432, OSCAL-1132, OSCAL-1632 and OSCAL-1421 (trade name, manufactured by JGC Catalysts and Chemicals Co., Ltd.) can be mentioned.

The content ratio of the solid content (nonvolatile component) of the binder component other than the above-mentioned alkoxysilane and silicate is preferably 100 parts by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the solid content of the conductive composite, and is preferably 100 parts by mass. More than 5000 parts by mass is more preferable, and 100 parts by mass or more and 2000 parts by mass or less is further preferable. When the content ratio of the binder component is at least the above lower limit value, the strength of the conductive layer can be improved. On the other hand, if the content ratio of the binder component is excessive, the content ratio of the conductive composite decreases, so that the conductivity of the conductive layer may decrease.

[Highly conductive agent]
The conductive polymer dispersion liquid of this embodiment may contain a highly conductive agent in order to further improve the conductivity. Here, the π-conjugated conductive polymer, the polyanion, the above-mentioned hydroxypyridine compound (1), and the above-mentioned binder component are not classified as high conductivity agents.
Highly conductive agents include saccharides, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having one or more hydroxy groups and one or more carboxy groups, and compounds having amide groups. It is preferably at least one compound selected from the group consisting of a compound having an imide group, a lactam compound, and a compound having a glycidyl group.
As the highly conductive agent, a compound having two or more hydroxy groups (divalent alcohol) or a compound having an amide group is preferable, and ethylene glycol, propylene glycol, 1,3-propanediol, and dimethyl sulfoxide are more preferable.
The highly conductive agent contained in the conductive polymer dispersion liquid of this embodiment may be one kind or two or more kinds.

The content ratio of the highly conductive agent in the conductive polymer dispersion of this embodiment is preferably 1 part by mass or more and 100,000 parts by mass or less, and 10 parts by mass or more and 10,000 parts by mass with respect to 100 parts by mass of the conductive composite. More preferably, it is 50 parts by mass or less, and further preferably 50 parts by mass or more and 5000 parts by mass or less. When the content ratio of the high conductive agent is not less than the lower limit value, the effect of improving the conductivity by adding the high conductivity agent is sufficiently exhibited, and when it is not more than the upper limit value, the concentration of the π-conjugated conductive polymer is lowered. It is possible to prevent a decrease in conductivity due to the above.

[Other additives]
The conductive polymer dispersion liquid of this embodiment may contain other additives.
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, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used. However, the additive is a compound other than the conductive complex, the hydroxypyridine compound (1), the dispersion medium, the highly conductive agent, and the binder component.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having an epoxy group, a vinyl group or an amino group.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.
When the conductive polymer dispersion liquid contains the above additive, the content ratio thereof is appropriately determined according to the type of the additive, and is, for example, 0.001 part by mass with respect to 100 parts by mass of the conductive composite. The range may be 5 parts by mass or less.

<Especially preferred embodiment 1>
When the conductive polymer dispersion liquid of this embodiment contains at least one of monohydroxypyridine and dihydroxypyridine as the hydroxypyridine compound (1), propylene glycol monomethyl ether, methanol or ethanol, water, and water are used as dispersion media. It is particularly preferable to contain ethylene glycol or propylene glycol or dimethylsulfoxide or 1,3-propanediol, and to contain one or more alkoxysilanes or water-soluble resins as binder components.
The content of water with respect to the total mass of the conductive polymer dispersion is preferably 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 80% by mass or less, and further preferably 50% by mass or more and 70% by mass or less. preferable.
The content of the monohydric alcohol with respect to the total mass of the conductive polymer dispersion is preferably 10% by mass or more and 49% by mass or less, more preferably 20% by mass or more and 45% by mass or less, and 30% by mass or more and 40% by mass or less. Is even more preferable. Here, the content of propylene glycol monomethyl ether is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and further preferably 4% by mass or more and 12% by mass or less.
The content of divalent alcohol with respect to the total mass of the conductive polymer dispersion is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and 4% by mass or more and 10% by mass or less. Is even more preferable.
In the above-mentioned particularly preferable embodiment, the conductive layer having good wettability to the resin base material and having excellent adhesiveness, durability and light resistance to the resin base material of the formed conductive layer can be particularly easily formed. Can be formed.

