Conductive laminate, method for manufacturing the same, and capacitor

Abstract

To provide a conductive laminate in which a conductive layer having good conductivity and excellent adhesion is formed on a metal substrate surface, a method for manufacturing the conductive laminate, and a capacitor.SOLUTION: The conductive laminate includes a metal substrate and a conductive layer which is in close contact with at least a part of a surface of the metal substrate. The conductive layer is a cured product of a conductive polymer dispersion which contains: a conductive composite containing a π-conjugated conductive polymer and a polyanion; an alkoxysilyl group-containing acrylic resin; a polyester resin; and an aqueous dispersion medium.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a conductive laminate including a conductive layer containing a π-conjugated conductive polymer, a method for manufacturing the same, and a capacitor.

Background Art

[0002] As a technology related to the manufacture of electronic devices, a conductive layer may be formed on the surface of a resin substrate. Since the π-conjugated conductive polymer is excellent in conductivity and transparency, it has attracted attention as a material for forming a conductive layer (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Since the conductive polymer dispersion of Patent Document 1 contains a polyolefin-based resin, the adhesion to a polyolefin-based substrate is particularly excellent. On the other hand, the adhesion to the surface of a metal substrate is not always satisfactory.

[0005] The present invention provides a conductive laminate in which a conductive layer having good conductivity and excellent adhesion is formed on the surface of a metal substrate, a method for manufacturing the same, and a capacitor.

Means for Solving the Problems

[0006] [1] A conductive laminate including a metal substrate and a conductive layer in close contact with at least a part of the surface of the metal substrate, wherein the conductive layer is a cured product of a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. [2] The conductive laminate according to [1], wherein the carbon number of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less. [3] The conductive laminate according to [1] or [2], wherein the polyester resin has at least one selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxy group. [4] The conductive laminate according to any one of [1] to [3], wherein the polyanion is polystyrene sulfonic acid. [5] The conductive laminate according to any one of [1] to [4], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). [6] The conductive laminate according to any one of [1] to [5], wherein the metal substrate is formed of aluminum or tantalum. [7] A capacitor comprising the conductive laminate according to any one of [1] to [6]. [8] A method for producing a conductive laminate, comprising a step of applying a paint to at least a part of a metal substrate, drying and curing a coating film made of the paint to form a conductive layer, wherein the paint is a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. [9] The method for producing a conductive laminate according to [8], wherein the carbon number of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less.

[10] The method for producing a conductive laminate according to [8] or [9], wherein the polyester resin has at least one selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxy group. [Effect of the Invention]

[0007] The conductive layer provided in the conductive laminate of the present invention has good conductivity and excellent adhesion to the surface of the metal substrate.

[0008] The present invention is considered to contribute to SDGs Goal 12, "Responsibility for Production and Consumption."

[0009] In this specification and the claims, the lower and upper limit values of the numerical range indicated by "~" are included in the numerical range.

Brief Description of the Drawings

[0010]

Figure 1

Embodiments for Carrying Out the Invention

[0011] ≪Conductive Laminate≫ The first aspect of the present invention is a conductive laminate including a metal substrate and a conductive layer in close contact with at least a part of the surface of the metal substrate. The conductive layer included in the conductive laminate of this aspect is a cured product of a conductive polymer dispersion containing a conductive composite including a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. Hereinafter, the conductive polymer dispersion will be described.

[0012] [Conductive Composite] The conductive composite contained in the conductive polymer dispersion includes 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 the polyanion, only some of the anion groups dope the π-conjugated conductive polymer, and there are surplus anion groups that do not participate in the doping. Since the surplus anion groups are hydrophilic groups, the conductive composite has water dispersibility.

[0013] (π-Conjugated Conductive Polymer) As the π-conjugated conductive polymer, any organic polymer whose main chain is composed of a π-conjugated system may be used. 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.

[0014] 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), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxytiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxytiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-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 π-conjugated conductive polymer contained in the conductive composite may be one type or two or more types.

[0015] (Polyanion) A polyanion is a polymer having two or more monomer units having anionic groups in the molecule. The anionic groups of this polyanion function as dopants for the π-conjugated conductive polymer and improve 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 polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylate esters having a sulfo group, polymethacrylate esters having a sulfo group (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzene sulfonic acid), poly(2-acrylamido-2-methylpropane sulfonic acid), polymers having a sulfo group such as 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-methylpropane carboxylic acid), polyisoprene carboxylic acid. The polyanion may be a homopolymer obtained by polymerizing a single monomer, or may be a copolymer obtained by polymerizing two or more monomers. Among these polyanions, polymers having a sulfo group are preferred and polystyrene sulfonic acid is more preferred because the conductivity can be made higher. The polyanion may be used alone or in combination of two or more. The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is the average molecular weight on a mass basis measured by gel filtration chromatography and determined in terms of pullulan.

