JP7777976B2 - Conductive polymer dispersion, conductive laminate and method for producing the same - Google Patents

Description

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

Conventionally, antistatic properties have been required for glass for liquid crystal displays. Patent Document 1 discloses display glass that has a functional side (side A) on which TFT elements are formed and a non-functional back side (side B). The document describes that an organic film for antistatic purposes is formed on side B, and that this organic film may contain specific silane compounds or amine compounds. The document also describes that, because display glass is sometimes washed with water during the manufacturing process, it is preferable that side B have a water contact angle of 25 degrees or more.

Patent No. 6734842

However, although the surface resistance of the display glass disclosed in Patent Document 1 is reduced by the presence of the organic film, it is still only 1×10 ¹² to 1×10 ¹⁷ Ω/sq., which is not necessarily sufficient. In addition, there is also the problem that the compound that constitutes the organic film and imparts antistatic properties is easily affected by humidity.

The present invention provides a conductive polymer dispersion that can impart sufficient antistatic properties to a glass substrate, has excellent durability and abrasion resistance when exposed to high temperatures and humidity, and is capable of forming a conductive layer with a surface water contact angle of 30 degrees or more. It also provides a method for producing a conductive laminate using the conductive polymer dispersion. It also provides a conductive laminate having a conductive layer formed by curing a coating film of the conductive polymer dispersion.

[1] A conductive polymer dispersion for use in a method for producing a conductive laminate, the method comprising applying a conductive polymer dispersion to the surface of a glass substrate, drying and curing the coating, and forming a conductive layer having a surface with a contact angle with water of 30 degrees or more, the conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an alkoxysilane compound, and a dispersion medium.
[2] The conductive polymer dispersion according to [1], wherein the content of each of the transition metal, the metal oxide, the carbon nanotube, and the inorganic acid is less than 0.0001 parts by mass per part by mass of the conductive composite.
[3] The conductive polymer dispersion according to [1] or [2], wherein the contact angle is 40 to 70 degrees.
[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the conductive polymer dispersion contains one or more tetraalkoxysilanes and one or more trialkoxysilanes.
[5] The conductive polymer dispersion according to [4], wherein, when the total amount of substance of the one or more tetraalkoxysilanes contained in 100 g of the conductive polymer dispersion is [A] mmol and the total amount of substance of the one or more trialkoxysilanes contained in 100 g of the conductive polymer dispersion is [B] mmol, the molar ratio [B]/[A] is 0.10 to 0.30 and the value of [A]+[B] is 8.0 to 15.0 mmol.
[6] The conductive polymer dispersion liquid according to [4] or [5], wherein the tetraalkoxysilane includes at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
[7] The conductive polymer dispersion liquid according to any one of [4] to [6], wherein the trialkoxysilane includes at least one selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxysilane.
[8] The conductive polymer dispersion liquid according to any one of [1] to [7], further containing an acetylene-based surfactant.
[9] The conductive polymer dispersion liquid according to any one of [1] to [8], further containing a diol compound.
[10] The conductive polymer dispersion according to any one of [1] to [9], wherein the dispersion medium contains water, and the content of water relative to the total mass of the conductive polymer dispersion is 40 mass % or more.
[11] The conductive polymer dispersion according to any one of [1] to [9], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrenesulfonic acid.
[12] A conductive laminate comprising a glass substrate and a conductive layer formed on at least one surface of the glass substrate, the conductive layer being made of a cured product of the conductive polymer dispersion according to any one of [1] to [11], wherein the contact angle of the surface of the conductive layer with water is 30 degrees or more.
[13] The conductive laminate according to [12], wherein the surface resistance of the conductive layer is 100 to 5,000 Ω/sq.
[14] A method for producing a conductive laminate, comprising: applying the conductive polymer dispersion according to any one of [1] to [11] to a surface of a glass substrate, drying and curing the coating, and forming a conductive layer having a surface with a contact angle to water of 30 degrees or more.

By applying the conductive polymer dispersion of the present invention to a glass substrate, it is possible to impart sufficient antistatic properties to the glass substrate, and to form a conductive layer that is excellent in durability and abrasion resistance against exposure to high temperatures and high humidity and has a surface water contact angle of 30 degrees or more.
According to the method for producing a conductive laminate of the present invention, a conductive laminate having a conductive layer formed on the surface of a glass substrate can be easily obtained, and the presence of the conductive layer imparts sufficient antistatic properties to the glass substrate. In addition, the conductive layer has excellent durability and abrasion resistance against exposure to high temperatures and high humidity, and the surface has a water contact angle of 30 degrees or more.
The conductive laminate of the present invention exhibits excellent antistatic properties, is excellent in durability and abrasion resistance when exposed to high temperatures and humidity, and has a conductive layer whose surface has a water contact angle of 30 degrees or more.

