Conductive polymer dispersion, conductive laminate and method for producing the same

Abstract

To provide a conductive laminate having a conductive release layer having both conductivity and releasability, a method for manufacturing the same, and a conductive polymer dispersion which is suitable for the manufacture method.SOLUTION: A conductive polymer dispersion contains a conductive composite body containing a π-conjugated conductive polymer and polyanion, silicone emulsion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. A content ratio represented by (alkoxysilyl group-containing acrylic resin / polyester resin) is preferably 5 / 95 to 50 / 50 based on the mass of a solid content.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer dispersion, a conductive laminate, and a method for producing the same. [Background technology]

[0002] One technique for manufacturing electronic devices involves forming a conductive layer on the surface of a resin substrate. π-conjugated conductive polymers have attracted attention as materials for forming conductive layers because of their excellent conductivity and transparency. Furthermore, a silicone-containing release layer may be further laminated on the surface of the conductive layer. Such a conductive release film is disclosed in Patent Document 1. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2020-204009 Summary of the Invention [Problem to be solved by the invention]

[0004] 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 enabling them to be used in a variety of applications. If a release layer containing silicone is further laminated on the surface of the conductive layer, easy peelability (releasability) can be imparted to the surface. However, there is a problem in that the number of steps required to laminate the release layer on the surface of the conductive layer increases.

[0005] The present invention provides a conductive laminate having a conductive release layer that combines conductivity and releasability, a method for producing the same, and a conductive polymer dispersion suitable for the production method. [Means for solving the problem]

[0006] [1] A conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, a silicone emulsion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. [2] The conductive polymer dispersion according to [1], wherein the content of water contained in the aqueous dispersion medium is 40 parts by mass or more per part by mass of the conductive composite. [3] The conductive polymer dispersion liquid according to [1] or [2], wherein the number of carbon atoms in the 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 the content ratio expressed by (the alkoxysilyl group-containing acrylic resin / the polyester resin) is 5 / 95 to 50 / 50 based on the mass of the solid content. [6] The conductive polymer dispersion according to any one of [1] to [5], further comprising a basic compound. [7] The conductive polymer dispersion according to any one of [1] to [6], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene) or the polyanion is polystyrenesulfonic acid. [8] A conductive laminate comprising a substrate and a conductive release layer formed on at least a portion of the surface of the substrate, wherein the conductive release layer is a cured product of the conductive polymer dispersion according to any one of [1] to [7]. [9] The conductive laminate according to [8], wherein the substrate is a polypropylene film.

[10] A method for producing a conductive laminate, comprising applying the conductive polymer dispersion according to any one of [1] to [7] to at least a part of the surface of a substrate to form a conductive layer. [Effects of the Invention]

[0007] In the conductive laminate of the present invention, the conductive release layer exhibits excellent conductivity and releasability, and further, the conductive release layer has excellent adhesion to the substrate. The manufacturing method of the present invention makes it possible to easily manufacture the above-mentioned excellent conductive laminate. The conductive polymer dispersion of the present invention is suitable for the above-mentioned manufacturing method and has excellent wettability to the substrate.

[0008] This invention is believed to contribute to SDG Goal 12, "Responsible Consumption and Production."

[0009] In this specification and claims, the lower and upper limits of numerical ranges indicated with "to" are included in the numerical range. DETAILED DESCRIPTION OF THE INVENTION

[0010] <<Conductive polymer dispersion>> A first aspect of the present invention is a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a silicone emulsion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium.

[0011] [Conductive composite] The conductive composite contained in the conductive polymer dispersion of this embodiment contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite dopes the π-conjugated conductive polymer to form a conductive composite having conductivity. In polyanions, only some of the anionic groups are doped into the π-conjugated conductive polymer, and there are excess anionic groups that are not involved in the doping. Because the excess anionic groups are hydrophilic groups, the conductive composite has water dispersibility.

[0012] (π-conjugated conductive polymer) The π-conjugated conductive polymer may be an organic polymer whose main chain is composed of a π-conjugated system, and examples thereof include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

[0013] 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.