[0016] The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less, more preferably 10 parts by mass or more and 700 parts by mass or less, and even more preferably 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer. If the content ratio of the polyanion is equal to or higher than the lower limit value, 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 lower than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

[0017] As the content of the conductive composite contained in the conductive polymer dispersion, it is preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.10% by mass or more and 2% by mass or less, and still more preferably 0.15% by mass or more and 1.0% by mass or less, based on the total mass of the conductive polymer dispersion. When it is at least the lower limit value of the above range, the conductivity of the conductive layer formed by applying the conductive polymer dispersion can be further improved. When it is at most the upper limit value of the above range, the dispersibility of the conductive composite in the conductive polymer dispersion can be enhanced, and a uniform conductive layer can be formed.

[0018] [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 other radically polymerizable monomers copolymerizable therewith. Here, the notation "(meth)acrylic" means "acrylic or methacrylic".

[0019] As the (meth)acrylic acid ester having an alkoxysilyl group, those represented by the following formula (Y) are preferable. (R 11 )3-Si-R 12 -O-C(=O)-C(-R 13 )=CH2···(Y) In the formula, the three Rs 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 Rs 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 the alkoxysilyl group.

[0020] Specific examples of the (meth)acrylate having an alkoxysilyl group include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and the like. The monomer having an alkoxysilyl group that constitutes the repeating unit of the alkoxysilyl group-containing acrylic resin may be only one kind or two or more kinds.

[0021] In the alkoxysilyl group-containing acrylic resin, the number of carbon atoms of the repeating unit (monomer unit) having an alkoxysilyl group is preferably 6 or more and 20 or less, more preferably 7 or more and 17 or less, and even more preferably 8 or more and 14 or less. When it is in the above range, the self-crosslinkability with the above-mentioned polyester resin is enhanced, and the adhesion of the conductive layer formed using the conductive polymer dispersion of this embodiment to the substrate is further improved.

[0022] In the alkoxysilyl group-containing acrylic resin, the content ratio of the repeating unit (monomer unit) having an 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 with respect to the total mass of the monomer having an alkoxysilyl group and other radically polymerizable monomers copolymerizable with this monomer. Note that the ratio being 100% by mass means a homopolymer of the monomer having an alkoxysilyl group.

[0023] Examples of the other radically 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, or vinyl silane compounds. One or more of these can be used as copolymerizable monomers.

[0024] (Manufacturing method) The manufacturing method of the alkoxysilyl group-containing acrylic resin is not particularly limited, and for example, it can be manufactured by emulsion polymerization. When applying emulsion polymerization, 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 the monomers constituting the alkoxysilyl group-containing acrylic resin are added to prepare an emulsion. Then, this emulsion is dropped into the reaction tank and added to carry out emulsion radical polymerization. The reaction temperature depends on the reactivity of the monomers used, but is preferably 60 to 100 °C, and the reaction time is preferably 4 to 10 hours.

[0025] As the surfactant used in emulsion polymerization, one or more of an anionic surfactant, a nonionic reactive surfactant, and a non-reactive surfactant can be used. It is preferable to use an anionic surfactant.

[0026] As the polymerization initiator used in emulsion polymerization, general radical polymerizable initiators such as water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, or oil-soluble peroxides such as benzoyl peroxide and t-butyl hydroperoxide, or azo compounds such as azobisisobutyronitrile can be mentioned.

[0027] The alkoxysilyl group-containing acrylic resin obtained by emulsion polymerization may be added to a dispersion medium such as water to form a dispersion. When the solid content concentration increases, it becomes difficult to obtain a uniform dispersion. Therefore, the mass of the solid content (non-volatile component) of the alkoxysilyl group-containing acrylic resin is preferably 30% by mass or less based on the total mass of the dispersion.

[0028] The content of the alkoxysilyl group-containing acrylic resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50000 parts by mass or less, more preferably 100 parts by mass or more and 10000 parts by mass or less, and even more preferably 200 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the conductive composite. If it is equal to or higher than the above lower limit value, the adhesion of the conductive layer to the substrate is further improved, and if it is equal to or lower than the above upper limit value, it is possible to prevent a decrease in conductivity due to a decrease in the content of the conductive composite.

[0029] [Polyester resin] The polyester resin contained in the conductive polymer dispersion liquid 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 enhancing water dispersibility. The acid group may form a salt. Further, the polyester resin used in this embodiment is preferably a saturated polyester resin containing no reactive double bond from the viewpoint of enhancing the weather resistance of the conductive layer.