This invention is believed to contribute to SDG Goal 12, "Responsible Consumption and Production."

In this specification and claims, the lower and upper limits of numerical ranges indicated with "~" are considered to be included in the numerical range.

<Water contact angle>
In the present invention, the contact angle of the surface of the conductive layer formed on the glass substrate with water (water contact angle) is a value measured in accordance with the sessile drop method of JIS R3257 (1999).

<<Conductive polymer dispersion>>
A first aspect of the present invention is a conductive polymer dispersion for use in a method for producing a conductive laminate, the method comprising applying the conductive polymer dispersion to the surface of a glass substrate, drying and curing the coating, and forming a conductive layer having a surface with a contact angle with water of 30 degrees or more.
The conductive polymer dispersion of this embodiment can be used in the production method of the third embodiment described below, and can be used as a material for the conductive laminate of the second embodiment described below.

The conductive polymer dispersion of this embodiment contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, an alkoxysilane compound, and a dispersion medium.
The conductive complex in the conductive polymer dispersion may be in a dispersed state or a dissolved state, and in this specification, no distinction is made between the dispersed state and the dissolved state unless otherwise specified.

[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 dopes the π-conjugated conductive polymer to form a conductive composite having conductivity.
In polyanions, only some of the anionic groups are doped into the π-conjugated conductive polymer, and there are excess anionic groups that are not involved in the doping. Because the excess anionic groups are hydrophilic groups, 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, and examples thereof include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, 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 preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

Examples of polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), and poly(3-iodothiophene). thiophene), 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-dodecyl oxythiophene), 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-di dodecyloxythiophene), 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), and poly(3-methyl-4-carboxybutylthiophene).
Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), 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), and poly(3-methyl-4-hexyloxypyrrole).
Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid).
Among these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred because of its excellent conductivity, transparency, and heat resistance.
The conductive composite may contain one type of π-conjugated conductive polymer, or two or more types of polymers.

(Polyanion)
A polyanion is a polymer having two or more monomer units each having an anionic group in the molecule. The anionic group of the polyanion functions as a dopant for a π-conjugated conductive polymer, improving 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 polymers having a sulfo group, such as polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid; and polymers having a carboxy group, such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprene carboxylic acid. The polyanion may be a homopolymer formed by polymerizing a single monomer, or a copolymer formed by polymerizing two or more monomers.
Among these polyanions, polymers having sulfo groups are preferred, and polystyrene sulfonic acid is more preferred, since they can further increase the conductivity.
The polyanions may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably from 20,000 to 1,000,000, and more preferably from 100,000 to 500,000. The mass average molecular weight is the average molecular weight based on mass measured using gel filtration chromatography and calculated as pullulan.

The content of polyanion in the conductive composite is preferably in the range of 1 to 1,000 parts by mass, more preferably 10 to 700 parts by mass, and even more preferably 100 to 500 parts by mass, per 100 parts by mass of π-conjugated conductive polymer. If the content of polyanion is above the 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 content of polyanion is below the upper limit, a sufficient amount of π-conjugated conductive polymer can be contained, ensuring sufficient conductivity.

The content of the conductive complex relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.01 mass % or more and 2 mass % or less, more preferably 0.1 mass % or more and 1 mass % or less, and even more preferably 0.3 mass % or more and 0.8 mass % or less.
When the content is at least as large as 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 the content is equal to or less than the upper limit of the above range, the dispersibility of the conductive complex in the conductive polymer dispersion can be improved, and a uniform conductive layer can be formed.

[Alkoxysilane Compound]
The one or more alkoxysilane compounds contained in the conductive polymer dispersion of this embodiment are compounds having 1 to 4 alkyl groups (alkoxy groups) bonded to a silicon atom via an oxygen atom. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may be linear or branched.
In addition to the alkoxy group, 1 to 3 alkyl groups may be directly bonded to the silicon atom. The number of carbon atoms in the alkyl groups directly bonded to the silicon atom is preferably 1 to 6, and more preferably 1 to 3. The alkyl groups may be linear or branched.