<Especially preferred embodiment 2>
When the conductive polymer dispersion liquid of this embodiment contains a monohydroxypyridine compound having a carboxyl group as the hydroxypyridine compound (1), propylene glycol monomethyl ether, methanol or ethanol, water, and dimethyl sulfoxide are used as dispersion media. And, as a binder component, it is particularly preferable to contain one or more kinds of water-soluble resins.
The content of water with respect to the total mass of the conductive polymer dispersion is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and further preferably 40% by mass or more and 50% by mass or less. preferable.
The content of the monohydric alcohol with respect to the total mass of the conductive polymer dispersion is preferably 10% by mass or more and 50% by mass or less, more preferably 20% by mass or more and 45% by mass or less, and 30% by mass or more and 40% by mass or less. Is even more preferable. Here, the content of propylene glycol monomethyl ether is preferably 3% by mass or more and 20% by mass or less, more preferably 6% by mass or more and 15% by mass or less, and further preferably 9% by mass or more and 12% by mass or less.
The content of dimethyl sulfoxide with respect to the total mass of the conductive polymer dispersion is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and 15% by mass or more and 25% by mass or less. More preferred.
In the above-mentioned particularly preferable embodiment, the conductive layer having good wettability to the resin base material and having excellent adhesiveness, durability and light resistance to the resin base material of the formed conductive layer can be particularly easily formed. Can be formed.

<Especially preferred embodiment 3>
When the conductive polymer dispersion liquid of this embodiment contains monohydroxypyridine having an alkyl group as the hydroxypyridine compound (1), propylene glycol monomethyl ether, methanol or ethanol, water, ethylene glycol or It is particularly preferable to contain propylene glycol and one or more water-soluble resins as a binder component.
The content of water with respect to the total mass of the conductive polymer dispersion is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and further preferably 40% by mass or more and 50% by mass or less. preferable.
The content of the monohydric alcohol with respect to the total mass of the conductive polymer dispersion is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 65% by mass or less, and 40% by mass or more and 60% by mass or less. Is even more preferable. Here, the content of propylene glycol monomethyl ether is preferably 3% by mass or more and 20% by mass or less, more preferably 6% by mass or more and 15% by mass or less, and further preferably 9% by mass or more and 12% by mass or less.
The content of divalent alcohol with respect to the total mass of the conductive polymer dispersion is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 20% by mass or less, and 4% by mass or more and 10% by mass or less. Is even more preferable.
In the above-mentioned particularly preferable embodiment, the conductive layer having good wettability to the resin base material and having excellent adhesiveness, durability and light resistance to the resin base material of the formed conductive layer can be particularly easily formed. Can be formed.

<Especially preferred embodiment 4>
When the conductive polymer dispersion liquid of this embodiment contains at least one of monohydroxypyridine and dihydroxypyridine as the hydroxypyridine compound (1) and contains two or more kinds of alkoxysilanes as a binder component, it is used as a dispersion medium. , Propylene Glycol Monomethyl Ether, Methanol or Ethanol, Water, Ethylene Glycol or Propylene Glycol.
The content of water with respect to the total mass of the conductive polymer dispersion is preferably 30% by mass or more and 70% by mass or less, more preferably 35% by mass or more and 60% by mass or less, and further preferably 40% by mass or more and 50% by mass or less. preferable.
The content of the monohydric alcohol with respect to the total mass of the conductive polymer dispersion is preferably 10% by mass or more and 49% by mass or less, more preferably 20% by mass or more and 40% by mass or less, and 25% by mass or more and 35% by mass or less. Is even more preferable. Here, the content of propylene glycol monomethyl ether is preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less, and further preferably 3% by mass or more and 6% by mass or less.
The content of divalent alcohol with respect to the total mass of the conductive polymer dispersion is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and 4% by mass or more and 10% by mass or less. Is even more preferable.
In the above-mentioned particularly preferable embodiment, the viscosity is such that the viscosity can be easily applied by the spin coating method, the wettability to the glass substrate is good, and the adhesiveness and durability of the formed conductive layer to the glass substrate are good. A conductive layer having excellent properties and light resistance can be formed particularly easily.