[0030] Examples of the polyester resin having an acid group include polyester resins (hereinafter referred to as "polyester resin (1)") which are polycondensates of a dicarboxylic acid component and a diglycol component and have an alkali metal salt of an acid group (such as a sulfo group, a carboxy group, a phosphoric acid group, etc.). Since this polyester resin (1) has a large polarity, it has excellent water dispersibility and can be stably dispersed in water without using an emulsifier or a stabilizer.

[0031] Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,5-dimethyl terephthalic 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 acid may be used alone or in combination of two or more. The dicarboxylic acid component preferably contains a dicarboxylic acid having a sulfonic acid alkali metal salt type substituent (-SO 3- X + , (X + is an alkali metal ion)) in which the sulfo group is neutralized by an alkali metal.

[0032] Dicarboxylic acids having a sulfonic acid alkali metal salt type substituent are compounds in which the sulfonic acid group in the dicarboxylic acid having a sulfonic acid group is converted to an alkali metal salt. Examples of the dicarboxylic acid having a sulfonic acid group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, or derivatives thereof. Examples of the alkali metal include sodium, potassium, and the like. As the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent, the sodium salt of 5-sulfoisophthalic acid and its derivatives are preferred.

[0033] As the dicarboxylic acid component other than the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent in the dicarboxylic acid component, aromatic dicarboxylic acids are preferred, and terephthalic acid and isophthalic acid are more preferred.

[0034] The content ratio of the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent is preferably 5 mol% or more and 30 mol% or less, more preferably 10 mol% or more and 25 mol% or less in all the dicarboxylic acid components. When it is within the above range, the crosslinking of the self-crosslinkable resin in the conductive layer becomes appropriate, and the adhesion of the conductive layer to the substrate is further improved.

[0035] Examples of the diglycol component forming the polyester resin (1) include diethylene glycol, aliphatic glycols having 2 to 8 carbon atoms, or alicyclic glycols having 6 to 12 carbon atoms. Specific examples of the aliphatic glycols having 2 to 8 carbon atoms or alicyclic glycols having 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-xylene glycol, triethylene glycol, and the like. The diglycol component may be used alone or in combination of two or more.

[0036] The number average molecular weight of the polyester resin (1) is preferably 2,000 or more and 30,000 or less, and more preferably 10,000 or more and 27,000 or less. The number average molecular weight of the polyester resin (1) is the number-average molecular weight determined based on the calibration curve of elution time vs. molecular weight obtained in advance from a polystyrene standard substance with known molecular weight by measuring the elution time using gel permeation chromatography (GPC). If the number average molecular weight of the polyester resin (1) is at least the lower limit value, the adhesion of the conductive layer becomes higher, and if it is at most the upper limit value, the water dispersibility of the polyester resin (1) becomes higher.

[0037] The method for producing the polyester resin (1) is not particularly limited. For example, a method in which a dicarboxylic acid component and a diglycol component are subjected to an esterification or transesterification reaction at 130°C or higher and 200°C or lower, and then a polycondensation reaction is carried out at 200°C or higher and 250°C or lower under reduced pressure conditions can be mentioned. Examples of the reaction catalyst used in the method for producing the 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 obtained polyester resin (1) may be added to water to form an aqueous dispersion. Since it becomes difficult to obtain a uniform dispersion as the solid content (non-volatile component) concentration of the aqueous dispersion of the polyester resin (1) increases, the solid content concentration is preferably 30% by mass or less.

[0038] The content of the polyester resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50000 parts by mass or less, more preferably 100 parts by mass or more and 10000 parts by mass or less, and still more preferably 200 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the conductive composite. If it is above the above lower limit value, the adhesion of the conductive layer to the substrate is further improved, and if it is below the above upper limit value, it is possible to prevent a decrease in conductivity due to a decrease in the content of the conductive composite.

[0039] [Self-crosslinkable resin] The alkoxysilyl group-containing acrylic resin, when combined with the polyester resin (1) and included together with the conductive composite, self-crosslinks during the formation of the conductive layer to become a self-crosslinkable resin. The excess anion groups that do not participate in the doping of the polyanion of the conductive composite can function as a catalyst for promoting the above self-crosslinking.

[0040] In order to obtain appropriate self-crosslinking, the content ratio represented by (alkoxysilyl group-containing acrylic resin / polyester resin (1)) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, and still more preferably 20 / 80 to 80 / 20 on a mass basis of the solid content. When it is in the above range, the mechanical strength of the formed conductive layer is further improved, and the adhesion of the conductive layer to the substrate is further improved.