The conductive polymer dispersion of this embodiment preferably contains one or more tetraalkoxysilanes and one or more trialkoxysilanes.
The number of carbon atoms in the alkyl groups constituting each alkoxy group of the tetraalkoxysilane is preferably 1 to 6, and more preferably 1 to 3. The alkyl groups may be linear or branched.
The number of carbon atoms in the alkyl groups constituting each alkoxy group of the trialkoxysilane is preferably 1 to 6, and more preferably 1 to 3. The alkyl groups may be linear or branched.
In addition to the alkoxy group, a hydrogen atom or an alkyl group is preferably bonded to the silicon atom of the trialkoxysilane. The number of carbon atoms in the alkyl group directly bonded to the silicon atom is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may be linear or branched.

When the total amount of substance of the one or more tetraalkoxysilanes contained in 100 g of the conductive polymer dispersion of this embodiment is [A] mmol and the total amount of substance of the one or more trialkoxysilanes is [B] mmol, the molar ratio [B]/[A] is preferably 0.10 to 0.30, more preferably 0.13 to 0.25, and even more preferably 0.17 to 0.22.
Furthermore, within the above-mentioned preferred range of molar ratio, the value of [A] + [B] per 100 g is preferably 8.0 to 15.0 mmol, more preferably 10.0 to 15.0 mmol, and even more preferably 12.0 to 15.0 mmol.
When the molar ratio and sum are within the above-mentioned preferred ranges, the glass substrate can be imparted with excellent antistatic properties, and the durability and abrasion resistance to exposure to high temperatures and high humidity can be further improved, and a conductive layer having a surface water contact angle of 30 degrees or more can be more easily formed.

The tetraalkoxysilane preferably includes at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
The trialkoxysilane preferably includes at least one selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxysilane.
The above-described suitable alkoxysilane compound can impart excellent antistatic properties to a glass substrate, and can more easily form a conductive layer having even better durability and abrasion resistance against exposure to high temperatures and high humidity, and a surface water contact angle of 30 degrees or more.

[Acetylenic surfactants]
The conductive polymer dispersion of this embodiment preferably contains one or more acetylene-based surfactants. The inclusion of an acetylene-based surfactant enhances wettability to the surface of the glass substrate, enabling the formation of a conductive layer with a uniform thickness. As a result, excellent antistatic properties can be imparted, and a conductive layer with even better durability and abrasion resistance against exposure to high temperatures and high humidity and a surface water contact angle of 30 degrees or more can be more easily formed.

Acetylenic surfactants are nonionic compounds that have at least one triple bond between carbon atoms in the molecule. Suitable acetylene surfactants include wetting agents manufactured by Nissin Chemical Industry Co., Ltd., such as Dynol 604, Dynol 607, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104PA, Surfynol 104S, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol SE, Surfynol SE-F, Surfynol PSA-336, and Surfynol 2502.

The number of carbon atoms in the molecule of the acetylene surfactant is preferably 11 to 100, more preferably 12 to 70, even more preferably 13 to 50, and most preferably 14 to 40. When the number of carbon atoms is within these preferred ranges, the wettability is further improved.
The acetylene surfactant preferably has a hydroxyl group or an oxygen atom forming an ether bond in the molecule, which further improves wettability.

The content of the acetylene surfactant relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.0001 mass % or more and 0.5 mass % or less, more preferably 0.001 mass % or more and 0.1 mass % or less, and even more preferably 0.005 mass % or more and 0.05 mass % or less.
The preferred content of the compound (I) above further enhances wettability to the surface of the glass substrate, making it easier to form a conductive layer of uniform thickness, which results in excellent antistatic properties, even more excellent durability and abrasion resistance against exposure to high temperatures and humidity, and makes it easier to form a conductive layer with a water contact angle of 30 degrees or more on the surface.

[Diol compound]
The conductive polymer dispersion of this embodiment preferably contains one or more diol compounds, where the diol compounds are compounds other than acetylene-based surfactants.
By including a diol compound, it is possible to impart excellent antistatic properties to the glass substrate, to further improve durability and abrasion resistance against exposure to high temperatures and high humidity, and to more easily form a conductive layer having a water contact angle of 30 degrees or more on the surface.

A diol compound is an organic compound containing two hydroxy groups. Suitable diol compounds include, for example, ethylene glycol, diethylene glycol, propylene glycol, and butanediol (1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol).

The diol compound may be an unsaturated diol compound having one or more double or triple bonds between carbon atoms in the molecule. The inclusion of an unsaturated diol compound can further enhance the antistatic properties (conductivity) of the conductive layer to be formed. Suitable unsaturated diol compounds include, for example, cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, 2-butyne-1,4-diol, 2,4-hexadiyne-1,6-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 2,5-dimethyl-3-hexyne-2,5-diol.
The unsaturated diol compound preferably has 10 or less carbon atoms in the molecule.