<Manufacturing method of conductive polymer dispersion>
Examples of the method for producing the conductive polymer dispersion liquid of this embodiment include a method of adding a dispersion medium, a binder component, a hydroxypyridine compound (1), and the like to the aqueous dispersion liquid of the conductive composite.
The aqueous dispersion of the conductive composite may be obtained by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of a polyanion, or a commercially available one may be used.

The chemical oxidative polymerization can be carried out using a known catalyst and an oxidizing agent. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.

≪Conductive laminate≫
A second aspect of the present invention is a conductive laminate comprising a base material and a conductive layer formed on at least one surface of the base material and composed of a cured layer of the conductive polymer dispersion liquid of the first aspect. Is.

[Conductive layer]
The average thickness of the conductive layer provided on at least one surface of the base material is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and 30 nm or more and 30 μm or less. Is even more preferable.
When the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and when it is at least the upper limit value, the adhesion of the conductive layer to the substrate is further improved.

As a measure of the good conductivity of the conductive layer of this embodiment, for example, 1 × 10 ¹ Ω / sq. 1 × 10 ⁵ Ω / sq. It preferably has the following surface resistance values, 1 × 10 ² Ω / sq. 1 × 10 ⁴ Ω / sq. It is more preferable to have the following surface resistance value, and 1 × 10 ² Ω / sq. 1 × 10 ³ Ω / sq. It preferably has the following surface resistance values.

[Base material]
The base material constituting the conductive laminate of this embodiment may be a base material made of an insulating material or a base material made of a conductive material. The shape of the base material is not particularly limited, and examples thereof include a shape mainly composed of a flat surface such as a film or a substrate.
Examples of the insulating material include glass, synthetic resin, and ceramics.
Examples of the conductive material include metals, conductive metal oxides, carbon and the like.

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

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

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

A known polarizing film can also be used as the film base material.
As the polarizing film, for example, a film including a pair of transparent films and a polarizing layer arranged between them is known.
Examples of the transparent resin constituting the transparent film include triacetyl cellulose, polyethylene terephthalate, polycarbonate, polycycloolefin, polystyrene, polyvinyl alcohol, acrylic resin and the like.
The thickness of the transparent film can be, for example, 10 μm or more and 500 μm or less, and is preferably 20 μm or more and 300 μm or less from the viewpoint of achieving both thinness and strength.
Examples of the polarizing layer include those in which a dichroic substance is attached to a hydrophilic film and uniaxially stretched to orient the dichroic substance. Examples of the hydrophilic film include a polyvinyl alcohol film and a partially saponified film of an ethylene-vinyl acetate copolymer. Examples of the dichroic substance include iodine and a dichroic dye.
The thickness of the polarizing layer can be, for example, 10 μm or more and 500 μm or less, and is preferably 20 μm or more and 300 μm or less from the viewpoint of achieving both thinness and polarization property.

When the conductive film is used for optical applications, it is preferable that the film base material is 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.

≪Manufacturing method of conductive laminate≫
A third aspect of the present invention is a method for producing a conductive laminate, which comprises applying the conductive polymer dispersion liquid of the first aspect to at least one surface of a base material. By the production method of this aspect, the conductive laminate of the second aspect can be produced.

As a method of applying (applying) the conductive polymer dispersion liquid of the first aspect to an arbitrary surface of the base material, for example, a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, and a knife coater. , Fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc., air spray, airless spray, rotor dampening, etc. A dipping method or the like can be applied.

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

By drying a coating film made of a conductive polymer dispersion liquid coated on a base material and removing the dispersion medium, a conductive layer (conductive film) formed by curing the coating film is formed. A laminate can be obtained.
Examples of the method for drying the coating film include heat drying and vacuum drying. As the heat drying, for example, a method such as hot air heating or infrared heating can be adopted.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, but is usually in the range of 50 ° C. or higher and 150 ° C. or lower. Here, the heating temperature is a set temperature of the drying device. The preferable drying time in the above heating temperature range is preferably 1 minute or more and 30 minutes or less, and more preferably 5 minutes or more and 15 minutes or less.