[0041] [Aqueous dispersion medium] The aqueous dispersion medium contained in the conductive polymer dispersion is water or a mixture of water and an organic solvent.

[0042] Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, and the like. Examples of the alcohol 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, ethylene glycol monomethyl ether, etc.; and dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc. Examples of the ether solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, etc. Examples of the 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, diacetone alcohol, etc. Examples of the ester solvents include ethyl acetate, propyl acetate, butyl acetate, etc. Examples of the aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, etc. Examples of the solvents not classified above include dimethyl sulfoxide. The organic solvent may be used alone or in combination of two or more.

[0043] From the viewpoint of enhancing the dispersibility of the conductive composite, the dispersion medium of the conductive polymer dispersion preferably has a high water content, and preferably contains an organic solvent from the viewpoint of enhancing the dispersibility of the alkoxysilyl group-containing acrylic resin. The organic solvent is preferably a water-soluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a solubility of 1 g or more in 100 g of water at 20°C, and the water-insoluble organic solvent is an organic solvent having a solubility of less than 1 g in 100 g of water at 20°C. As the water-soluble organic solvent, one or more selected from the alcohol solvents are preferred.

[0044] The dispersion medium of the conductive polymer dispersion is preferably an aqueous dispersion medium containing water. The content ratio of water to the total mass of the aqueous dispersion medium is preferably, for example, 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 40% by mass or less.

[0045] [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, defoamers, coupling agents, antioxidants, ultraviolet absorbers, etc. can be used. Examples of the surfactant include nonionic, anionic, and cationic surfactants. From the viewpoint of storage stability, nonionic surfactants are preferred. In addition, polymer surfactants such as polyvinylpyrrolidone may be added. Examples of the inorganic conductive agent include metal ions, conductive carbon, etc. The metal ions can be generated by dissolving a metal salt in water. Examples of the coupling agent include silane coupling agents having an epoxy group, a vinyl group, or an amino group. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, etc. 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, benzoate-based ultraviolet absorbers, etc.

[0046] When the conductive polymer dispersion contains the above additives, the content ratio can be appropriately determined according to the type of the additive. For example, it can be in the range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the conductive composite.

[0047] <Manufacturing Method of Conductive Polymer Dispersion> As a method for producing the conductive polymer dispersion of the present aspect, for example, a method of adding a polyester resin, an acrylic resin containing an alkoxysilyl group, and, if necessary, other additives to an aqueous dispersion of a conductive composite can be mentioned. The aqueous dispersion of the conductive composite may be obtained by chemically oxidatively 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, since the conductive composite functions as a catalyst for promoting the self-crosslinking of the self-crosslinkable resin, it is preferably prepared as a self-crosslinking resin in which the polyester resin and the acrylic resin containing an alkoxysilyl group are mixed in advance, and the conductive composite is mixed with the self-crosslinkable resin immediately before coating to obtain a conductive polymer dispersion.

[0048] [Conductive layer] The formation range of the conductive layer provided in the conductive laminate of the present aspect may be the entire surface or a part of any surface of the metal substrate. When the conductive layer is formed only on a part of the surface of the metal substrate, for example, the conductive layer may be a fine conductive pattern such as a circuit or an electrode, or the region where the conductive layer is provided and the region where it is not provided may exist on the same surface and be roughly divided.

[0049] As the average thickness of the conductive layer, for example, 10 nm or more and 100 μm or less is preferable, 20 nm or more and 50 μm or less is more preferable, and 30 nm or more and 30 μm or less is even more preferable. If the average thickness of the conductive layer is at least the lower limit value, high conductivity can be exhibited, and if it is at most the upper limit value, the adhesion of the conductive layer to the substrate is further improved.

[0050] [Metal substrate] The shape of the metal substrate is not particularly limited, and examples thereof include a plate shape, a foil shape, a rod shape, and any other shape. A fine porous structure may be formed on the surface of the metal substrate, or it may be a smooth surface. The metal constituting the metal substrate is not particularly limited, and examples thereof include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, etc. These metals are known as valve metals used as anodes of capacitors. An oxide film may be formed on the surface of the metal substrate. That is, in the conductive laminate of the present embodiment, the conductive layer may be in close contact with the oxide film on the surface of the metal substrate (the oxide film is regarded as the surface of the metal substrate).

[0051] ≪Manufacturing method of conductive laminate≫ The second aspect of the present invention is a method for manufacturing a conductive laminate, which includes a step of applying the conductive polymer dispersion liquid described in the first aspect to at least a part of the surface of a metal substrate, drying and curing the coating film made of the coating material, and forming a conductive layer. By the manufacturing method of the present embodiment, the conductive laminate of the first aspect can be manufactured.