[0014] (polyanion) A polyanion is a polymer having two or more monomer units with an anionic group in the molecule. The anionic group of this polyanion functions as a dopant for a π-conjugated conductive polymer, improving the conductivity of the π-conjugated conductive polymer. The anionic group of the polyanion is preferably a sulfo group or a carboxy group. Specific examples of such polyanions include polymers having sulfo groups, such as polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid esters having sulfo groups, polymethacrylic acid esters having sulfo groups (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid; and polymers having carboxy groups, such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprene carboxylic acid. The polyanion may be a homopolymer formed by polymerizing a single monomer, or a copolymer formed by polymerizing two or more types of monomers. Among these polyanions, polymers having sulfo groups are preferred, and polystyrene sulfonic acid is more preferred, since they can further increase the conductivity. The polyanions may be used alone or in combination of two or more. The mass-average molecular weight of the polyanion is preferably from 20,000 to 1,000,000, and more preferably from 100,000 to 500,000. The mass-average molecular weight is the average molecular weight based on mass measured using gel filtration chromatography and calculated as pullulan.

[0015] The content of the polyanion in the conductive composite is preferably in the range of 1 part by mass to 1,000 parts by mass, more preferably 10 parts by mass to 700 parts by mass, and even more preferably 100 parts by mass 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, resulting in higher conductivity. 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, thereby ensuring sufficient conductivity.

[0016] The content of the conductive complex contained in the conductive polymer dispersion of this embodiment is preferably 0.01 mass % or more and 5.0 mass % or less, more preferably 0.10 mass % or more and 2 mass % or less, and even more preferably 0.15 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 large as the lower limit of the above range, the conductivity of the conductive release layer formed by applying the conductive polymer dispersion can be further improved. When the content is equal to or less than the upper limit of the above range, the dispersibility of the conductive complex in the conductive polymer dispersion can be improved, and a uniform conductive release layer can be formed.

[0017] [Silicone emulsion] A silicone emulsion is formed by dispersing a silicone compound in an aqueous dispersion medium. A surfactant (emulsifier) ​​may also be included to form an emulsion of the silicone compound. As the silicone-based compound, silicone-based compounds contained in known mold release agents can be used. Here, silicone refers to a polymer collectively called organopolysiloxane, which has a main chain (silicone skeleton) in which organic groups (e.g., alkyl groups, phenyl groups, etc.) are bonded to siloxane bonds. As the organopolysiloxane, polydimethylsiloxane (PDMS) is preferred, and polydimethylsiloxanes having reactive or non-reactive functional groups in part are also preferred. In addition, acrylic resins and alkyd resins having organopolysiloxane in their side chains can also be used as the silicone-based compound.

[0018] As the silicone compound, a curable silicone is preferred because it exhibits stable releasability and excellent film-forming properties. The curable silicone may be either an addition curable silicone or a condensation curable silicone. When curable silicone reacts, it forms a three-dimensional crosslinked structure and cures. Examples of addition-curable silicones include linear polymers having siloxane bonds, including polydimethylsiloxane having vinyl groups at both ends of the linear chain, and hydrogensilane. A platinum-based curing catalyst may be used to accelerate the curing. Specific examples of addition-curable silicones include KM-3951, X-52-6068, X-52-151, and X-52-6069 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0019] The content of solids (non-volatile content) of the silicone emulsion relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.1 mass% or more and 4.0 mass% or less, more preferably 0.5 mass% or more and 3.5 mass% or less, even more preferably 1.0 mass% or more and 3.0 mass% or less, and most preferably 1.5 mass% or more and 2.5 mass% or less. When the content is at least as large as the lower limit of the above range, excellent releasability can be imparted to the conductive release layer. When the content is equal to or less than the upper limit of the above range, the conductivity of the conductive release layer can be sufficiently maintained, and excellent adhesion of the conductive release layer to the substrate can be maintained.

[0020] [Hardening agent] The conductive polymer dispersion of this embodiment may contain a curing agent that accelerates the curing of the curable silicone. The curing agent is selected depending on the type of curable silicone used. In the case of addition reaction type silicone, it is preferable to use a platinum catalyst as a curing agent. Specific examples of platinum catalysts include CAT-PL-50T and CAT-PM-10A (manufactured by Shin-Etsu Chemical Co., Ltd.). In the case of condensation reaction type silicone resins, it is preferable to use an organotin catalyst (for example, an organotin acylate catalyst) as a curing agent. A specific example of the organotin catalyst is CAT-PS-8S (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0021] [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 that can be copolymerized with the alkoxysilyl group. Here, the term "(meth)acrylic" means "acrylic or methacrylic".

[0022] 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 )=CH2 (Y) In the formula, 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 three R 11 At least one of the 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. 11 )3-Si-R 12 - corresponds to an alkoxysilyl group.