The content of diol compounds other than unsaturated diol compounds (saturated diol compounds having no double or triple bonds between carbon atoms in the molecule) relative to the total mass of the conductive polymer dispersion of this embodiment 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 even more preferably 3% by mass or more and 6% by mass or less.
When the content is in the above-mentioned preferred range, it is possible to impart excellent antistatic properties to the glass substrate, to provide even more excellent durability and abrasion resistance against exposure to high temperatures and high humidity, and to more easily form a conductive layer having a water contact angle of 30 degrees or more on the surface.

The content of the unsaturated diol compound relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass or less, and even more preferably 1% by mass or more and 3% by mass or less.
When the content is in the above-mentioned preferred range, it is possible to impart excellent antistatic properties to the glass substrate, to provide even more excellent durability and abrasion resistance against exposure to high temperatures and high humidity, and to more easily form a conductive layer having a water contact angle of 30 degrees or more on the surface.

[Dispersion medium]
Examples of the dispersion medium contained in the conductive polymer dispersion of this embodiment include water, an organic solvent, and a mixture of water and an organic solvent.

Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.
Examples of alcohol-based solvents include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether and dimethyl ether.
Examples of ketone solvents include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol.
Examples of the ester solvent include ethyl acetate, propyl acetate, and butyl acetate.
Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene.
The organic solvents may be used alone or in combination of two or more.

Since the conductive composite has high dispersibility in water, the dispersion medium of the conductive polymer dispersion of this embodiment is preferably an aqueous dispersion medium containing water.
The content of water relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 40% by mass or more, more preferably 50% by mass to 90% by mass, and even more preferably 60% by mass to 80% by mass.
When the content is in the above-mentioned preferred range, it is possible to impart excellent antistatic properties to the glass substrate, to provide even more excellent durability and abrasion resistance against exposure to high temperatures and high humidity, and to more easily form a conductive layer having a water contact angle of 30 degrees or more on the surface.

The content of the monohydric alcohol relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 10% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less.
When the content is in the above-mentioned preferred range, it is possible to impart excellent antistatic properties to the glass substrate, to provide even more excellent durability and abrasion resistance against exposure to high temperatures and high humidity, and to more easily form a conductive layer having a water contact angle of 30 degrees or more on the surface.

[Other additives]
The conductive polymer dispersion of this embodiment may contain other additives.
The additives are not particularly limited as long as they can achieve the effects of the present invention, and for example, surfactants, antifoaming agents, antioxidants, ultraviolet absorbers, etc. can be used.
However, the additives are other than the above-mentioned π-conjugated conductive polymers, polyanions, alkoxysilane compounds, acetylene-based surfactants, diol compounds, and dispersion media.
The surfactant may be a nonionic, anionic, or cationic surfactant, with the nonionic surfactant being preferred from the standpoint of storage stability. A polymer surfactant such as polyvinylpyrrolidone may also be added.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and sugars.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.

When the conductive polymer dispersion contains the additive, the content ratio is determined appropriately depending on the type of additive, but can be, for example, in the range of 0.001 parts by mass to 50 parts by mass per 100 parts by mass of the conductive composite.

The conductive layer formed from the conductive polymer dispersion of this embodiment is provided with conductivity by the conductive complex, so it does not need to contain other conductive substances. From this perspective, the conductive polymer dispersion of this embodiment preferably does not contain transition metals (Groups 3 to 11 elements), metal oxides, carbon nanotubes, or inorganic acids. If these are contained as unavoidable impurities, the content of each is preferably less than 0.0001 parts by mass per part by mass of the conductive complex.

<Method of manufacturing conductive polymer dispersion>
Examples of a method for producing the conductive polymer dispersion of this embodiment include a method in which each component, such as an alkoxysilane compound, a diol compound, a monohydric alcohol, an acetylene-based surfactant, and a stabilizer, is added sequentially to an aqueous dispersion of a conductive composite.

The aqueous dispersion of the conductive complex may be obtained by chemically oxidatively polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous solution of a polyanion, or a commercially available product may be used.

<Conductive laminate>
A second aspect of the present invention is a conductive laminate comprising a glass substrate and a conductive layer formed on at least one surface of the glass substrate and comprising a cured product of the conductive polymer dispersion of the first aspect.