[0052] As a method of applying (coating) the conductive polymer dispersion liquid to an arbitrary surface of the substrate, for example, methods using coaters such as 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, screen coater, etc., methods using sprayers such as air spray, airless spray, rotor damming, etc., dipping methods such as dip, etc. can be applied.

[0053] The coating amount of the conductive polymer dispersion liquid on the substrate is not particularly limited, but considering uniform coating without unevenness, conductivity and film strength, as a solid content, it is preferably in the range of 0.01 g / m 2 or more and 10.0 g / m 2 or less.

[0054] It is preferable to dry the coating film composed of the conductive polymer dispersion applied on the substrate to remove the dispersion medium. In this drying process, the self-crosslinking of the self-crosslinkable resin is promoted, the mechanical strength of the formed conductive layer is increased, and the adhesion to the substrate is improved. Examples of the method for drying the coating film include heat drying and vacuum drying. As the heat drying, for example, methods such as hot air heating and infrared heating can be adopted. When applying heat drying, the heating temperature is appropriately set according to the dispersion medium used, but usually it is within the range of 50°C or higher and 200°C or lower. Here, the heating temperature is the set temperature of the drying device. As the preferable drying time within the above heating temperature range, it is preferably 0.5 minutes or more and 30 minutes or less, and more preferably 1 minute or more and 15 minutes or less.

[0055] By drying the coating film, a self-crosslinkable resin contained in the coating film is self-crosslinked, and a conductive laminate in which a conductive layer (conductive film) formed by curing the coating film is obtained can be obtained. In addition, a part of the alkoxysilyl groups contained in the alkoxysilyl group-containing acrylic resin contained in the coating film reacts with the hydroxyl groups in the oxide film on the surface of the metal substrate, and the adhesion of the formed conductive layer to the surface of the metal substrate is further improved.

[0056] ≪Capacitor≫ The conductive laminate of the first aspect can function as a constituent member of a capacitor. That is, the metal substrate constituting the conductive laminate functions as an anode, and the conductive layer adhering to the surface of the metal substrate can function as a solid electrolyte layer. For example, a capacitor can be manufactured by a known manufacturing method having a step of applying a conductive polymer dispersion on the surface of a dielectric layer (oxide film) formed on the surface of an anode made of a porous body of valve metal and drying it to form a solid electrolyte layer.

[0057] As a general structure of a capacitor, for example, as shown in FIG. 1, there is one including an anode 11 made of a porous body of valve metal, a dielectric layer 12 made of an oxide of valve metal, a solid electrolyte layer 14 formed on the surface of the dielectric layer 12, and a cathode 13 provided on the outermost side. The cathode 13 is provided on the side opposite to the anode 11 with the dielectric layer 12 and the solid electrolyte layer 14 interposed therebetween.

[0058] Examples of the valve metal constituting the anode 11 include aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, etc. Among these, aluminum, tantalum, and niobium are preferable. Specific examples of the anode 11 include those obtained by etching an aluminum foil to increase the surface area and then subjecting the surface to an oxidation treatment, and those obtained by subjecting the surface of a sintered body of tantalum particles or niobium particles to an oxidation treatment to form pellets. Those treated in this way become porous bodies with uneven surfaces formed thereon.

[0059] The dielectric layer 12 is a layer formed by oxidizing the surface of the anode 11. For example, it is formed by anodizing the surface of the metal anode 11 in an electrolytic solution such as an ammonium adipate aqueous solution. Similar to the anode 11, unevenness is also formed on the dielectric layer 12.

[0060] As the cathode 13, a metal layer made of a conductive substance such as a conductive layer formed from a conductive paste or an aluminum foil can be used.

[0061] The solid electrolyte layer 14 is formed on the surface of the dielectric layer 12. The solid electrolyte layer 14 covers at least a part of the surface of the dielectric layer 12, and may cover the entire surface of the dielectric layer 12. The thickness of the solid electrolyte layer 14 may be constant or may not be constant. For example, a thickness of 1 μm or more and 100 μm or less can be mentioned.

