JP7523372B2 - Conductive polymer dispersion, conductive laminate and method for producing same - Google Patents

Description

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

One technique for manufacturing electronic devices is to form a conductive layer on the surface of a resin substrate. π-conjugated conductive polymers have been attracting attention as materials for forming conductive layers because of their excellent conductivity and transparency. In addition, a release layer containing silicone may be further laminated on the surface of the conductive layer. Such a conductive release film is disclosed in Patent Document 1.

JP 2020-204009 A

The conductive polymer dispersion of Patent Document 1 contains a polyolefin resin, and therefore has particularly excellent adhesion to polyolefin substrates. Polyolefins have excellent processability, which has the advantage of allowing them to be used in a variety of applications. On the other hand, polyesters, such as PET, are often crystalline and have excellent thermal expansion and contraction properties and mechanical properties. For this reason, a conductive layer with improved adhesion to polyester substrates is required. In addition, when a release layer containing silicone is further laminated on the surface of the conductive layer, the conductive layer is required to have both high adhesion to polyester substrates and high adhesion to the laminated release layer.

The present invention provides a conductive polymer dispersion capable of forming a conductive layer having excellent adhesion to both the substrate and the release layer in a conductive laminate having a substrate/conductive layer/release layer laminated therein, and a conductive laminate and a method for producing the same.

[1] A conductive polymer dispersion liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and a dispersion medium.
[2] The conductive polymer dispersion according to [1], wherein the dispersion medium contains water, and the content of the water per 1 part by mass of the conductive composite is 40 parts by mass or more.
[3] The conductive polymer dispersion liquid according to [1] or [2], wherein the number of carbon atoms of a repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less.
[4] The conductive polymer dispersion liquid according to any one of [1] to [3], wherein the polyester resin has one or more groups selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxyl group.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein a content ratio represented by (the alkoxysilyl group-containing acrylic resin/the polyester resin) is 80/20 to 20/80 based on the mass of the solid content.
[6] The conductive polymer dispersion according to any one of [1] to [5], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene) or the polyanion is polystyrenesulfonic acid.
[7] A conductive laminate comprising a substrate and a conductive layer formed on at least a part of a surface of the substrate, the conductive layer being a cured product of the conductive polymer dispersion according to any one of [1] to [6].
[8] The conductive laminate according to [7], wherein the substrate is a PET film.
[9] The conductive laminate according to [7] or [8], wherein a release layer containing a silicone compound is further laminated on a surface of the conductive layer.
[10] A method for producing a conductive laminate, comprising: applying the conductive polymer dispersion according to any one of [1] to [6] to at least a part of a surface of a substrate to form a conductive layer.

According to the present invention, in a conductive laminate in which a substrate/conductive layer/release layer are laminated in this order, a conductive layer that has excellent adhesion to both the substrate and the release layer can be formed.

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 the numerical ranges indicated with "~" are considered to be included in the numerical range.

≪Conductive polymer dispersion liquid≫
A first aspect of the present invention is a conductive polymer dispersion liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and a dispersion medium. It is a liquid.

[Conductive composite]
The conductive complex contained in the conductive polymer dispersion of this embodiment contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive complex is doped into the π-conjugated conductive polymer to form a conductive complex having electrical conductivity.
In the polyanion, only a part of the anionic groups is doped into the π-conjugated conductive polymer, and there are excess anionic groups that are not involved in the doping. Since 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, polyphenylenevinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophenevinylene-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-dodecyloxythiophene), 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, thereby improving 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 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 (e.g., 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 in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized.
Among these polyanions, polymers having a sulfo group are preferred, and polystyrene sulfonic acid is more preferred, since they can provide higher electrical conductivity.
The polyanions may be used alone or in combination of two or more kinds.
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 an average molecular weight based on mass measured by gel filtration chromatography and calculated in terms of pullulan.

The content of the polyanion in the conductive complex is preferably in the range of 1 to 1000 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 the π-conjugated conductive polymer. If the content of the polyanion is equal to or greater than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, and the conductivity becomes higher. On the other hand, if the content of the polyanion is equal to or less than the upper limit, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

The content of the conductive complex contained in the conductive polymer dispersion of this embodiment is preferably 0.01 mass % or more and 5 mass % or less, more preferably 0.1 mass % or more and 2 mass % or less, and even more preferably 0.2 mass % or more and 1.0 mass % or less, relative to the total mass of the conductive polymer dispersion.
When the content is at least as high as the lower limit of the above range, the conductivity of the conductive layer formed by coating the conductive polymer dispersion can be further improved.
When it 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.

[Alkoxysilyl Group-Containing Acrylic Resin]
The alkoxysilyl group-containing acrylic resin is a homopolymer of a (meth)acrylic acid ester having an alkoxysilyl group, or a copolymer with another radically polymerizable monomer that is copolymerizable therewith.
Here, the term "(meth)acrylic" means "acrylic or methacrylic".