When the coated conductive polymer dispersion contains the above-mentioned silicon oxide-containing compound such as alkoxysilane, silicate, and silica as the binder component, the coating film is heated to react the binder components with each other. A cured conductive layer can be formed.
When the coated conductive polymer dispersion contains a thermosetting monomer or oligomer as a binder component, the coating film is heated and the binder components are reacted with each other to form a cured conductive layer. be able to.
When the coated conductive polymer dispersion contains a photocurable monomer or oligomer as a binder component, the coating film is irradiated with ultraviolet rays or electron beams and cured by reacting the binder components with each other. A conductive layer can be formed.

(Production Example 1) Synthesis of polyanion 206 g of sodium styrene sulfonate is dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water is added to the solution at 80 ° C. for 20 minutes. The solution was added dropwise and the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution, and about 1000 ml of the solvent of the obtained polystyrene sulfonate-containing solution was removed by an ultrafiltration method. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonic acid was washed with water. This washing operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Production Example 2) Synthesis of Conductive Composite 14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 in 2000 ml of ion-exchanged water were added. Mix at 20 ° C. The obtained mixed solution was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added, and the mixture was slowly added for 3 hours. The mixture was stirred and reacted.
2000 ml of ion-exchanged water was added to the reaction solution after the reaction, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, about 2000 ml of solvent was removed by an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the residual liquid. , About 2000 ml of solvent was removed by ultrafiltration. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous dispersion of polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) having a solid content concentration of 1.2% by mass.

(Example 1)
To 25 g (solid content 0.3 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 10 g of propylene glycol monomethyl ether, 29.2 g of methanol, 29.2 g of ion-exchanged water, and 5.0 g of ethylene glycol were added. , 1.6 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04, SiO ₂ equivalent solid content concentration 28.8% by mass) was added as a binder component, and the mixture was stirred at room temperature for 24 hours. Then, 95 mg of 4-hydroxypyridine was added as a hydroxypyridine compound, and the mixture was stirred at room temperature for 1 hour to obtain a conductive polymer dispersion.
Next, the obtained conductive polymer dispersion was applied to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60) using a bar coater (wet film thickness 30 μm) to form a coating film. The coating film was dried by heating at a drying temperature of 120 ° C. for 10 minutes to remove the dispersion medium to obtain a conductive film.

(Example 2)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that 4-hydroxypyridine was changed to 3-hydroxypyridine. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 3)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that 4-hydroxypyridine was changed to 2,4-dihydroxypyridine. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 4)
To 25 g (solid content 0.3 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 10 g of propylene glycol monomethyl ether, 25 g of methanol, 16.7 g of ion-exchanged water, and 20 g of dimethyl sulfoxide were added as binder components. 3.3 g of a water-dispersed polyester resin (manufactured by Takamatsu Oil & Fat Co., Ltd., propylene glycol A6451G, solid content concentration 30% by mass) was added, and the mixture was stirred at room temperature for 2 hours. Then, 139 mg of 2-hydroxynicotinic acid was added as a hydroxypyridine compound, and the mixture was stirred at room temperature for 1 hour to obtain a conductive polymer dispersion. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 5)
To 25 g (solid content 0.3 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 10 g of propylene glycol monomethyl ether, 40 g of ethanol, 16 g of ion-exchanged water, and 5.0 g of propylene glycol were added as binder components. 4.0 g of an aqueous dispersion polyester resin (manufactured by GOO CHEMICAL CO., LTD., RZ-105, solid content concentration 25% by mass) was added, and the mixture was stirred at room temperature for 2 hours. Then, 123 mg of 2,6-dimethyl-4-hydroxypyridine was added as a hydroxypyridine compound, and the mixture was stirred at room temperature for 1 hour to obtain a conductive polymer dispersion. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 6)
Conductivity in the same manner as in Example 1 except that ethylene glycol was changed to 1,3-propanediol, tetraethoxysilane was changed to 5.0 g, and propylene glycol monomethyl ether was changed to 7.0 g. A polymer dispersion was obtained. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 7)
To 25 g (solid content 0.3 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 5 g of propylene glycol monomethyl ether, 22 g of methanol, 40 g of ion-exchanged water, and 5 g of ethylene glycol were added and dispersed in water as a binder component. 3.3 g of a polyester resin (manufactured by Takamatsu Oil & Fat Co., Ltd., pesresin A6451G, solid content concentration 30% by mass) was added, and the mixture was stirred at room temperature for 2 hours. Then, 380 mg of 4-hydroxypyridine was added as a hydroxypyridine compound, 63 mg of bis (4-hydroxyphenyl) sulfone was further added as a phenolic antioxidant, and the mixture was stirred at room temperature for 1 hour to obtain a conductive polymer dispersion. .. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 8)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that ethylene glycol was changed to dimethyl sulfoxide and 63 mg of bis (4-hydroxyphenyl) sulfone was added as a phenolic antioxidant. Using the obtained conductive polymer dispersion, a conductive film was obtained in the same manner as in Example 1.