[0062] [Electrolytic solution] The capacitor may have an electrolytic solution that impregnates the solid electrolyte layer. Examples of the solvent constituting the electrolyte solution include alcohol solvents such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, and glycerin; lactone solvents such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone; sulfur solvents such as sulfolane, dimethyl sulfoxide, and dimethyl sulfone; amide solvents such as N-methylformamide, N,N-dimethylformamide, N-methylacetamide, and N-methylpyrrolidinone; nitrile solvents such as acetonitrile and 3-methoxypropionitrile; and water. Examples of the electrolyte constituting the electrolyte solution include organic acids such as adipic acid, glutaric acid, succinic acid, benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, maleic acid, toluic acid, enanthic acid, malonic acid, formic acid, 1,6-decanedicarboxylic acid, and 5,6-decanedicarboxylic acid; octanedicarboxylic acids such as 1,7-octanedicarboxylic acid; azelaic acid and sebacic acid; or boric acid, a polyhydric alcohol complex compound of boric acid obtained from boric acid and a polyhydric alcohol; inorganic acids such as phosphoric acid, carbonic acid, and silicic acid, etc. as the anion component, and primary amines (methylamine, ethylamine, propylamine, butylamine, ethylenediamine, etc.), secondary amines (dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine, etc.), tertiary amines (trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo(5,4,0)-undecene-7, etc.), tetraalkylammonium (tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, etc.), etc. as the cation component; and the like.

[0063] The capacitor is not limited to the above configuration, and a separator may be provided between the dielectric layer and the cathode. Examples of the capacitor having a separator provided between the dielectric layer and the cathode include a wound capacitor. Examples of the separator include sheets (including nonwoven fabrics) made of, for example, cellulose, polyvinyl alcohol, polyester, polyethylene, polystyrene, polypropylene, polyimide, polyamide, polyvinylidene fluoride, etc., and nonwoven fabrics of glass fibers. The density of the separator is, for example, 0.1 g / cm 3 or more and 1.0 g / cm 3 or less. When providing a separator, a method of impregnating the separator with carbon paste or silver paste to form a cathode can also be applied.

Example

[0064] (Production Example 1) Production of Polystyrene Sulfonic Acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and while stirring at 80 °C, a solution of 1.14 g of ammonium persulfate oxidant previously dissolved in 10 ml of water was added dropwise over 20 minutes, and this solution was stirred for 12 hours. To the obtained sodium polystyrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10 mass% was added to obtain a polystyrene sulfonic acid-containing solution. Next, approximately 1000 ml of the solvent of the polystyrene sulfonic acid-containing solution was removed by ultrafiltration, 2000 ml of ion-exchanged water was added to the residue, and approximately 2000 ml of the solvent was removed by ultrafiltration to wash the polystyrene sulfonic acid with water. This water washing operation was repeated 3 times. The water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

[0065] (Production Example 2) Preparation of PEDOT-PSS Aqueous Dispersion A solution in which 0.5 g of 3,4-ethylenedioxythiophene and 1.5 g of polystyrene sulfonic acid were 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 obtained mixed solution was kept at 20 °C, and while stirring, a solution prepared by dissolving 0.03 g of ferric sulfate in 4.97 g of ion-exchanged water and a solution prepared by dissolving 1.1 g of ammonium persulfate in 8.9 g of ion-exchanged water were slowly added, and the resulting reaction solution was stirred for 24 hours to react. By the above reaction, a PEDOT-PSS aqueous dispersion containing a conductive composite (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene), which is a π-conjugated conductive polymer, and polystyrene sulfonic acid, and water as a dispersion medium was obtained. To this dispersion, 13.2 g of Duolite C255LFH (manufactured by Sumika Chemtex Corporation, cation exchange resin) and 13.2 g of Duolite A368S (manufactured by Sumika Chemtex Corporation, anion exchange resin) were added, and after filtration to remove the ion exchange resin, a PEDOT-PSS aqueous dispersion (solid content 1.3% by mass) from which the oxidizing agent and the catalyst were removed was obtained.

[0066] (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-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermometer, and a stirrer. Then, the temperature inside the flask was raised from 130 °C to 170 °C over 2 hours for transesterification reaction, and then 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 for esterification reaction. Next, the temperature was gradually raised and the pressure was reduced, and finally a polycondensation reaction was carried out at a reaction temperature of 250 °C and a vacuum degree of 5 mmHg or less for 1 hour. Then, it was cooled, and ion-exchanged water was added under normal pressure to obtain polyester resin A with a non-volatile content (solid content) of 25% by mass.

[0067] (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) as a surfactant were charged into a beaker. Then, while stirring the inside of the beaker, 40 g of 3-methacryloyloxypropyltrimethoxysilane was added to prepare a monomer emulsion. Next, 37.5 g of ion-exchanged water, 1 g of a surfactant (Eleminol RS-3000), and 0.5 g of potassium persulfate were charged into a four-necked flask equipped with a condenser, a monomer dropping funnel, a thermometer, and a stirrer. Then, after nitrogen substitution while stirring the inside of the flask, heating was started, and the monomer emulsion was added dropwise at 75°C over 4 hours. After the dropping was completed, the reaction was advanced by maintaining the liquid temperature at 75 to 85°C, and it was cooled 4 hours after the dropping 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.