The (meth)acrylic acid ester having an alkoxysilyl group is preferably one represented by the following formula (Y).
(R ₁₁ ) ₃ -Si-R ₁₂ -OC(=O)-C(-R ₁₃ )=CH ₂ ...(Y)
In the formula, the three R ₁₁ are each independently an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and at least one of the three R ₁₁ is the above alkoxy group. In the formula, R ₁₂ is an alkylene group having 1 to 6 carbon atoms or a single bond, and R ₁₃ is a hydrogen atom or a methyl group. In the formula, (R ₁₁ ) ₃ -Si-R ₁₂ - corresponds to an alkoxysilyl group.

Specific examples of (meth)acrylic acid esters having an alkoxysilyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.
The above-mentioned monomer having an alkoxysilyl group constituting the repeating unit of the alkoxysilyl group-containing acrylic resin may be of only one type, or of two or more types.

In the alkoxysilyl group-containing acrylic resin, the repeating unit (monomer unit) having an alkoxysilyl group preferably has 6 or more and 20 or less carbon atoms, more preferably 7 or more and 17 or less carbon atoms, and even more preferably 8 or more and 14 or less carbon atoms.
When the content is within the above range, the self-crosslinking property with the polyester resin described above is enhanced, and the adhesiveness of the conductive layer formed using the conductive polymer dispersion of this embodiment to the substrate and the adhesiveness to the release layer are further improved.

In the alkoxysilyl group-containing acrylic resin, the content of the repeating unit (monomer unit) having the alkoxysilyl group is preferably 10% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and even more preferably 80% by mass or more and 100% by mass or less, based on the total mass of the monomer having the alkoxysilyl group and other radically polymerizable monomers copolymerizable with this monomer. Note that this percentage of 100% by mass means that it is a homopolymer of the monomer having an alkoxysilyl group.

Examples of the other radical polymerizable monomers include vinyl esters, unsaturated carboxylic acid esters, unsaturated carboxylic acid amides, unsaturated nitriles, unsaturated carboxylic acids, allyl compounds, nitrogen-containing vinyl monomers, hydrocarbon vinyl monomers, and vinyl silane compounds. One or more of these may be used as copolymerizable monomers.

(Production method)
The method for producing the alkoxysilyl group-containing acrylic resin is not particularly limited, and it can be produced, for example, by emulsion polymerization.
When emulsion polymerization is applied, for example, 10 to 1000 parts by mass of ion-exchanged water, 1 to 10 parts by mass of a polymerization initiator, and 1 to 20 parts by mass of a surfactant are added to a reaction tank. On the other hand, 10 to 1000 parts by mass of ion-exchanged water and 1 to 20 parts by mass of a surfactant are added to a dropping tank, and 100 parts by mass of a monomer constituting an alkoxysilyl group-containing acrylic resin are added to prepare an emulsion, and then this emulsion is added dropwise to the reaction tank to carry out emulsion radical polymerization. The reaction temperature depends on the reactivity of the monomer used, but is preferably 60 to 100° C., and the reaction time is preferably 4 to 10 hours.

As the surfactant used in the emulsion polymerization, one or more of anionic surfactants, nonionic reactive surfactants, and non-reactive surfactants can be used. It is preferable to use anionic surfactants.

Polymerization initiators used in emulsion polymerization include general radical polymerization initiators, such as water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, oil-soluble peroxides such as benzoyl peroxide and t-butyl hydroperoxide, and azo compounds such as azobisisobutyronitrile.

The alkoxysilyl group-containing acrylic resin obtained by emulsion polymerization may be added to a dispersion medium such as water to form a dispersion. If the solids concentration becomes high, it becomes difficult to obtain a uniform dispersion, so the mass of the solids (non-volatile components) of the alkoxysilyl group-containing acrylic resin is preferably 30 mass% or less relative to the total mass of the dispersion.

The content of the alkoxysilyl group-containing acrylic resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50,000 parts by mass or less, more preferably 100 parts by mass or more and 10,000 parts by mass or less, and even more preferably 200 parts by mass or more and 1,000 parts by mass or less, relative to 100 parts by mass of the conductive composite.
When the content is equal to or greater than the above lower limit, the adhesion of the conductive layer to the substrate and the release layer is further improved, and when the content is equal to or less than the above upper limit, a decrease in conductivity due to a decrease in the content of the conductive complex can be prevented.

[Polyester resin]
The polyester resin contained in the conductive polymer dispersion of this embodiment is a resin having an ester bond formed by polycondensation of a polyvalent carboxylic acid and a polyalcohol. The polyester resin used in this embodiment preferably has an acid group from the viewpoint of improving water dispersibility. The acid group may form a salt. In addition, the polyester resin used in this embodiment is preferably a saturated polyester resin that does not contain a reactive double bond from the viewpoint of improving the weather resistance of the conductive layer.

An example of a polyester resin having an acid group is a polyester resin (hereinafter referred to as “polyester resin (1)”) which is a polycondensation product of a dicarboxylic acid component and a diglycol component and has an alkali metal salt of an acid group (such as a sulfo group, a carboxy group, or a phosphate group).
This polyester resin (1) has a high polarity and therefore has excellent water dispersibility, and can be stably dispersed in water without the use of an emulsifier or stabilizer.

Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and orthophthalic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
The dicarboxylic acids may be used alone or in combination of two or more.
The dicarboxylic acid component preferably contains a dicarboxylic acid having an alkali metal sulfonate type substituent (—SO ³⁻ X ⁺ , (X ⁺ is an alkali metal ion)) in which the sulfo group is neutralized with an alkali metal.

