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

Abstract

To provide a conductive polymer dispersion capable of forming a conductive layer in which blueness derived from a polythiophene-based conductive polymer is alleviated as compared with a conventional one (color coordinate b * is positively shifted as compared with a conventional one), a conductive laminate having the conductive layer, and a method for producing the same.SOLUTION: A conductive polymer dispersion comprising: a polythiophene-based conductive polymer; and at least one dye whose aqueous solution has an absorption maximum in a range of 350 to 550nm. The dye is preferably a water-soluble dye having a dissolution rate of 0. 1g or more in an aqueous 100g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer dispersion containing a polythiophene-based conductive polymer, a conductive laminate, and a method for producing a conductive laminate. [Background technology]

[0002] Conductive layers containing polythiophene-based conductive polymers, such as PEDOT-PSS, are formed on the surface of transparent substrates such as glass or resin films, and are sometimes used as circuit boards or electrodes. When used in touch panels or displays, high transparency is often required for the circuit boards, but because PEDOT-PSS is inherently blue, the conductive layer also exhibits a blue color (see, for example, Patent Document 1). This blue hue (bluish tint) is particularly pronounced in conductive layers (low-resistivity films) with a surface resistance of 1000 Ω / Sq. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-138012 Summary of the Invention [Problem to be solved by the invention]

[0004] Conductive layers made of indium tin oxide (ITO), which is widely used as a transparent conductive substrate, have a yellowish color tone, so a conductive layer made of PEDOT-PSS may also be required to have a color tone similar to that of the ITO substrate.

[0005] The present invention provides a conductive polymer dispersion capable of forming a conductive layer in which the blue tinge inherent in polythiophene-based conductive polymers is alleviated compared to conventional methods (the color coordinate b* is shifted more positively than conventional methods), a conductive laminate including the conductive layer, and a method for producing the same. [Means for solving the problem]

[0006] [1] A conductive polymer dispersion containing a polythiophene-based conductive polymer, a solvent, and at least one dye whose aqueous solution has a maximum absorption wavelength in the range of 350 to 550 nm. [2] The conductive polymer dispersion according to [1], wherein the polythiophene-based conductive polymer is poly(3,4-ethylenedioxythiophene) or a derivative of poly(3,4-ethylenedioxythiophene). [3] The conductive polymer dispersion according to [1] or [2], further comprising a polyanion, wherein the polyanion forms a conductive complex together with the polythiophene-based conductive polymer. [4] The conductive polymer dispersion according to [3], wherein the polyanion is polystyrene sulfonic acid. [5] The conductive polymer dispersion liquid according to any one of [1] to [4], wherein the dye is a water-soluble dye having a solubility of 0.1 g or more in 100 g of water. [6] The conductive polymer dispersion liquid according to [5], wherein the water-soluble dye is at least one selected from the group consisting of azo dyes and anthraquinone dyes. [7] The conductive polymer dispersion according to any one of [1] to [6], wherein the total content of the dyes is 1 to 100 parts by mass per 100 parts by mass of the solid content of the conductive composite. [8] The conductive polymer dispersion according to any one of [1] to [7], which contains at least one binder component selected from the group consisting of a thermoplastic resin, a curable monomer, a curable oligomer, and a silicon oxide compound. [9] A method for producing a conductive laminate, comprising applying the conductive polymer dispersion according to any one of [1] to [8] to at least a part of the surface of a substrate.

[10] A conductive laminate comprising a substrate and a conductive layer formed on at least a part of the surface of the substrate, the conductive layer being made of a cured product of the conductive polymer dispersion according to any one of [1] to [8]. [Effects of the Invention]

[0007] By using the conductive polymer dispersion of the present invention, a conductive layer can be formed in which the blue tinge derived from polythiophene is alleviated (the color coordinate b* is shifted to the positive side). Furthermore, in the conductive polymer dispersion of the present invention, the dye is stably dissolved, and the formed conductive layer has good heat resistance and is less likely to fade. According to the method for producing a conductive laminate of the present invention, a conductive laminate having the above-described excellent conductive layer can be easily produced.