[0068] (Production Example 5) Preparation of alkoxysilyl group-containing acrylic resin C An alkoxysilyl group-containing acrylic resin C having a non-volatile content of 25% by mass was obtained in the same manner as in Production Example 4, except that 40 g of 3-methacryloyloxypropyltrimethoxysilane was changed to 40 g of 3-acryloyloxypropyltrimethoxysilane.

[0069] (Production Example 6) Preparation of alkoxysilyl group-containing acrylic resin D An alkoxysilyl group-containing acrylic resin D having a non-volatile content of 25% by mass was obtained in the same manner as in Production Example 4, except that 40 g of 3-methacryloyloxypropyltrimethoxysilane was changed to 40 g of 3-methacryloyloxypropyltriethoxysilane.

[0070] (Production Example 7) Preparation of alkoxysilyl group-containing acrylic resin E An alkoxysilyl group-containing acrylic resin E having a non-volatile content of 25% by mass was obtained in the same manner as in Production Example 4, except that 40 g of 3-methacryloyloxypropyltrimethoxysilane was changed to 40 g of 3-acryloyloxypropyltriethoxysilane.

[0071] (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 at a solid content mass ratio of 50 / 50 to obtain a self-crosslinking resin F with a non-volatile content (solid content) of 25% by mass.

[0072] (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 at a solid content mass ratio of 50 / 50 to obtain a self-crosslinking resin G with a non-volatile content (solid content) of 25% by mass.

[0073] (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 at a solid content mass ratio of 50 / 50 to obtain a self-crosslinking resin H with a non-volatile content (solid content) of 25% by mass.

[0074] (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 at a solid content mass ratio of 50 / 50 to obtain a self-crosslinking resin I with a non-volatile content (solid content) of 25% by mass.

[0075] (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 at a solid content mass ratio of 25 / 75 to obtain a self-crosslinking resin J with a non-volatile content (solid content) of 25% by mass.

[0076] (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 at a solid content mass ratio of 75 / 25 to obtain a self-crosslinking resin K with a non-volatile content (solid content) of 25% by mass.

[0077] (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 at a solid content mass ratio of 10 / 90 to obtain a self-crosslinkable resin L with a nonvolatile content (solid content) of 25% by mass.

[0078] (Production Example 15) Preparation of Self-Crosslinkable 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 at a solid content mass ratio of 90 / 10 to obtain a self-crosslinkable resin M with a nonvolatile content (solid content) of 25% by mass.

[0079] (Example 1) 60 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 40 g of the self-crosslinkable resin F, and 100 g of methanol were mixed to prepare a conductive polymer dispersion. Next, it was coated on an aluminum substrate (aluminum foil) using a #8 bar coater and dried at 150°C for 10 minutes to obtain a conductive laminate provided with a conductive layer. The results of measuring the surface resistance value and the adhesion of the conductive layer are shown in Table 1.

[0080] (Example 2) A conductive laminate was produced and measured in the same manner as in Example 1, except that the PEDOT-PSS aqueous dispersion was changed to 20 g and the self-crosslinkable resin F was changed to 80 g in Example 1. The results are shown in Table 1.

[0081] (Example 3) A conductive laminate was produced and measured in the same manner as in Example 1, except that the PEDOT-PSS aqueous dispersion was changed to 80 g and the self-crosslinkable resin F was changed to 20 g in Example 1. The results are shown in Table 1.

[0082] (Example 4) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin G in Example 1. The results are shown in Table 1.

[0083] (Example 5) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin H in Example 1. The results are shown in Table 1.

[0084] (Example 6) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin I in Example 1. The results are shown in Table 1.

[0085] (Example 7) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin J in Example 1. The results are shown in Table 1.

[0086] (Example 8) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin K in Example 1. The results are shown in Table 1.

[0087] (Example 9) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin L in Example 1. The results are shown in Table 1.

[0088] (Example 10) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin M in Example 1. The results are shown in Table 1.

[0089] (Example 11) A conductive laminate was produced and measured in the same manner as in Example 1, except that the aluminum substrate was changed to a tantalum substrate in Example 1. The results are shown in Table 1.

[0090] (Comparative Example 1) A conductive laminate was produced and measured in the same manner as in Example 1, except that 40 g of the self-crosslinkable resin F was changed to 40 g of water in Example 1. The results are shown in Table 1.

[0091] (Comparative Example 2) A conductive laminate was produced and measured in the same manner as in Example 1, except that 60 g of the PEDOT-PSS aqueous dispersion was changed to 60 g of water. The results are shown in Table 1.