A dicarboxylic acid having an alkali metal sulfonate type substituent is a compound in which the sulfo group in a dicarboxylic acid having a sulfo group is converted into an alkali metal salt.
Examples of the dicarboxylic acid having a sulfo group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and derivatives thereof, etc. Examples of the alkali metal include sodium and potassium.
As the dicarboxylic acid having an alkali metal sulfonate type substituent, the sodium salt of 5-sulfoisophthalic acid and its derivatives are preferred.

As the dicarboxylic acid component other than the dicarboxylic acid having an alkali metal sulfonate type substituent, aromatic dicarboxylic acids are preferred, and terephthalic acid and isophthalic acid are more preferred. The aromatic nucleus of aromatic dicarboxylic acids has a high affinity with hydrophobic plastics and is excellent in hydrolysis resistance.

The content of the dicarboxylic acid having an alkali metal sulfonate type substituent in the total dicarboxylic acid component is preferably from 5 mol % to 30 mol %, and more preferably from 10 mol % to 20 mol %.
When the content is within the above range, crosslinking of the self-crosslinking resin in the conductive layer becomes appropriate, and the adhesion of the conductive layer to the substrate and the release layer is further improved.

Examples of the diglycol component forming the polyester resin (1) include diethylene glycol, aliphatic glycols having from 2 to 8 carbon atoms, and alicyclic glycols having from 6 to 12 carbon atoms. Specific examples of the aliphatic glycols having from 2 to 8 carbon atoms, and alicyclic glycols having from 6 to 12 carbon atoms, include ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, neopentyl glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,6-hexanediol, p-xylylene glycol, and triethylene glycol. One type of diglycol component may be used alone, or two or more types may be used in combination.

The number average molecular weight of the polyester resin (1) is preferably from 2,000 to 30,000, and more preferably from 10,000 to 27,000. The number average molecular weight of the polyester resin (1) is a numerical molecular weight determined based on a calibration curve of elution time vs. molecular weight obtained in advance by measuring the elution time using gel permeation chromatography (GPC) and using polystyrene standard substances with known molecular weights.
When the number average molecular weight of the polyester resin (1) is equal to or more than the lower limit, the adhesion of the conductive layer is increased, and when it is equal to or less than the upper limit, the water dispersibility of the polyester resin (1) is increased.

The method for producing polyester resin (1) is not particularly limited, and examples thereof include a method in which a dicarboxylic acid component and a diglycol component are subjected to an esterification or transesterification reaction at 130° C. or more and 200° C. or less, and then a polycondensation reaction is carried out under reduced pressure at 200° C. or more and 250° C. or less. Examples of reaction catalysts used in the method for producing polyester resin (1) include metal acetates such as zinc acetate and manganese acetate, metal oxides such as antimony oxide and germanium oxide, and titanium compounds.
The polyester resin (1) thus obtained may be added to water to form an aqueous dispersion. When the solid content (non-volatile component) concentration of the aqueous dispersion of the polyester resin (1) is high, it becomes difficult to obtain a uniform dispersion, so the solid content concentration is preferably 30% by mass or less.

The content of the polyester resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50,000 parts by mass or less, more preferably 100 parts by mass or more and 10,000 parts by mass or less, and even more preferably 200 parts by mass or more and 1,000 parts by mass or less, relative to 100 parts by mass of the conductive composite.
When the content is equal to or greater than the above lower limit, the adhesion of the conductive layer to the substrate and the release layer is further improved, and when the content is equal to or less than the above upper limit, a decrease in conductivity due to a decrease in the content of the conductive complex can be prevented.

[Self-crosslinking resin]
The alkoxysilyl group-containing acrylic resin is combined with the polyester resin (1) and contained in the conductive complex, and self-crosslinks during the formation of the conductive layer to become a self-crosslinking resin. The excess anion groups of the polyanion of the conductive complex that are not involved in the doping can function as a catalyst to promote the self-crosslinking.

In order to obtain a suitable degree of self-crosslinking, the content ratio represented by (alkoxysilyl group-containing acrylic resin/polyester resin (1)) is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and even more preferably 40/60 to 60/40, based on the mass of the solid content.
When the content is within the above range, the mechanical strength of the conductive layer formed is further improved, and the adhesiveness of the conductive layer to the substrate and the release layer is further improved.

[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; and dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol.
Examples of the ether solvent include diethyl ether, dimethyl ether, and propylene glycol dialkyl ether.
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, 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.
An example of a solvent not classified into the above categories is dimethyl sulfoxide.
The organic solvents may be used alone or in combination of two or more kinds.

From the viewpoint of enhancing the dispersibility of the conductive composite, the dispersion medium of the conductive polymer dispersion of this embodiment is preferably water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent.
Here, a water-soluble organic solvent is an organic solvent that dissolves in an amount of 1 g or more in 100 g of water at 20°C, and a water-insoluble organic solvent is an organic solvent that dissolves in an amount of less than 1 g in 100 g of water at 20°C.
The water-soluble organic solvent is preferably one or more selected from alcohol-based solvents.
From the viewpoint of further enhancing the dispersibility of the conductive composite, the alcohol-based solvent is preferably contained in combination with water.