[0023] Specific examples of (meth)acrylic acid esters having an alkoxysilyl group include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltrimethoxysilane. The above-mentioned monomers having an alkoxysilyl group that constitute the repeating units of the alkoxysilyl group-containing acrylic resin may be of one type only, or may be of two or more types.

[0024] 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 release layer formed using the conductive polymer dispersion of this embodiment to the substrate is further improved.

[0025] 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 monomer copolymerizable with this monomer. Note that this proportion of 100% by mass means that the resin is a homopolymer of the monomer having the alkoxysilyl group.

[0026] Examples of the other radical polymerizable monomer 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 vinylsilane compounds, and one or more of these may be used as copolymerizable monomers.

[0027] (Manufacturing 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 employed, for example, 10 to 1,000 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 vessel. Separately, 10 to 1,000 parts by mass of ion-exchanged water and 1 to 20 parts by mass of a surfactant are added to a dropping vessel, and 100 parts by mass of a monomer constituting the alkoxysilyl group-containing acrylic resin is added to produce an emulsion. This emulsion is then added dropwise to the reaction vessel to carry out emulsion radical polymerization. The reaction temperature, which varies depending on the reactivity of the monomers used, is preferably 60 to 100°C, and the reaction time is preferably 4 to 10 hours.

[0028] The surfactant used in emulsion polymerization may be one or more of anionic surfactants, nonionic reactive surfactants, and non-reactive surfactants, with anionic surfactants being preferred.

[0029] Examples of the polymerization initiator used in emulsion polymerization include general radical polymerization initiators, for example, 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.

[0030] The alkoxysilyl group-containing acrylic resin obtained by emulsion polymerization may be added to a dispersion medium such as water to form a dispersion. Since a high solids concentration makes it difficult to obtain a uniform dispersion, 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.

[0031] 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 2,000 parts by mass or less, relative to 100 parts by mass of the conductive composite. If the content is equal to or greater than the above lower limit, the adhesion of the conductive release layer to the substrate is further improved, and if 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.

[0032] [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 polycarboxylic 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. Furthermore, 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 release layer.

[0033] Examples of polyester resins having acid groups include polyester resins (hereinafter referred to as "polyester resin (1)") that are polycondensates of dicarboxylic acid components and diglycol components and have alkali metal salts of acid groups (such as sulfo groups, carboxy groups, and phosphate groups). This polyester resin (1) has a high polarity and is therefore excellent in water dispersibility, and can be stably dispersed in water without the use of an emulsifier or stabilizer.

[0034] 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 is a sulfonic acid alkali metal salt type substituent (-SO ) in which the sulfo group is neutralized with an alkali metal. 3- X + , (X + Preferably, the dicarboxylic acid comprises a dicarboxylic acid having an alkali metal ion).

[0035] 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 dicarboxylic acids having a sulfo group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalenic acid-2,7-dicarboxylic acid, and derivatives thereof. Examples of alkali metals 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.

[0036] Among the dicarboxylic acid components, the dicarboxylic acid component other than the dicarboxylic acid having an alkali metal sulfonate salt type substituent is preferably an aromatic dicarboxylic acid, more preferably terephthalic acid or isophthalic acid. The aromatic nucleus of the aromatic dicarboxylic acid has a high affinity with hydrophobic plastics and is excellent in hydrolysis resistance.

[0037] The content of the dicarboxylic acid having an alkali metal sulfonate type substituent is preferably 5 mol % or more and 30 mol % or less, and more preferably 10 mol % or more and 25 mol % or less, of the total dicarboxylic acid components. Within the above range, the crosslinking of the self-crosslinking resin in the conductive release layer becomes appropriate, and the adhesion of the conductive release layer to the substrate is further improved.

[0038] 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.

[0039] The number average molecular weight of the polyester resin (1) is preferably from 2,000 to 30,000, more preferably from 10,000 to 27,000. The number average molecular weight of the polyester resin (1) is a numerical molecular weight determined by measuring the elution time using gel permeation chromatography (GPC) and based on a calibration curve of elution time versus molecular weight obtained in advance from polystyrene standard substances of known molecular weight. If the number average molecular weight of the polyester resin (1) is equal to or greater than the lower limit, the adhesiveness of the conductive release layer will be higher, and if it is equal to or less than the upper limit, the water dispersibility of the polyester resin (1) will be higher.

[0040] 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 higher and 200° C. or lower, and then subjected to a polycondensation reaction under reduced pressure at 200° C. or higher and 250° C. or lower. Examples of reaction catalysts used in the production method for 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. When the solid content (non-volatile component) concentration of the aqueous dispersion of polyester resin (1) becomes high, it becomes difficult to obtain a uniform dispersion, so the solid content concentration is preferably 30 mass % or less.