[0092] (Comparative Example 3) A conductive laminate was produced and measured in the same manner as in Example 1, except that 40 g of the self-crosslinkable resin F was changed to 40 g of the polyester resin A. The results are shown in Table 1.

[0093] (Comparative Example 4) An attempt was made to produce a conductive laminate in the same manner as in Example 1, except that 40 g of the self-crosslinkable resin F was changed to 40 g of the alkoxysilyl group-containing acrylic resin B. However, the coating film did not conform to the glass surface, was highly elastic, and it was difficult to form the conductive layer, so the test was aborted.

[0094] (Comparative Example 5) A conductive laminate was produced and measured in the same manner as in Comparative Example 1, except that the aluminum substrate was changed to a tantalum substrate. The results are shown in Table 1.

[0095] (Comparative Example 6) A conductive laminate was produced and measured in the same manner as in Comparative Example 2, except that the aluminum substrate was changed to a tantalum substrate. The results are shown in Table 1.

[0096] (Comparative Example 7) A conductive laminate was produced and measured in the same manner as in Comparative Example 3, except that the aluminum substrate was changed to a tantalum substrate. The results are shown in Table 1.

[0097] (Comparative Example 8) A conductive laminate was produced and measured in the same manner as in Comparative Example 4, except that the aluminum substrate was changed to a tantalum substrate. The results are shown in Table 1.

[0098] <Evaluation> [Surface resistivity] For each conductive laminate, the surface resistivity of the conductive layer was measured using a resistivity meter (manufactured by Nitto Seiko Analytic Co., Ltd., High Resista) under the condition of an applied voltage of 10 V. The measurement results of the surface resistivity are shown in Table 1. Note that "Ω / □" in the table means ohm per square. "1.0E+05" represents "1.0×10 5 ", and the same applies to others.

[0099] [Adhesion] The adhesion of the formed conductive layer to each metal substrate was evaluated by measuring the number of squares that did not peel off for a total of 100 squares with a size of 1 mm square in accordance with the cross-cut tape peeling test in JIS K 5600:1999. The results are shown in Table 1. In the results of Table 1, the larger the number of molecules (the number of squares that did not peel off), the greater the adhesion of the conductive layer to each metal substrate.

[0100]

Table 1

[0101] Since the conductive layers of Examples 1 to 11 are cured products of a paint composed of a conductive composite, an alkoxysilyl group-containing acrylic resin, and a polyester resin, they have good conductivity and excellent adhesion to the surface of the metal substrate. Since the conductive layers of Comparative Examples 1 and 5 are cured products of a paint that does not contain an alkoxysilyl group-containing acrylic resin and a polyester resin, their adhesion to the surface of the metal substrate is poor. Since the conductive layers of Comparative Examples 2 and 6 are cured products of a paint that does not contain a conductive composite, their conductivity is poor, and furthermore, their adhesion to the surface of the metal substrate is also poor. It is considered that the reason for the poor adhesion is that the polyanion constituting the conductive composite does not exist, so the above self-crosslinking did not proceed. Since the conductive layers of Comparative Examples 3 and 7 are cured products of paints that do not contain an alkoxysilyl group-containing acrylic resin, they have poor conductivity and furthermore, poor adhesion to the surface of the metal substrate. It is considered that the reason for the poor adhesion is that the above-mentioned self-crosslinking did not proceed because the alkoxysilyl group-containing acrylic resin was absent.

Claims

**Claim 1** A conductive laminate comprising a metal substrate and a conductive layer adhered to at least a part of the surface of the metal substrate, wherein the conductive layer is a cured product of a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. **Claim 2** The conductive laminate according to claim 1, wherein the carbon number of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less. **Claim 3** The conductive laminate according to claim 2, wherein the polyester resin has one or more selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxyl group. **Claim 4** The conductive laminate according to claim 3, wherein the polyanion is polystyrene sulfonic acid. **Claim 5** The conductive laminate according to claim 4, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). **Claim 6** The conductive laminate according to claim 5, wherein the metal substrate is formed of aluminum or tantalum. **Claim 7** A capacitor comprising the conductive laminate according to any one of claims 1 to 6. **Claim 8** A method for manufacturing a conductive laminate, comprising a step of applying a paint to at least a part of a metal substrate, drying and curing a coating film made of the paint to form a conductive layer, wherein the paint is a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. **Claim 9** The method for manufacturing a conductive laminate according to claim 8, wherein the carbon number of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less. **Claim 10** The method for manufacturing a conductive laminate according to claim 9, wherein the polyester resin has one or more selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxyl group.

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