Since the conductive complex 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 dispersion medium in the conductive polymer dispersion of this embodiment is, for example, preferably from 10 mass % to 50 mass %, and more preferably from 20 mass % to 40 mass %.
Furthermore, the dispersion medium of the conductive polymer dispersion of this embodiment contains water, and the content of water per 1 part by mass of the conductive composite is preferably 40 parts by mass or more, more preferably 50 parts by mass or more and 1,000 parts by mass or less, even more preferably 80 parts by mass or more and 800 parts by mass or less, and particularly preferably 90 parts by mass or more and 400 parts by mass or less.
As the dispersion medium other than water, the above-mentioned water-soluble organic solvents are preferable.

The content ratio of the water-soluble organic solvent to the total mass of the dispersion medium of the conductive polymer dispersion liquid of this embodiment is, for example, preferably 50% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and even more preferably 70% by mass or more and 80% by mass or less.

[Other additives]
The conductive polymer dispersion may contain other additives.
The additives are not particularly limited as long as the effects of the present invention can be obtained. For example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbing agents, etc. can be used.
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 inorganic conductive agent include metal ions, conductive carbon, etc. Metal ions can be generated by dissolving a metal salt in water.
The antifoaming agent includes silicone resin, polydimethylsiloxane, silicone oil, and the like.
The coupling agent may be 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, 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 appropriately determined depending on the type of additive, but can be, for example, in the range of 0.001 parts by mass to 10 parts by mass per 100 parts by mass of the conductive composite.

<Method of producing conductive polymer dispersion>
An example of a method for producing the conductive polymer dispersion of this embodiment is a method in which a dispersion medium, the above-mentioned polyester resin, and an alkoxysilyl group-containing acrylic resin are added to an aqueous dispersion of a conductive complex.
The aqueous dispersion of the conductive complex may be obtained by chemically oxidizing and polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous solution of a polyanion by a known method, or a commercially available product may be used.
In the prepared conductive polymer dispersion, the conductive complex functions as a catalyst that promotes self-crosslinking of the self-crosslinking resin. Therefore, it is preferable to prepare a self-crosslinking resin by previously mixing the polyester resin and the alkoxysilyl group-containing acrylic resin, and to mix the conductive complex with the self-crosslinking resin immediately before coating to obtain the conductive polymer dispersion.

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

[Conductive layer]
The conductive layer may be formed over the entire surface of any surface of the substrate, or over a portion of the entire surface. In the conductive film, it is preferable that a conductive layer of substantially uniform thickness is formed over substantially the entire surface of one surface or the other surface of the film substrate. When a conductive layer is formed only over a portion 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 the conductive layer may be provided on the same surface and the conductive layer may be not provided on the same surface and may be roughly divided.

The average thickness of the conductive layer is, for example, preferably from 10 nm to 100 μm, more preferably from 20 nm to 50 μm, and even more preferably from 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 adhesion of the conductive layer to the substrate and the release layer described below is further improved.

(Action and Effect)
The conductive layer contains the self-crosslinking resin in addition to the conductive complex, and therefore the adhesion to the substrate and the release layer described below is improved. Although the details of this mechanism are not yet clear, the lack of either the alkoxysilyl group-containing acrylic resin or the polyester resin does not improve the adhesion (see the comparative example described below), so it is considered that the physicochemical interaction occurring in the coexistence of these contributes to the improvement of the adhesion of the conductive layer. In addition, as shown in the comparative example described below, it is not enough for the alkoxysilyl group-containing acrylic resin and the polyester resin to simply coexist, and the coexistence of the conductive complex that acts as a catalyst for the self-crosslinking of these is necessary to improve the adhesion.

[Base material]
The substrate may be a substrate made of an insulating material or a substrate made of a conductive material. The shape of the substrate is not particularly limited, and examples thereof include a shape mainly having a flat surface, such as a film or a substrate.
Examples of insulating materials include glass, synthetic resin, and ceramics.
The conductive material may be a metal, a conductive metal oxide, carbon, or the like.

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

The synthetic resin for the film substrate may be either amorphous or crystalline.
The film substrate may be either unstretched or stretched.
The film substrate may be subjected to a surface treatment such as a corona discharge treatment, a plasma treatment, or a flame treatment in order to further improve the adhesion of the conductive layer.

The average thickness of the film substrate is preferably 5 μm to 500 μm, more preferably 20 μm to 200 μm. If the average thickness of the film substrate is equal to or more than the lower limit, the film is less likely to break, and if the average thickness is equal to or less than the upper limit, the film can have sufficient flexibility.
The average thickness of the film substrate is determined by measuring the thickness at 10 randomly selected points and averaging the measured values.

(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. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease, so among the above glass substrates, an alkali-free glass is preferred. Here, the alkali-free glass refers to a glass composition in which the content of the alkali component is 0.1 mass% or less with respect to the total mass of the glass composition.

The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, and more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is equal to or more than the lower limit, the glass substrate is less likely to break, and if the average thickness is equal to or less than the upper limit, the conductive laminate can be made thinner.
The average thickness of the glass substrate is determined by measuring the thickness at 10 randomly selected points and averaging the measured values.