[Conductive layer]
The conductive layer may be formed on the entire surface of the substrate or on a part of the surface. When the conductive layer is formed on only a part of the surface of the substrate, the conductive layer may be, for example, a fine conductive pattern such as a circuit or an electrode, or may be roughly divided into a region where the conductive layer is provided and a region where the conductive layer is not provided on the same surface.

The average thickness of the conductive layer is, for example, preferably 10 nm to 100 μm, more preferably 20 nm to 50 μm, and even more preferably 30 nm to 30 μm.
When the average thickness of the conductive layer is equal to or greater than the lower limit, high conductivity can be exhibited, and when the average thickness is equal to or less than the upper limit, the adhesiveness of the conductive layer to the substrate is further improved.

(water contact angle)
The water contact angle of the surface of the conductive layer of the conductive laminate of this embodiment is 30 degrees or more. A larger water contact angle is preferable because it facilitates the process of removing water after washing the conductive layer surface with water. From the viewpoint of removing water from the conductive layer surface in this manner, the water contact angle of this embodiment may be, for example, 40 to 70 degrees, 45 to 65 degrees, or 50 to 60 degrees.

(Surface resistance value)
The surface resistance value of the conductive layer of the conductive laminate of this embodiment can be, for example, 100 to 5,000 Ω/sq., preferably 100 to 3,000 Ω/sq., more preferably 100 to 2,000 Ω/sq., and even more preferably 100 to 1,000 Ω/sq.

When the conductive layer of the conductive laminate of this embodiment is subjected to the abrasion resistance evaluation method described below, the rate of change in surface resistivity can be, for example, 1.00 to 1.20. Of these, 1.00 to 1.15 is preferred, 1.00 to 1.10 is more preferred, and 1.00 to 1.05 is even more preferred.

When the conductive layer of the conductive laminate of this embodiment is subjected to the durability evaluation method described below, the rate of change in surface resistivity can be, for example, 1.00 to 1.50. Of these, 1.00 to 1.40 is preferred, 1.00 to 1.30 is more preferred, and 1.00 to 1.20 is even more preferred.

When the conductive layer of the conductive laminate of this embodiment is subjected to the durability and abrasion resistance evaluation method described below, the rate of change in surface resistivity can be, for example, 1.00 to 2.00. Of these, 1.00 to 1.80 is preferred, 1.00 to 1.60 is more preferred, and 1.00 to 1.40 is even more preferred.

[Glass substrate]
Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, and a quartz glass substrate. Since the conductivity of the conductive layer tends to decrease when the substrate contains an alkali component, alkali-free glass is preferred among the glass substrates. Here, alkali-free glass refers to a glass composition having an alkali component content of 0.1 mass % or less relative to the total mass of the glass composition.

When the glass substrate is a glass plate, the average thickness thereof is not particularly limited and may be, for example, from 0.1 mm to 10 mm.
The average thickness of the glass plate is determined by measuring the thickness at 10 randomly selected points and averaging the measured values.

<Method for manufacturing conductive laminate>
A third aspect of the present invention is a method for producing a conductive laminate, comprising applying the conductive polymer dispersion of the first aspect to a surface of a glass substrate, and drying and curing the coating to form a conductive layer having a surface with a contact angle with water of 30 degrees or more.
The manufacturing method of this embodiment can manufacture the conductive laminate of the second embodiment.

Examples of methods for coating (applying) the conductive polymer dispersion onto any surface of a substrate include methods using a coater such as a gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, or screen coater; methods using a sprayer such as an air spray, airless spray, or rotor dampening; and immersion methods such as dipping.

The amount of the conductive polymer dispersion to be applied to the substrate is not particularly limited, but in consideration of uniform and even application, conductivity, and film strength, the amount is preferably in the range of 0.01 g/ ^m2 or more and 10.0 g/ ^m2 or less in terms of solid content.

The conductive layer can be formed by drying the coating film made of the conductive polymer dispersion applied onto the substrate to remove at least a portion of the dispersion medium and curing the coating film.
Methods for drying the coating film include heat drying, vacuum drying, etc. Heat drying can be performed using, for example, hot air heating or infrared heating.
When heat drying is applied, the heating temperature is appropriately set depending on the dispersion medium used, but is usually within the range of 50° C. to 200° C. Here, the heating temperature is the set temperature of the drying device. A suitable drying time within the above heating temperature range is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 15 minutes.

(Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1,000 ml of ion-exchanged water, and while stirring at 80°C, 1.14 g of an oxidizing agent solution of ammonium persulfate previously dissolved in 10 ml of water was added dropwise over 20 minutes, and the solution was stirred for 12 hours.
To the resulting sodium polystyrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and approximately 1000 ml of the resulting polystyrene sulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the remaining solution, and approximately 2000 ml of the solution was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This water-washing procedure was repeated three times.
Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid (PSS).