(Example 9)
To 40 g (solid content 0.48 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 5.0 g of propylene glycol monomethyl ether, 24 g of methanol, 15 g of ion-exchanged water, and 9.0 g of ethylene glycol were added, and a binder was added. Tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04, SiO ₂ equivalent solid content concentration 28.8% by mass) and methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-13, SiO ₂ equivalent solid content) 2.0 g (concentration: 33.7% by mass) was added, and the mixture was stirred at room temperature for 24 hours. Then, 95 mg of 4-hydroxypyridine was added as a hydroxypyridine compound, 60 mg of bis (4-hydroxyphenyl) sulfide was further added as a phenolic antioxidant, and the mixture was stirred at room temperature for 1 hour to obtain a conductive polymer dispersion. ..
Next, the obtained conductive polymer dispersion was applied to non-alkali glass (Eagle XG 75 mm × 75 mm × 0.7 mm manufactured by Corning) using a spin coater (MS-B100 manufactured by Mikasa, rotation speed 700 rpm). Then, a coating film was formed. The coating film was heated and dried at a drying temperature of 120 ° C. for 30 minutes to obtain conductive glass.

(Example 10)
To 40 g (solid content 0.48 g) of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 5.0 g of propylene glycol monomethyl ether, 28 g of methanol, 15 g of ion-exchanged water, and 9.0 g of ethylene glycol were added, and a binder was added. Tetraethoxysilane (KBE-04, SiO ₂ equivalent solid content concentration 28.8% by mass) and 3-glycidoxypropyltrimethoxysilane (KBM-403, SiO2 manufactured by Shin-Etsu Chemical Co., Ltd.) as components. ₍₂₎ Converted solid content concentration (25.4% by mass) (0.3 g) was added, and the mixture was stirred at room temperature for 24 hours. Then, 190 mg of 4-hydroxypyridine was added as a hydroxypyridine compound, 63 mg of bis (4-hydroxyphenyl) sulfone was further added as a phenolic antioxidant, and the mixture was stirred at room temperature for 1 hour to obtain a conductive polymer dispersion. .. Using the obtained conductive polymer dispersion, conductive glass was obtained in the same manner as in Example 9.

(Comparative Example 1)
A conductive film was obtained in the same manner as in Example 1 except that the hydroxypyridine compound was not added.

(Comparative Example 2)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxypyridine was changed to pyridine.

(Comparative Example 3)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxypyridine was changed to imidazole.

(Comparative Example 4)
A conductive film was obtained in the same manner as in Example 7 except that the hydroxypyridine compound was not added.

(Comparative Example 5)
Conductive glass was obtained in the same manner as in Example 9 except that the hydroxypyridine compound was not added.

(Comparative Example 6)
A conductive polymer dispersion was obtained in the same manner as in Example 9 except that 190 mg of methyl gallate was added as a phenolic antioxidant without adding a hydroxypyridine compound, and a conductive glass was obtained in the same manner as in Example 9. Got

<Evaluation>
The results of the following evaluation items are shown in Table 1.