[Release layer]
In the conductive laminate of this embodiment, a release layer containing a silicone compound may be further laminated on the surface of the conductive layer. A conductive film having a release layer laminated on the surface of the conductive layer is sometimes called a conductive release film.

The release layer may have a similar structure to that of a release layer provided in a known release film. The silicone-based compound contained in the release layer contributes to the exertion of releasability (easy peelability).

As the silicone-based compound, a silicone-based compound contained in a known mold release agent can be used. Here, silicone is a polymer collectively called organopolysiloxane, which has a main chain (silicone skeleton) in which an organic group (e.g., an alkyl group or a phenyl group) is bonded to a siloxane bond. As the organopolysiloxane, polydimethylsiloxane (PDMS) is preferable, and polydimethylsiloxane having a reactive functional group or a non-reactive functional group in part is also preferable. In addition, acrylic resins and alkyd resins having organopolysiloxane in the side chain can also be used as the silicone-based compound.

The silicone compound contained in the release layer is preferably a cured product of a curable silicone, since it exhibits stable releasability and excellent film-forming properties during production.
The curable silicone may be either an addition curable silicone or a condensation curable silicone. When the curable silicone reacts, it forms a three-dimensional crosslinked structure and cures.
The addition curing silicone may be a linear polymer having a siloxane bond, and may include a polydimethylsiloxane having vinyl groups at both ends of the linear chain, and a hydrogen silane. A platinum-based curing catalyst may be used to accelerate the curing.
Specific examples of addition curing silicones include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, and X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.).
The addition curing type silicone is preferably dissolved or dispersed in an organic solvent.

The content of the silicone-based compound in the release layer of this embodiment can be, for example, 20% by mass or more and 100% by mass or less, and is preferably in the range of 80% by mass or more and 100% by mass or less, based on the total mass of the release layer.
The release layer of this embodiment may contain binder components other than silicone-based compounds, as well as known additives such as adhesion improvers and antistatic agents, as long as the adhesion of the conductive layer to the release layer is not impaired and the releasability of the release layer is not impaired.

The average thickness of the release layer is, for example, preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and even more preferably 30 nm or more and 500 nm or less.
When the average thickness of the release layer is equal to or greater than the lower limit, higher releasability can be exhibited, and when it is equal to or less than the upper limit, adhesion to the conductive layer is further improved.

The release layer of the conductive release film of this embodiment may cover the entire surface of the conductive layer, or may cover only a portion of the conductive layer, with the remainder of the conductive layer being exposed on the surface.

(Action and Effect)
Since the conductive layer on which the release layer is laminated contains an alkoxysilyl group-containing acrylic resin and a polyester resin, the conductive layer can exhibit sufficient adhesion (adhesiveness) even to the release layer containing a silicone compound. As a result, the release layer can exhibit excellent releasability with respect to an object attached to the release layer without peeling off from the conductive laminate, which is the main body.
The release layer is basically an insulating layer, and therefore the surface covered with the release layer and not exposed to the conductive layer does not exhibit conductivity basically, but the presence of the conductive layer inside makes it possible to prevent the conductive laminate itself from being charged.

<Method for manufacturing conductive laminate>
A third aspect of the present invention is a method for producing a conductive laminate, the method comprising: applying the conductive polymer dispersion of the first aspect to at least a part of a surface of a substrate to form a conductive layer. The conductive laminate of the second aspect can be produced by the production method of this aspect.

Methods for applying the conductive polymer dispersion to any surface of a substrate include, for example, 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 applied to the substrate is not particularly limited, but in consideration of uniform and even application and the electrical 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.

It is preferable to remove the dispersion medium by drying the coating film made of the conductive polymer dispersion applied onto the substrate. In this drying treatment, the self-crosslinking of the self-crosslinking resin is promoted, the mechanical strength of the formed conductive layer is increased, and the adhesion to the substrate and the release layer is improved.
Methods for drying the coating film include heat drying, vacuum drying, etc. Examples of heat drying that can be used include hot air heating and infrared heating.
When applying heat drying, 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.

When the coating film dries, the self-crosslinking resin contained in the coating film self-crosslinks, and the coating film hardens to form a conductive layer (conductive film), resulting in a conductive laminate.

There are no particular limitations on the method for laminating the release layer on the surface of the conductive layer, and an example of such a method is to coat the surface of the conductive layer with a release agent composition containing a silicone compound and dry the resulting coating to obtain a release layer.

The release agent composition contains a silicone-based compound. The description of the silicone-based compound is the same as that of the second embodiment, and therefore will not be repeated here.
In addition to the silicone-based compound, the release agent composition may contain additives such as an organic solvent, a curing catalyst, a binder component other than the silicone-based compound, an adhesion improver, and an antistatic agent, if necessary. When an addition curing type silicone is used as the silicone-based compound, it is preferable to add at least one of toluene and methyl ethyl ketone as the organic solvent. The mixing ratio and mixing method of each material contained in the release agent composition are determined by conventional methods.
The method of applying the release agent composition to the conductive layer and the method of drying and curing the applied coating film can be the same as the application method and drying/curing method used when forming the conductive layer.
By the above-mentioned method, the conductive laminate according to the present invention can be produced.