[0041] 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 2,000 parts by mass or less, relative to 100 parts by mass of the conductive composite. If the content is equal to or greater than the above lower limit, the adhesion of the conductive release layer to the substrate is further improved, and if 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.

[0042] [Self-crosslinking resin] The alkoxysilyl group-containing acrylic resin, when combined with the polyester resin (1) and contained in the conductive composite, undergoes self-crosslinking during the formation of the conductive release layer, becoming a self-crosslinking resin. The excess anion groups of the polyanion in the conductive composite that are not involved in doping can function as a catalyst to promote the self-crosslinking.

[0043] To obtain a suitable degree of self-crosslinking, the content ratio of (alkoxysilyl group-containing acrylic resin / polyester resin (1)) is preferably 5 / 95 to 50 / 50, more preferably 10 / 90 to 40 / 60, and even more preferably 20 / 80 to 30 / 70, based on the mass of the solid content. When the content is within the above range, the mechanical strength of the formed conductive release layer is further improved, and the adhesiveness of the conductive release layer to the substrate is further improved.

[0044] [Aqueous dispersion medium] The aqueous dispersion medium contained in the conductive polymer dispersion of this embodiment is water or a mixture of water and an organic solvent.

[0045] 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 ketone solvents include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol. Examples of the ester solvent include ethyl acetate, propyl acetate, and butyl acetate. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene. An example of a solvent that does not fall into the above categories is dimethyl sulfoxide. The organic solvents may be used alone or in combination of two or more.

[0046] The aqueous dispersion of this embodiment is preferably a mixed solvent of water and a water-soluble organic solvent, from the viewpoint of enhancing the dispersibility of the silicone emulsion and polyester resin. 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.

[0047] Since the conductive composite has high dispersibility in water, from the viewpoint of enhancing the dispersibility of the conductive composite, the content ratio of water relative to the total mass of the aqueous dispersion medium is, for example, preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less. Furthermore, 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 1000 parts by mass or less, even more preferably 80 parts by mass or more and 800 parts by mass or less, and particularly preferably 100 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 preferred.

[0048] The content ratio of the water-soluble organic solvent relative to the total mass of the aqueous dispersion medium in the conductive polymer dispersion of this embodiment is, for example, preferably 50 mass % or more and 95 mass % or less, more preferably 60 mass % or more and 90 mass % or less, and even more preferably 70 mass % or more and 85 mass % or less.

[0049] [Basic compounds] The conductive polymer dispersion of this embodiment may contain one or more basic compounds. By containing a basic compound, the wettability of the conductive polymer dispersion to the substrate can be improved. Examples of basic compounds include inorganic alkalis, amine compounds, and nitrogen-containing aromatic cyclic compounds.

[0050] Examples of inorganic alkalis include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium hydrogen carbonate, potassium hydrogen carbonate, and ammonium hydrogen carbonate.

[0051] The content of the basic compound contained in the conductive polymer dispersion of this embodiment is, for example, preferably 0.1 mM or more and 50 mM or less, more preferably 0.5 mM or more and 20 mM or less, and even more preferably 1 mM or more and 10 mM or less. When the content is at least as large as the lower limit of the above range, the wettability of the conductive polymer dispersion to the substrate can be further improved. When the content is equal to or less than the upper limit of the above range, interference with the self-crosslinking of the self-crosslinking resin can be prevented.

[0052] [Other additives] The conductive polymer dispersion may contain other additives. The additives are not particularly limited as long as they can achieve the effects of the present invention, and examples thereof include surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, and ultraviolet absorbers. 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 inorganic conductive agents include metal ions, conductive carbon, etc. 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 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.

[0053] When the conductive polymer dispersion contains the additive, the content thereof is determined appropriately depending on the type of additive, but can be, for example, in the range of 0.001 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the conductive composite.

[0054] <Method of manufacturing conductive polymer dispersion> Examples of a method for producing the conductive polymer dispersion of this embodiment include a method in which a silicone emulsion, a polyester resin, an alkoxysilyl group-containing acrylic resin, and, if necessary, a basic compound are added to an aqueous dispersion of a conductive complex. The aqueous dispersion of the conductive complex may be obtained by chemically oxidatively polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous solution of 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 in advance by mixing the polyester resin and the alkoxysilyl group-containing acrylic resin, and then mix the conductive complex with the self-crosslinking resin immediately before coating to obtain the conductive polymer dispersion.