(Production Example 2) Production of PEDOT-PSS aqueous dispersion 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 were dissolved in 2000 ml of ion-exchanged water and mixed at 20°C.
The resulting mixed solution was kept at 20°C and, while stirring, 29.64 g of ammonium persulfate and 8.0 g of an oxidation catalyst solution of ferric sulfate dissolved in 200 ml of ion-exchanged water were slowly added, followed by stirring for 3 hours to allow the reaction to proceed.
To the resulting reaction solution, 2000 ml of ion-exchanged water was added, and about 2000 ml of the solution was removed by ultrafiltration. This procedure was repeated three times.
Next, 200 ml of sulfuric acid diluted to 10% by mass and 2,000 ml of ion-exchanged water were added to the resulting solution, and about 2,000 ml of the solution was removed by ultrafiltration. 2,000 ml of ion-exchanged water was added to the solution, and about 2,000 ml of the solution was removed by ultrafiltration. This procedure was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and approximately 2000 ml of the solution was removed by ultrafiltration. This procedure was repeated five times to obtain a polystyrene sulfonate-doped poly(3,4-ethylenedioxythiophene) aqueous dispersion (PEDOT-PSS aqueous dispersion) with a solids concentration of 1.2% by mass.

Example 1
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.00 g (9.6 mmol, Shin-Etsu Chemical Co., Ltd. KBE-04) of [A] tetraethoxysilane, 0.30 g (1.7 mmol, Shin-Etsu Chemical Co., Ltd. KBE-13) of [B] methyltriethoxysilane, 5.00 g (Tokyo Chemical Industry Co., Ltd.) of ethylene glycol as a diol compound, 30.00 g of pure water and 37.64 g of methanol as dispersion media, 0.01 g of Dynol 604 (acetylene-based surfactant, Nissin Chemical Industry Co., Ltd.) as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone (Tokyo Chemical Industry Co., Ltd.) and 0.05 g of bis(4-hydroxyphenyl)sulfide (Tokyo Chemical Industry Co., Ltd.) as stabilizers were added, and the mixture was stirred and mixed at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was about 55% by mass, the molar ratio of alkoxysilane [B/A] was 0.18, and the total amount of alkoxysilane added was 11.3 mmol/100 g.

Example 2
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.40 g (11.5 mmol) of [A] tetraethoxysilane, 0.60 g (3.4 mmol) of [B] methyltriethoxysilane, 2.00 g of 2-butyne-1,4-diol (Tokyo Chemical Industry Co., Ltd.) as a diol compound, 30.00 g of pure water and 39.89 g of methanol as dispersion media, 0.01 g of Surfynol 420 (an acetylene-based surfactant, Nissin Chemical Industry Co., Ltd.) as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 55% by mass, the molar ratio of alkoxysilanes [B/A] was 0.30, and the total amount of alkoxysilanes was 14.9 mmol/100 g.

Example 3
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Preparation Example 2, 1.75 g (8.4 mmol) of [A] tetraethoxysilane, 0.22 g (1.2 mmol) of [B] methyltriethoxysilane, 5.00 g of ethylene glycol as a diol compound, 30.00 g of pure water and 37.92 g of methanol as dispersion media, 0.01 g of Dynol 604 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 55% by mass, the molar ratio of alkoxysilanes [B/A] was 0.14, and the total amount of alkoxysilanes was 9.6 mmol/100 g.

Example 4
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.20 g (10.6 mmol) of [A] tetraethoxysilane, 0.35 g (1.8 mmol) of [B] ethyltriethoxysilane, 5.00 g of propylene glycol (Tokyo Chemical Industry Co., Ltd.) as a diol compound, 30.00 g of purified water and 37.34 g of ethanol (Tokyo Chemical Industry Co., Ltd.) as dispersion media, 0.01 g of Surfynol 420 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 55% by mass, the molar ratio of alkoxysilanes [B/A] was 0.17, and the total amount of alkoxysilanes was 12.4 mmol/100 g.

Example 5
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 1.50 g (7.2 mmol) of [A] tetraethoxysilane, 0.30 g (1.6 mmol) of [B] ethyltriethoxysilane, 5.00 g of propylene glycol as a diol compound, 30.00 g of pure water and 38.09 g of ethanol as dispersion media, 0.01 g of Dynol 604 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 55% by mass, the molar ratio of alkoxysilanes [B/A] was 0.22, and the total amount of alkoxysilanes was 8.8 mmol/100 g.