(Production Example 1)
206 g of sodium styrenesulfonate was dissolved in 1000 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.
1000ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution to obtain a polystyrene sulfonic acid-containing solution. Next, about 1000ml of the solvent was removed from the polystyrene sulfonic acid-containing solution by ultrafiltration, 2000ml of ion-exchanged water was added to the remaining liquid, and about 2000ml of the solvent was removed by ultrafiltration to wash the polystyrene sulfonic acid with water. This water washing operation was repeated three times.
Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2)
A solution of 0.5 g of 3,4-ethylenedioxythiophene and 1.5 g of polystyrene sulfonic acid dissolved in 15.0 g of ion-exchanged water was mixed at 20° C. Next, 89.5 g of ion-exchanged water was added.
The resulting mixed solution was kept at 20° C., and while stirring, a solution of 0.03 g of ferric sulfate dissolved in 4.97 g of ion-exchanged water and a solution of 1.1 g of ammonium persulfate dissolved in 8.9 g of ion-exchanged water were slowly added, and the resulting reaction solution was stirred for 24 hours to cause a reaction.
By the above reaction, a PEDOT-PSS aqueous dispersion was obtained, which contains a conductive complex (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, which are π-conjugated conductive polymers, and water, which is a dispersion medium.
To this dispersion, 13.2 g of Duolite C255LFH (a cation exchange resin manufactured by Sumika Chemtex Corporation) and 13.2 g of Duolite A368S (anion exchange resin manufactured by Sumika Chemtex Corporation) were added, and the ion exchange resin was removed by filtration to obtain an aqueous dispersion of PEDOT-PSS (solid content 1.3% by mass) from which the oxidant and the catalyst had been removed.

(Production Example 3) Preparation of polyester resin A 854 g of dimethyl terephthalate, 355 g of 5-sodium sulfoisophthalic acid, 186 g of ethylene glycol, 742 g of diethylene glycol, and 1 g of zinc acetate as a reaction catalyst were charged into a four-neck flask equipped with a distillation tube, a nitrogen inlet tube, a thermometer, and a stirrer. The temperature in the flask was then raised from 130°C to 170°C over 2 hours to carry out an ester exchange reaction, after which 730 g of isophthalic acid and 1 g of antimony trioxide were added, and the temperature was raised from 170°C to 200°C over 2 hours to carry out an esterification reaction. Next, the temperature was gradually raised and the pressure was reduced, and finally the reaction temperature was set to 250°C and the degree of vacuum was set to 5 mmHg or less to carry out a polycondensation reaction for 1 hour. After that, the mixture was cooled and ion-exchanged water was added under normal pressure to obtain a polyester resin A having a non-volatile content (solid content) of 25% by mass.

(Production Example 4) Preparation of Alkoxysilyl Group-Containing Acrylic Resin B 18 g of ion-exchanged water and 3 g of Eleminol RS-3000 (manufactured by Sanyo Chemical Industries, Ltd., anionic surfactant, active ingredient 50% by mass) were placed in a beaker. Then, 40 g of 3-methacryloxypropyltrimethoxysilane was added while stirring the contents of the beaker to prepare a monomer emulsion.
Next, 37.5 g of ion-exchanged water, 1 g of surfactant (Eleminol RS-3000), and 0.5 g of potassium persulfate were charged into a four-bottom flask equipped with a condenser, a monomer dropping funnel, a thermometer, and a stirrer. After that, the flask was purged with nitrogen while stirring, heating was started, and the monomer emulsion was dropped at 75°C over 4 hours. The reaction was allowed to proceed by maintaining the liquid temperature at 75 to 85°C even after the dropwise addition was completed, and the mixture was cooled 4 hours after the dropwise addition was completed. After cooling, ion-exchanged water was further added to obtain an alkoxysilyl group-containing acrylic resin B having a non-volatile content (solid content) of 25% by mass.

(Production Example 5) Preparation of Alkoxysilyl Group-Containing Acrylic Resin C Alkoxysilyl group-containing acrylic resin C having a nonvolatile content of 25 mass % was obtained in the same manner as in Production Example 4, except that 40 g of 3-acryloxypropyltrimethoxysilane was used instead of 40 g of 3-methacryloxypropyltrimethoxysilane.

(Production Example 6) Preparation of Alkoxysilyl Group-Containing Acrylic Resin D Alkoxysilyl group-containing acrylic resin D having a nonvolatile content of 25 mass % was obtained in the same manner as in Production Example 4, except that 40 g of 3-methacryloxypropyltriethoxysilane was used instead of 40 g of 3-methacryloxypropyltriethoxysilane.

(Production Example 7) Preparation of Alkoxysilyl Group-Containing Acrylic Resin E An alkoxysilyl group-containing acrylic resin D having a nonvolatile content of 25 mass% was obtained in the same manner as in Production Example 4, except that 40 g of 3-acryloxypropyltriethoxysilane was used instead of 40 g of 3-methacryloxypropyltrimethoxysilane.

(Production Example 8) Preparation of self-crosslinking resin F The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solid content mass ratio of 50/50 to obtain a self-crosslinking resin F having a non-volatile content (solid content) of 25 mass%.