[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. In this specification and claims, "color coordinates" refer to color coordinates defined by CIE1976. DETAILED DESCRIPTION OF THE INVENTION

[0010] <<Conductive polymer dispersion>> A first aspect of the present invention is a conductive polymer dispersion liquid containing a polythiophene-based conductive polymer, a solvent, and at least one dye having a maximum absorption wavelength in the range of 350 to 550 nm in the solvent.

[0011] <Polythiophene-based conductive polymer> 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). Among these, poly(3,4-ethylenedioxythiophene) is particularly preferred because of its excellent conductivity, transparency, and heat resistance. The polythiophene-based conductive polymer of this embodiment may be a derivative in which any hydrogen atom in the molecule is optionally substituted.

[0012] <Solvent> The solvent contained in the conductive polymer dispersion is preferably one that can dissolve (i.e., disperse) the polythiophene-based conductive polymer and the dye. The hydrophilicity of the polythiophene-based conductive polymer increases when it forms a conductive complex with a polyanion, which will be described later. When a conductive complex is not formed, an organic solvent is preferred as the solvent. There are no particular restrictions on the type of organic solvent, and a water-soluble organic solvent that can also dissolve the water-soluble dye is preferred. Suitable organic solvents will be described later.

[0013] In this specification, the conductive polymer dispersion to which a water-soluble organic solvent has been added is sometimes referred to as a coating composition (paint). The coating composition contains a water-soluble organic solvent, which enhances the wettability of the coating composition with respect to the substrate.

[0014] <Dye> The dye contained in the conductive polymer dispersion of this embodiment may be any dye that has a maximum absorption wavelength of 350 to 550 nm in its aqueous solution. Furthermore, the dye preferably has a maximum absorption wavelength of 350 to 550 nm in the solvent that constitutes the conductive polymer dispersion. By including this dye, the blue tint of the conductive layer made of the cured product of the conductive polymer dispersion of this embodiment can be reduced, and the color coordinate b* can be shifted more positively than in conventional cases. The amount of the dye contained in the aqueous solution can be, for example, 10 mg to 400 mg.

[0015] The dye is preferably soluble in the solvent. When the conductive polymer dispersion contains a sufficient amount of water, the dye is preferably soluble in water, and more preferably a water-soluble dye having a solubility of 0.1 g or more in 100 g of water at 20°C.

[0016] The water-soluble dye is preferably one or more selected from azo dyes and anthraquinone dyes. Here, azo dyes refer to dyes having an -N=N- bond in the molecule, and anthraquinone dyes refer to dyes having an anthraquinone skeleton in the molecule. The use of these dyes enhances the heat resistance of the conductive layer formed from the cured product of the conductive polymer dispersion of this embodiment, making it less susceptible to fading due to heat. Furthermore, since there is no chemical interference with the polythiophene conductive polymer, it is easy to adjust the color tone without adversely affecting the conductivity.

[0017] Specific preferred water-soluble dyes include, for example, anthraquinone dyes such as carminic acid, alizarin, and alizarin red S; azo dyes such as chrome yellow, tropaeolin O, methyl orange, and 4-phenylazophenol; and flavonoid dyes such as rutin, hesperidin, and chalcone.

[0018] In order for the water-soluble dye to exhibit a color tone within the desired range, the pH of the conductive polymer dispersion of this embodiment is preferably acidic, and is preferably not more than pH 4, and more preferably not more than pH 3. When the conductive polymer dispersion of this embodiment contains a polyanion having a sulfo group, the pH will be not more than 3 unless neutralized.

[0019] The content of the dye contained in the conductive polymer dispersion of this embodiment is preferably 1 to 100 parts by mass relative to 100 parts by mass of the conductive composite described below. The content of the dye contained in the conductive polymer dispersion of this embodiment is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polythiophene-based conductive polymer.

[0020] <Polyanion> The conductive polymer dispersion of this embodiment preferably further contains a polyanion, and the polyanion and the polythiophene-based conductive polymer preferably form a conductive complex. A polyanion is a polymer containing two or more monomer units with an anionic group in the molecule. The anionic group of the polyanion functions as a dopant for the polythiophene-based conductive polymer, improving the conductivity of the polythiophene-based conductive polymer. The polyanion constituting the conductive composite has only a portion of the anionic groups doped into the polythiophene-based conductive polymer, and has excess anionic groups that are not involved in the doping. Because the excess anionic groups are hydrophilic, the conductive composite has water dispersibility.