Example 6
To 40 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.00 g (9.6 mmol) of [A] tetraethoxysilane, 0.40 g (2.1 mmol) of [B] ethyltriethoxysilane, 2.00 g of 2-butyne-1,4-diol as a diol compound, 30.00 g of pure water and 25.49 g of ethanol as dispersion media, 0.01 g of Dynol 604 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 70% by mass, the molar ratio of alkoxysilanes [B/A] was 0.22, and the total amount of alkoxysilanes was 11.7 mmol/100 g.

Example 7
To 40 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.40 g (11.5 mmol) of [A] tetraethoxysilane, 0.35 g (2.0 mmol) of [B] methyltriethoxysilane, 5.00 g of ethylene glycol as a diol compound, 25.00 g of pure water and 27.12 g of methanol as dispersion media, 0.01 g of Dynol 604 as a surfactant, and 0.06 g of bis(4-hydroxyphenyl)sulfone and 0.06 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 65% by mass, the molar ratio of alkoxysilanes [B/A] was 0.17, and the total amount of alkoxysilanes was 13.5 mmol/100 g.

(Example 8)
To 60 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.60 g (12.5 mmol) of [A] tetraethoxysilane, 0.42 g (2.4 mmol) of [B] methyltriethoxysilane, 2.00 g of 2-butyne-1,4-diol as a diol compound, 20.00 g of pure water and 14.85 g of methanol as dispersion media, 0.01 g of Dynol 604 as a surfactant, and 0.06 g of bis(4-hydroxyphenyl)sulfone and 0.06 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 79% by mass, the molar ratio of alkoxysilanes [B/A] was 0.19, and the total amount of alkoxysilanes was 14.9 mmol/100 g.

(Comparative Example 1)
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 2.50 g (12.0 mmol) of [A] tetraethoxysilane, 5.00 g of ethylene glycol as a diol compound, 30.00 g of pure water and 37.39 g of methanol as dispersion media, 0.01 g of Surfynol 420 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 55% by mass, the molar ratio of alkoxysilanes [B/A] was 0, and the total amount of alkoxysilanes was 12 mmol/100 g.

(Comparative Example 2)
To 25 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 4.00 g (19.2 mmol) of [A] tetraethoxysilane, 1.00 g (5.6 mmol) of [B] methyltriethoxysilane, 5.00 g of ethylene glycol as a diol compound, 30.00 g of pure water and 34.89 g of methanol as dispersion media, 0.01 g of Surfynol 420 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 55% by mass, the molar ratio of alkoxysilanes [B/A] was 0.29, and the total amount of alkoxysilanes was 25 mmol/100 g.

(Comparative Example 3)
To 46.67 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 1.00 g (4.8 mmol) of [A] tetraethoxysilane, 0.18 g (1.01 mmol) of [B] methyltriethoxysilane, 4.2 g of dimethyl sulfoxide as a dispersion medium, 21.17 g of pure water, 26.67 g of methanol, 0.01 g of Surfynol 420 as a surfactant, and 0.05 g of bis(4-hydroxyphenyl)sulfone and 0.05 g of bis(4-hydroxyphenyl)sulfide as stabilizers were added, and the mixture was stirred at room temperature for 3 days to obtain a conductive polymer dispersion. The water content of this dispersion was approximately 67% by mass, the molar ratio of alkoxysilanes [B/A] was 0.21, and the total amount of alkoxysilanes was 5.8 mmol/100 g.

<Evaluation>
The conductive polymer dispersion obtained in each example was applied to alkali-free glass (Corning Eagle XG, 75 mm x 75 mm x 0.7 mm) using a spin coater (MS-B100 manufactured by Mikasa Co., Ltd., rotation speed 700 rpm) to form a coating film. The coating film was dried by heating at a drying temperature of 120°C for 30 minutes to produce a conductive laminate.
The results for the following evaluation items are shown in Table 1.

[Surface resistance value]
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 10V.

[Water contact angle]
The water contact angle of the conductive layer was measured using a contact angle meter (Dropmaster DMs-401 manufactured by Kyowa Interface Science Co., Ltd.) in accordance with the JIS standard, 30 seconds after forming a droplet on the conductive layer surface.

[Wear resistance]
The initial surface resistance value X of the conductive laminate (before testing) and the surface resistance value Y after a nonwoven fabric was moved back and forth 10 times under a load of 200 g on the surface of the conductive layer were measured. The rate of change in surface resistance (Y/X) before and after testing was calculated to evaluate abrasion resistance. The closer the rate of change is to 1, the higher the abrasion resistance.