(Production Example 9) Preparation of self-crosslinking resin G The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin C obtained in Production Example 5 were blended in a solid content mass ratio of 50/50 to obtain a self-crosslinking resin G having a non-volatile content (solid content) of 25 mass%.

(Production Example 10) Preparation of self-crosslinking resin H The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin D obtained in Production Example 6 were blended in a solid content mass ratio of 50/50 to obtain a self-crosslinking resin H having a non-volatile content (solid content) of 25 mass%.

(Production Example 11) Preparation of self-crosslinking resin I The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin E obtained in Production Example 7 were blended in a solid content mass ratio of 50/50 to obtain a self-crosslinking resin I having a non-volatile content (solid content) of 25 mass%.

(Production Example 12) Preparation of self-crosslinking resin J The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solid content mass ratio of 25/75 to obtain a self-crosslinking resin J having a non-volatile content (solid content) of 25 mass%.

(Production Example 13) Preparation of self-crosslinking resin K The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solid content mass ratio of 75/25 to obtain a self-crosslinking resin K having a non-volatile content (solid content) of 25 mass%.

(Production Example 14) Preparation of self-crosslinking resin L The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solid content mass ratio of 10/90 to obtain a self-crosslinking resin L having a non-volatile content (solid content) of 25 mass%.

(Production Example 15) Preparation of Self-Crosslinking Resin M The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solid content mass ratio of 90/10 to obtain a self-crosslinking resin M having a non-volatile content (solid content) of 25 mass%.

Example 1
20 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 70 g of methanol, and 10 g of the self-crosslinking resin F were mixed together to obtain a conductive polymer dispersion.
The conductive polymer dispersion was applied to a PET film using a #4 bar coater and dried for 1 minute at 120° C. to obtain a conductive film. The surface resistance of this conductive film was measured and the results are shown in Table 1.
Next, 1.5 g of addition-curing silicone KS-3703T (manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30 mass%, toluene solution), 25.5 g of toluene, 63 g of methyl ethyl ketone, and 0.03 g of platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed to obtain a coating material.
The above-mentioned material was applied to the surface of the conductive layer of the above-mentioned conductive film using a #8 bar coater and dried for 2 minutes at 150° C. to obtain a conductive release film in which a release layer was laminated on the conductive layer. The results of measuring the surface resistance, adhesion, and peel strength of this conductive release film are shown in Table 1.

Example 2
A conductive film and a conductive release film were produced in the same manner as in Example 1, except that the amount of self-crosslinking resin F was changed from 10 g to 5 g and the amount of methanol was changed to 75 g, and the respective measurements were carried out. The results are shown in Table 1.

Example 3
A conductive film and a conductive release film were produced in the same manner as in Example 1, except that the amount of self-crosslinking resin F was changed from 10 g to 15 g and the amount of methanol was changed to 65 g, and the respective measurements were carried out. The results are shown in Table 1.

Example 4
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the self-crosslinking resin G. The results are shown in Table 1.

Example 5
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the self-crosslinking resin H. The results are shown in Table 1.

Example 6
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the self-crosslinking resin I. The results are shown in Table 1.

(Example 7)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the self-crosslinking resin J. The results are shown in Table 1.

(Example 8)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the self-crosslinking resin K. The results are shown in Table 1.

Example 9
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F was changed to 10 g of the self-crosslinking resin L in Example 1. The results are shown in Table 1.

Example 10
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the self-crosslinking resin M. The results are shown in Table 1.

(Example 11)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that KS-3703T in Example 1 was replaced with KS-847T (Shin-Etsu Chemical Co., Ltd., solid content 30 mass%, toluene solution), which is an addition curing type silicone. The results are shown in Table 1.

(Comparative Example 1)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the polyester resin A. The results are shown in Table 1.

(Comparative Example 2)
A conductive film and a conductive release film were prepared and each measurement was carried out in the same manner as in Example 1, except that the 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the alkoxysilyl group-containing acrylic resin B. The results are shown in Table 1.

(Comparative Example 3)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the alkoxysilyl group-containing acrylic resin C. The results are shown in Table 1.

(Comparative Example 4)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the alkoxysilyl group-containing acrylic resin D. The results are shown in Table 1.

(Comparative Example 5)
A conductive film and a conductive release film were produced and each measurement was carried out in the same manner as in Example 1, except that the 10 g of the self-crosslinking resin F in Example 1 was changed to 10 g of the alkoxysilyl group-containing acrylic resin E. The results are shown in Table 1.

(Comparative Example 6)
Except for changing the amount of PEDOT-PSS aqueous dispersion (20 g) to water (20 g) in Example 1, a film sample was prepared and measured in the same manner as in the preparation of the conductive film and conductive release film in Example 1. The results are shown in Table 1.

<Evaluation>
[Surface resistance value]
For the conductive film of each example, the surface resistance value of the conductive layer was measured using a resistivity meter (Hiresta, manufactured by Nitto Seiko Analytech Co., Ltd.) under the condition of an applied voltage of 10 V. The measurement results of the surface resistance value are shown in Table 1.
For each example of conductive release film, a probe was placed on the release layer, and the surface resistance with the release layer interposed was measured using a resistivity meter (Hiresta, manufactured by Nitto Seiko Analytech Co., Ltd.) under the condition of an applied voltage of 10 V. The measurement results of the surface resistance are shown in Table 1. In the table, "Ω/□" means ohms per square. "1.0E+07" means "1.0×10 ⁷ ," and the same applies to the others. "OVER" indicates a high value exceeding the measurement limit.