[0055] <Conductive laminate> A second aspect of the present invention is a conductive laminate comprising a substrate and a conductive release layer formed on at least a portion of the surface of the substrate, wherein the conductive release layer is made of a cured product of the conductive polymer dispersion of the first aspect.

[0056] [Conductive release layer] The conductive release layer may be formed over the entire surface of any surface of the substrate, or only a part of it.In the conductive film, it is preferable that a conductive release layer of substantially uniform thickness is formed on almost the entire surface of one side or the other side of the film substrate.When a conductive release layer is formed only on a part of the surface of the substrate, for example, the conductive release layer may be a fine conductive pattern such as a circuit or an electrode, or the area where the conductive release layer is provided and the area where the conductive release layer is not provided may be present on the same surface and simply be roughly divided.

[0057] The average thickness of the conductive release layer is, for example, preferably 10 nm to 100 μm, more preferably 20 nm to 50 μm, and even more preferably 30 nm to 30 μm. If the average thickness of the conductive release layer is equal to or greater than the lower limit, high conductivity can be exhibited, and if it is equal to or less than the upper limit, the adhesion of the conductive release layer to the substrate can be further improved.

[0058] [Base material] The substrate may be made of an insulating material or 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. Examples of conductive materials include metals, conductive metal oxides, and carbon.

[0059] (Film substrate) When a film substrate is used as the substrate, the conductive laminate becomes a conductive film. Examples of the film substrate include plastic films made of synthetic resins, 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 elastomers, polyester-based elastomers, 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 release layer, the synthetic resin for the film substrate is preferably a polyolefin resin, and among these, polypropylene is preferred.

[0060] The synthetic resin for the film substrate may be amorphous or crystalline. The film substrate may be unstretched or stretched. The film substrate may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or flame treatment in order to further improve the adhesion of the conductive release layer.

[0061] The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is equal to or more than the lower limit, the film is less likely to break, and when 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 locations and averaging the measured values.

[0062] (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 release layer tends to decrease. Therefore, among the glass substrates, alkali-free glass is preferred. Here, alkali-free glass refers to a glass composition having an alkali component content of 0.1 mass % or less relative to the total mass of the glass composition.

[0063] 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 it 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 locations and averaging the measured values.

[0064] <Method for manufacturing conductive laminate> A third aspect of the present invention is a method for producing a conductive laminate, which comprises applying the conductive polymer dispersion of the first aspect to at least a part of the surface of a substrate to form a conductive release layer. By the production method of this aspect, the conductive laminate of the second aspect can be produced.

[0065] Examples of a method for coating (applying) the conductive polymer dispersion onto any surface of a substrate include a method using a coater such as a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an air doctor coater, a knife coater, a blade coater, a cast coater, or a screen coater; a method using a sprayer such as an air spray, an airless spray, or a rotor dampening; and an immersion method such as dipping.

[0066] The amount of conductive polymer dispersion to be applied to the substrate is not particularly limited, but taking into consideration the need for uniform and even application, conductivity, and film strength, it is recommended to apply a solid content of 0.01 g / m 2 More than 10.0g / m 2 The following ranges are preferred:

[0067] It is preferable to remove the dispersion medium by drying the coating film made of the conductive polymer dispersion applied to the substrate. This drying treatment promotes self-crosslinking of the self-crosslinking resin, thereby increasing the mechanical strength of the formed conductive release layer and improving its adhesion to the substrate. Methods for drying the coating film include heat drying, vacuum drying, etc. Heat drying can be performed using, for example, hot air heating or infrared heating. When heat drying is applied, the heating temperature is appropriately set depending on the dispersion medium used, but is usually within the range of 50°C to 200°C. Here, the heating temperature is the temperature set in 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.

[0068] When the coating film dries, the self-crosslinking resin contained in the coating film self-crosslinks, and the coating film is cured to obtain a conductive laminate having a conductive release layer (conductive film) formed thereon. [Example]

[0069] (Production Example 1) Production of polystyrene sulfonic acid 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, which had been dissolved in 10 ml of water in advance, was added dropwise over 20 minutes, and the solution was stirred for 12 hours. To the obtained sodium polystyrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added to obtain a polystyrene sulfonic acid-containing solution. Next, approximately 1000 ml of solvent was removed from the polystyrene sulfonic acid-containing solution by ultrafiltration, and 2000 ml of ion-exchanged water was added to the remaining solution, and approximately 2000 ml of solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed 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.