[Durability]
The initial surface resistance value X of the conductive laminate (before testing) and the surface resistance value Y' (surface resistance value after exposure to high temperature and high humidity) after leaving the surface of the conductive layer exposed to high temperature and high humidity conditions (temperature 85°C and humidity 85% RH) for 500 hours were measured. The rate of change in surface resistance (Y'/X) before and after testing was calculated to evaluate durability. The closer the rate of change is to 1, the higher the durability.

[Durability and abrasion resistance]
The initial surface resistance value X of the conductive laminate (before testing) and the surface resistance Y" (the surface resistance value of the conductive layer further rubbed after exposure to high temperature and high humidity) were measured after leaving the conductive layer surface exposed to high temperature and high humidity conditions (temperature 85°C and humidity 85% RH) for 500 hours and then moving a nonwoven fabric back and forth across the conductive layer surface 10 times with a load of 200 g. The rate of change in surface resistance before and after testing (Y"/X) was calculated to evaluate durability and abrasion resistance. The closer the rate of change is to 1, the higher the durability and abrasion resistance. In the table, "peeled" indicates that the conductive layer peeled off due to the rubbing treatment.

It was confirmed that the conductive layers formed on glass substrates using the conductive polymer dispersions of Examples 1 to 8 according to the present invention had excellent antistatic properties, excellent durability against exposure to high temperatures and high humidity, and excellent abrasion resistance, and that the water contact angle of the surface was 30 degrees or more.
Examples 1, 3 to 5, and 7 are comparative examples.

Claims (13)

A conductive polymer dispersion for use in a method for producing a conductive laminate, the method comprising: applying a conductive polymer dispersion to a surface of a glass substrate; drying and curing the coating; and forming a conductive layer having a surface with a contact angle to water of 30 degrees or more,
The conductive composite includes a π-conjugated conductive polymer and a polyanion, an alkoxysilane compound, a dispersion medium, and an unsaturated diol compound having one or more double bonds or triple bonds between carbon atoms in the molecule ,
The conductive polymer dispersion further contains an acetylene-based surfactant . The conductive polymer dispersion according to claim 1, wherein the content of each of the transition metal, metal oxide, carbon nanotubes, and inorganic acid is less than 0.0001 part by mass per 1 part by mass of the conductive composite. The conductive polymer dispersion according to claim 1 or 2, wherein the contact angle is 40 to 70 degrees. The conductive polymer dispersion according to any one of claims 1 to 3, wherein the conductive polymer dispersion contains one or more tetraalkoxysilanes and one or more trialkoxysilanes. When the total amount of the one or more tetraalkoxysilanes contained in 100 g of the conductive polymer dispersion is [A] mmol and the total amount of the one or more trialkoxysilanes contained in 100 g of the conductive polymer dispersion is [B] mmol,
5. The conductive polymer dispersion according to claim 4, wherein the molar ratio [B]/[A] is 0.10 to 0.30, and the value of [A]+[B] is 8.0 to 15.0 mmol. The conductive polymer dispersion according to claim 4 or 5, wherein the tetraalkoxysilane includes at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane. The conductive polymer dispersion liquid according to any one of claims 4 to 6, wherein the trialkoxysilane includes at least one selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, and propyltriethoxysilane. 8. The conductive polymer dispersion according to claim 1 , wherein a content of the unsaturated diol compound relative to a total mass of the conductive polymer dispersion is 0.5 mass % or more and 10 mass % or less. 9. The conductive polymer dispersion according to claim 1 , wherein the dispersion medium contains water, and the content of water relative to the total mass of the conductive polymer dispersion is 40 mass % or more. The conductive polymer dispersion according to any one of claims 1 to 8 , wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrenesulfonic acid. A conductive layer comprising a glass substrate and a conductive layer formed on at least one surface of the glass substrate, the conductive layer being made of a cured product of the conductive polymer dispersion according to any one of claims 1 to 10 ,
A conductive laminate, wherein the surface of the conductive layer has a contact angle with water of 30 degrees or more. 12. The conductive laminate according to claim 11 , wherein the surface resistance of the conductive layer is 100 to 5,000 Ω/sq. A method for producing a conductive laminate, comprising: applying the conductive polymer dispersion according to any one of claims 1 to 10 to a surface of a glass substrate, and drying and curing the coating to form a conductive layer having a surface with a contact angle to water of 30 degrees or more.