[Peeling force]
For the conductive release film of each example, the peel force was measured by the following method, and the releasability of the release layer was evaluated.
A 25 mm wide polyester adhesive tape (Nitto Denko Corporation, No. 31B) was attached to the surface of the release layer of the conductive release film, and a load of 1976 Pa was applied from above the adhesive tape and pressure treatment was performed at 25°C for 20 hours. Next, in accordance with JIS Z0237, the adhesive tape attached to the release layer was peeled off at an angle of 180° (peel speed 0.3 m/min) using a tensile tester to measure the peel force (unit: N). The measurement results are shown in Table 1. The smaller the peel force, the higher the releasability of the release layer.

[Adhesion]
For each conductive release film, the surface of the release layer was rubbed with a finger 10 times, and the degree of damage to the release layer was evaluated according to the following criteria. The results are shown in Table 1.
(Rating 1): The release layer completely falls off within the fifth finger rub, and the easy peeling property is lost. In other words, the adhesion between the release layer and the conductive layer is poor.
(Evaluation 2): The release layer remains until the fifth finger rub, but thereafter, by the tenth finger rub, the release layer falls off completely and the easy peeling property is lost. In other words, the adhesion between the release layer and the conductive layer is poor.
(Evaluation 3): The release layer did not fall off within 10 finger rubs, but the color of the release layer changed significantly and the ease of peeling decreased. In other words, the adhesion between the release layer and the conductive layer was normal.
(Evaluation 4): The release layer did not fall off within 10 finger rubs, and a small change was observed in the color of the release layer, but the peelability was hardly decreased. In other words, the adhesion between the release layer and the conductive layer was excellent.
(Evaluation 5): The release layer did not fall off within 10 finger rubs, the color of the release layer did not change, and the peelability did not decrease. In other words, the adhesion between the release layer and the conductive layer was particularly excellent.
In the above five-level evaluation criteria, the ease of peeling (releasability) is based on the results of testing the ease of peeling off an adhesive tape applied to a surface rubbed with a finger. The discoloration of the release layer represents the degree of peeling at the interface between the release layer and the conductive layer. If this interface is partially peeled off, the interface will rise when peeling off the adhesive tape applied to the surface of the release layer, and the peelability will decrease.

Since the conductive polymer dispersions of Examples 1 to 11 contain an alkoxysilyl group-containing acrylic resin and a polyester resin, the conductive layer formed from the coating film has good conductivity and excellent adhesion to the substrate and release layer.
The conductive polymer dispersion of Comparative Example 1 does not contain an alkoxysilyl group-containing acrylic resin, and therefore the conductive layer formed has poor adhesion to the substrate and the release layer.
The conductive polymer dispersions of Comparative Examples 2 to 5 did not contain a polyester resin, and therefore the conductive layers formed were inferior in adhesion to the substrate and the release layer.
The conductive polymer dispersion of Comparative Example 6 does not contain a conductive complex, and therefore the conductive layer formed has poor conductivity and poor adhesion to the substrate and release layer. The reason for the poor adhesion in Comparative Example 6 is believed to be that the self-crosslinking of the self-crosslinking resin was not promoted by the catalytic action of the conductive complex.
Examples 9 and 10 are comparative examples.

Claims (8)

A conductive polymer dispersion liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and a dispersion medium,
the content ratio represented by (the alkoxysilyl group-containing acrylic resin/the polyester resin) is 80/20 to 20/80 based on the mass of the solid content,
A conductive polymer dispersion liquid used for forming a conductive layer of the conductive laminate described below .
<Conductive laminate>
The conductive laminate has a substrate, a conductive layer formed on at least a portion of the surface of the substrate, and a release layer containing a silicone-based compound further laminated on the surface of the conductive layer, and the conductive layer is a cured product of the conductive polymer dispersion. The conductive polymer dispersion according to claim 1, wherein the dispersion medium contains water, and the content of the water per 1 part by mass of the conductive composite is 40 parts by mass or more. The conductive polymer dispersion according to claim 1 or 2, wherein the number of carbon atoms of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less. The conductive polymer dispersion according to any one of claims 1 to 3, wherein the polyester resin has one or more groups selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxyl group. The conductive polymer dispersion according to any one of claims 1 to 4 , wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrenesulfonic acid. The present invention comprises a substrate, a conductive layer formed on at least a portion of the surface of the substrate , and a release layer including a silicone-based compound further laminated on the surface of the conductive layer,
A conductive laminate, wherein the conductive layer is a cured product of the conductive polymer dispersion according to any one of claims 1 to 5 . The conductive laminate according to claim 6 , wherein the substrate is a PET film. A method for producing a conductive laminate, comprising: a step of applying the conductive polymer dispersion according to any one of claims 1 to 5 to at least a part of a surface of a substrate to form a conductive layer; and a step of laminating a release layer containing a silicone-based compound on a surface of the conductive layer.