[0070] (Production Example 2) Preparation of PEDOT-PSS aqueous dispersion 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 react. By the above reaction, a PEDOT-PSS aqueous dispersion was obtained containing a conductive composite (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 Co., Ltd.) and 13.2 g of Duolite A368S (an anion exchange resin manufactured by Sumika Chemtex Co., Ltd.) were added, and the ion exchange resin was removed by filtration to obtain a PEDOT-PSS aqueous dispersion (solid content 1.3% by mass) from which the oxidant and catalyst had been removed.

[0071] (Production Example 3) Preparation of Polyester Resin A A four-neck flask equipped with a distillation tube, nitrogen inlet tube, thermometer, and stirrer was charged with 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. The temperature in the flask was then raised from 130°C to 170°C over 2 hours to carry out an ester exchange reaction. 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 to carry out an esterification reaction. The temperature was then gradually raised and the pressure reduced, finally reaching 250°C, and a polycondensation reaction was carried out for 1 hour at a vacuum of 5 mmHg or less. The mixture was then cooled, and ion-exchanged water was added under normal pressure to obtain a polyester resin A with a nonvolatile content (solids content) of 25% by mass.

[0072] (Production Example 4) Preparation of Alkoxysilyl Group-Containing Acrylic Resin B A beaker was charged with 18 g of ion-exchanged water and 3 g of Eleminol RS-3000 surfactant (manufactured by Sanyo Chemical Industries, Ltd., anionic surfactant, active ingredient 50% by mass). Then, while stirring the contents 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 surfactant (Eleminol RS-3000), and 0.5 g of potassium persulfate were charged into a four-neck flask equipped with a condenser, a monomer dropping funnel, a thermometer, and a stirrer. The atmosphere in the flask was then replaced with nitrogen while stirring, and heating was initiated. The monomer emulsion was added dropwise at 75°C over 4 hours. The reaction was continued by maintaining the liquid temperature at 75-85°C even after the dropwise addition was complete, and the mixture was cooled 4 hours after the dropwise addition was completed. After cooling, additional ion-exchanged water was added to obtain an alkoxysilyl group-containing acrylic resin B with a nonvolatile content (solid content) of 25% by mass.

[0073] (Production Example 5) Preparation of Alkoxysilyl Group-Containing Acrylic Resin C An 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-methacryloyloxypropyltrimethoxysilane was replaced with 40 g of 3-acryloyloxypropyltrimethoxysilane.

[0074] (Production Example 6) Preparation of Alkoxysilyl Group-Containing Acrylic Resin D 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-methacryloyloxypropyltriethoxysilane was used instead of 40 g of 3-methacryloyloxypropyltriethoxysilane.

[0075] (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-methacryloyloxypropyltrimethoxysilane was replaced with 40 g of 3-acryloyloxypropyltriethoxysilane.

[0076] (Production Example 8) Preparation of Self-Crosslinking Resin F Polyester resin A obtained in Production Example 3 and alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solids mass ratio of 50 / 50 to obtain self-crosslinking resin F having a non-volatile content (solids content) of 25 mass%.

[0077] (Production Example 9) Preparation of Self-Crosslinking Resin G Polyester resin A obtained in Production Example 3 and alkoxysilyl group-containing acrylic resin C obtained in Production Example 5 were blended in a solid content mass ratio of 50 / 50 to obtain self-crosslinking resin G having a non-volatile content (solid content) of 25 mass%.

[0078] (Production Example 10) Preparation of Self-Crosslinking Resin H Polyester resin A obtained in Production Example 3 and alkoxysilyl group-containing acrylic resin D obtained in Production Example 6 were blended in a solids mass ratio of 50 / 50 to obtain self-crosslinking resin H having a non-volatile content (solids content) of 25 mass%.

[0079] (Production Example 11) Preparation of Self-Crosslinking Resin I Polyester resin A obtained in Production Example 3 and alkoxysilyl group-containing acrylic resin E obtained in Production Example 7 were blended in a solids mass ratio of 50 / 50 to obtain self-crosslinking resin I with a non-volatile content (solids content) of 25 mass%.

[0080] (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 solids mass ratio of 25 / 75 to obtain a self-crosslinking resin J having a non-volatile content (solids content) of 25 mass%.

[0081] (Production Example 13) Preparation of Self-Crosslinking Resin K Polyester resin A obtained in Production Example 3 and alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended in a solid content mass ratio of 75 / 25 to obtain self-crosslinking resin K having a non-volatile content (solid content) of 25 mass%.