[Measurement of surface resistance value]
For the conductive laminate of each example, the surface resistance value of the conductive layer was measured using a resistivity meter (Loresta manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under the condition of an applied voltage of 10 V.

[Measurement of haze]
The haze of the conductive glass of Examples 9 to 10 and Comparative Examples 5 to 6 was measured using a haze meter (NDH500 manufactured by Nippon Denshoku Co., Ltd.).

[Evaluation of durability]
For the conductive laminate of each example, the surface of the conductive layer is exposed to the surface resistance value (initial surface resistance value) measured within 1 hour after production and the high temperature and high humidity conditions (temperature 85 ° C. and humidity 85%). The surface resistance value (surface resistance value after high temperature and high humidity exposure) after being left in the state of being left for 500 hours was measured. The rate of change in surface resistance (surface resistance after exposure / initial surface resistance) was used as an index of durability. The closer the value of the rate of change of the surface resistance value is to 1, the higher the durability.

[Evaluation of light resistance]
For the conductive laminate of each example, the surface resistance value (initial surface resistance value) measured within 1 hour after production and a xenon light resistance tester (Ci4000 manufactured by DJK Co., Ltd., 6500 W water-cooled xenon arc lamp) were used. The surface resistance value (surface resistance value after xenon exposure) after being left for 100 hours with the surface of the conductive layer exposed was measured. The rate of change of the surface resistance value (surface resistance value after exposure / initial surface resistance value) was used as an index of light resistance. The closer the value of the rate of change of the surface resistance value is to 1, the higher the light resistance.

[Evaluation of haze]
For the conductive glasses of Examples 9 to 10 and Comparative Examples 5 to 6, the haze before and after the durability evaluation was measured, and the increase value of the haze (haze after exposure-initial haze) was evaluated. The smaller the increase value of the haze, the less the bleed-out of additives and the like, and the better the stability.

<Result>
The conductive layer of the conductive laminate formed from the conductive polymer dispersions of Examples 1 to 10 containing the hydroxypyridine compound (1) is excellent in durability, light resistance, and adhesiveness to a substrate. Was there. In addition, there was little bleed-out of the hydroxypyridine compound (1) and additives such as antioxidants in a high-temperature and high-humidity environment.
The conductive layer of the conductive laminate formed from the conductive polymer dispersions of Comparative Examples 1 to 6 containing no hydroxypyridine compound (1) has a good initial surface resistance value, but has good durability and light resistance. It was inferior. In addition, there were many bleed-outs of additives such as antioxidants in a high-temperature and high-humidity environment.

Claims (8)

A conductive polymer dispersion liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a hydroxypyridine compound represented by the following formula (1), and a dispersion medium.

[In the formula (1), R ¹ is a hydroxyl group, R ² is a carboxyl group or an alkyl group having 1 to 4 carbon atoms, m is an integer of 1 to 3, and n is an integer of 0 to 2. .. ] The hydroxypyridine compound is 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dihydroxypyridine, 2,3-dihydroxypyridine, 2,6-dimethyl-4-hydroxypyridine, 2,4-. Select from the group consisting of dihydroxy-6-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxyisonicotinic acid, 2-hydroxynicotinic acid, 6-hydroxynicotinic acid, and 3-hydroxy-2-pyridinecarboxylic acid. The conductive polymer dispersion liquid according to claim 1, which comprises at least one of the above-mentioned. The conductive polymer dispersion according to claim 1 or 2, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The conductive polymer dispersion according to any one of claims 1 to 3, wherein the polyanion is polystyrene sulfonic acid. The conductive polymer dispersion according to any one of claims 1 to 4, further containing a binder component. The conductive polymer dispersion according to claim 5, wherein the binder component contains at least one selected from the group consisting of a thermoplastic resin, a curable monomer, a curable oligomer, and silica. A conductive laminate comprising a base material and a conductive layer formed on at least one surface of the base material and composed of a cured layer of the conductive polymer dispersion liquid according to any one of claims 1 to 6. body. A method for producing a conductive laminate, which comprises applying the conductive polymer dispersion liquid according to any one of claims 1 to 6 to at least one surface of a base material.