[0082] (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 %.

[0083] (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 solids mass ratio of 90 / 10 to obtain a self-crosslinking resin M having a nonvolatile content (solid content) of 25 mass %.

[0084] Example 1 A conductive polymer dispersion was prepared by mixing 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 40 g of KM-3951 (addition-curing silicone emulsion, solids content 30%, aqueous dispersion, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 g of self-crosslinking resin F, 4 g of CAT-PM-10A (platinum catalyst, aqueous dispersion, manufactured by Shin-Etsu Chemical Co., Ltd.), and 540 g of methanol. Next, the mixture was applied to a polypropylene film using a #8 bar coater and dried at 120°C for 1 minute to obtain a conductive film provided with a conductive release layer. The surface resistance value, peel strength, adhesion, and wettability (visual repellency) of the applied conductive polymer dispersion to the polypropylene film of the obtained conductive film were measured. The results are shown in Table 1.

[0085] Example 2 A conductive film was produced and measured in the same manner as in Example 1, except that the amount of KM-3951 was increased to 80 g and the amount of CAT-PM-10A was increased to 8 g in Example 1. The results are shown in Table 1.

[0086] Example 3 A conductive film was produced and measured in the same manner as in Example 1, except that the amount of KM-3951 was reduced to 20 g and the amount of CAT-PM-10A was reduced to 2 g in Example 1. The results are shown in Table 1.

[0087] Example 4 A conductive film was produced and measured in the same manner as in Example 1, except that the amount of self-crosslinking resin F in Example 1 was increased to 80 g. The results are shown in Table 1.

[0088] Example 5 A conductive film was produced and measured in the same manner as in Example 1, except that the amount of self-crosslinking resin F in Example 1 was reduced to 20 g. The results are shown in Table 1.

[0089] Example 6 A conductive film was produced and measured in the same manner as in Example 1, except that KM-3951 in Example 1 was replaced with X-52-6068 (addition-curing silicone emulsion, solids content 30%, aqueous dispersion, manufactured by Shin-Etsu Chemical Co., Ltd.). The results are shown in Table 1.

[0090] Example 7 A conductive film was produced and measured in the same manner as in Example 1, except that self-crosslinking resin F in Example 1 was changed to self-crosslinking resin G. The results are shown in Table 1.

[0091] Example 8 A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F in Example 1 was changed to the self-crosslinking resin H. The results are shown in Table 1.

[0092] Example 9 A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F in Example 1 was changed to the self-crosslinking resin I. The results are shown in Table 1.

[0093] Example 10 A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F in Example 1 was changed to the self-crosslinking resin J. The results are shown in Table 1.

[0094] Example 11 A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F in Example 1 was changed to the self-crosslinking resin K. The results are shown in Table 1.

[0095] Example 12 A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F in Example 1 was changed to the self-crosslinking resin L. The results are shown in Table 1.

[0096] Example 13 A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F in Example 1 was changed to the self-crosslinking resin M. The results are shown in Table 1.

[0097] Example 14 A conductive film was produced and measured in the same manner as in Example 1, except that 0.3 g of sodium bicarbonate was added to the conductive polymer dispersion in Example 1. The results are shown in Table 1.

[0098] (Comparative Example 1) A coating material was prepared in the same manner as in Example 1, except that the PEDOT-PSS aqueous dispersion was not added, and a film was prepared by coating the coating material and then measured. The results are shown in Table 1.

[0099] (Comparative Example 2) A conductive film was produced and measured in the same manner as in Example 1, except that KM-3951 and CAT-PM-10A were not added. The results are shown in Table 1.

[0100] (Comparative Example 3) A conductive film was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F was not added. The results are shown in Table 1.

[0101] <Evaluation> [Surface resistance value] For the conductive film of each example, the surface resistance value of the conductive release 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. In the table, "Ω / □" means ohms per square. "1.0E+08" means "1.0 x 10 8 " and so on.

[0102] [Peeling force] For the conductive film of each example, the peel force was measured by the following method, and the releasability of the conductive release layer was evaluated. A 25 mm wide polyester adhesive tape (Nitto Denko Corporation, No. 31B) was attached to the surface of the conductive release layer of the conductive film, and a load of 1976 Pa was applied to the adhesive tape, followed by a pressure treatment at 25°C for 20 hours. Next, in accordance with JIS Z0237, the adhesive tape attached to the conductive release layer was peeled off at an angle of 180° (peel speed 0.3 m / min) using a tensile tester, and the peel force (unit: N / 25 mm) was measured. The measurement results are shown in Table 1. A smaller peel force indicates a higher releasability of the release layer.

[0103] [Adhesion] For each conductive film, the surface of the conductive release layer was rubbed with a finger 10 times, and the degree of damage to the conductive release layer was evaluated according to the following criteria. The results are shown in Table 1. (Rating 1): The conductive release layer completely falls off within the fifth finger rub, and the conductive release layer loses its conductivity and easy peelability. In other words, the adhesion between the conductive release layer and the polypropylene film is poor. (Rating 2): The conductive release layer remains after the first 5 finger rubs, but after the 10th rub, the conductive release layer falls off completely, losing conductivity and easy peelability. In other words, the adhesion between the release layer and the polypropylene film is poor. (Rating 3): The conductive release layer did not come off within 10 finger rubs, but the color of the conductive release layer changed significantly, and the conductivity and ease of peeling decreased. In other words, the adhesion between the conductive release layer and the polypropylene film was average. (Rating 4): The conductive release layer did not come off within 10 finger rubs, and although there was a slight change in the color of the conductive release layer, there was almost no decrease in conductivity or ease of peeling. In other words, the adhesion between the conductive release layer and the polypropylene film was excellent. (Rating 5): The conductive release layer did not fall off within 10 finger rubs, the color of the conductive release layer did not change, and the conductivity and ease of peeling were not reduced. In other words, the adhesion between the conductive release layer and the polypropylene film was particularly excellent. In the five-point evaluation criteria above, ease of peeling (releasability) is based on the results of testing the ease of peeling off adhesive tape applied to a surface that has been rubbed with a finger. Discoloration of the conductive release layer indicates the degree of peeling at the interface between the conductive release layer and the polypropylene film. If this interface is partially peeled off, the interface will lift up when peeling off adhesive tape applied to the surface of the conductive release layer, reducing peelability.

[0104] [Table 1]

[0105] The conductive polymer dispersions of Examples 1 to 14 contain a silicone emulsion, an alkoxysilyl group-containing acrylic resin, and a polyester resin, and therefore the conductive release layer formed from the coating film has good conductivity and releasability, and the conductive release layer has excellent adhesion to the substrate. The conductive polymer dispersion of Example 14 contains a basic compound, which improves wettability to the substrate. The paint of Comparative Example 1 does not contain a conductive complex, so not only is the conductivity of the formed coating film poor, but the releasability is also poor. This result shows that the conductive complex improves the releasability of the silicone emulsion in the examples. The conductive polymer dispersion of Comparative Example 2 does not contain a silicone emulsion, and therefore the releasability of the formed conductive layer is significantly poor. The conductive polymer dispersion of Comparative Example 3 does not contain a polyester resin or an alkoxysilyl group-containing acrylic resin, and therefore the conductive layer formed has poor adhesion to the substrate.

Claims

1. A conductive polymer dispersion liquid containing a conductive complex including a polyanion that is not a π-conjugated conductive polymer and a π-conjugated conductive polymer, a silicone emulsion, an alkoxysilyl group-containing acrylic resin different from the polyanion, a polyester resin different from the polyanion, and an aqueous dispersion medium.

2. The conductive polymer dispersion according to claim 1 , wherein the content of water contained in the aqueous dispersion medium is 40 parts by mass or more relative to 1 part by mass of the conductive composite.

3. 3. The conductive polymer dispersion according to claim 1, wherein the number of carbon atoms in the 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 according to claim 1 or 2, wherein the polyester resin has at least one group selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxyl group.

5. 5. The conductive polymer dispersion according to claim 4, wherein a content ratio expressed by (the alkoxysilyl group-containing acrylic resin / the polyester resin) is 5 / 95 to 50 / 50 based on the mass of the solid content.

6. The conductive polymer dispersion according to claim 1 or 2, further comprising a basic compound.

7. 3. The conductive polymer dispersion according to claim 1, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrenesulfonic acid.

8. A substrate and a conductive release layer formed on at least a portion of the surface of the substrate, 3. A conductive laminate, wherein the conductive release layer is a cured product of the conductive polymer dispersion according to claim 1.

9. The conductive laminate according to claim 8 , wherein the substrate is a polypropylene film.

10. A method for producing a conductive laminate, comprising: applying the conductive polymer dispersion according to claim 1 or 2 to at least a part of the surface of a substrate to form a conductive layer.

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