[0021] The anion group of the polyanion is preferably a sulfo group or a carboxy group. Specific examples of 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 (e.g., 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 monomers. Among these polyanions, polymers having sulfo groups are preferred, and polystyrene sulfonic acid is more preferred, since they can further increase the conductivity.

[0022] The weight-average molecular weight Mw of the polyanion is preferably from 20,000 to 1,000,000, and more preferably from 50,000 to 800,000. The weight-average molecular weight Mw is measured using gel filtration chromatography and is the average molecular weight on a mass basis calculated as pullulan.

[0023] The conductive polymer dispersion of this embodiment may contain one or more types of polyanions, and the conductive composite may contain one or more types of polythiophene-based conductive polymers.

[0024] 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 polythiophene-based conductive polymer. If the content of the polyanion is equal to or greater than the lower limit, the doping effect on the polythiophene-based 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 relative proportion of the polythiophene-based conductive polymer can be increased, thereby ensuring conductivity.

[0025] When the conductive polymer dispersion of this embodiment contains a conductive complex, the solvent preferably contains water, from the viewpoint of improving the dispersibility of the conductive complex. A solvent containing water may be particularly referred to as an aqueous solvent.

[0026] The content of water relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 30 to 90 mass %, more preferably 40 to 80 mass %. The content of the water-soluble organic solvent relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 10 to 50 mass %, more preferably 15 to 40 mass % or more. Within this range, the water-soluble organic solvent is particularly preferably a monohydric alcohol. Within the above preferred range, the wettability to the substrate can be improved and the dye can be sufficiently dissolved while maintaining the dispersion stability of the conductive complex in the conductive polymer dispersion.

[0027] The content of the conductive complex relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.1 mass % or more and 1.8 mass % or less, more preferably 0.2 mass % or more and 1.2 mass % or less, and even more preferably 0.3 mass % or more and 0.8 mass % or less. When the content is at least as large as the lower limit of the above range, the conductivity of the conductive layer formed by curing 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 the storage stability of the conductive polymer dispersion can be improved.

[0028] <Low boiling point solvent> The conductive polymer dispersion of this embodiment may contain one or more low-boiling point solvents. The low-boiling point solvent is an organic solvent having a boiling point of less than 150° C. at 1 atmosphere (101,325 Pascals). The boiling point is preferably 50° C. or higher and 100° C. or lower. By including a low-boiling point solvent, the dispersibility of the dye can be improved.

[0029] The low-boiling point solvent may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent, but is preferably a water-soluble organic solvent from the viewpoint of preventing phase separation of the conductive polymer dispersion of this embodiment. Here, the 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 the 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.

[0030] Examples of the water-soluble organic solvent include alcohol-based solvents, ether-based solvents, and ketone-based solvents. Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol (tert-butyl alcohol), 1-butanol, and 2-butanol. Examples of the ether solvent include diethyl ether and dimethyl ether. Examples of ketone solvents include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl ethyl ketone, and acetone. The water-soluble organic solvents may be used alone or in combination of two or more. The water-soluble organic solvent is preferably an alcohol-based solvent or a ketone-based solvent, as this improves the coatability of the conductive polymer dispersion onto the film substrate.

[0031] Examples of the non-water-soluble organic solvent include hydrocarbon solvents, etc. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, pentane, heptane, and octane. Examples of aromatic hydrocarbon solvents include benzene, toluene, and xylene.

[0032] The content of the low boiling point solvent relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, and even more preferably 20% by mass to 35% by mass. When the content is at least the lower limit of the above range, the solubility of the dye can be increased, and the wettability of the dye to the substrate can be increased. When the content is equal to or less than the upper limit of the above range, the dispersibility of the conductive composite can be improved.

[0033] <High boiling point solvent> The conductive polymer dispersion of this embodiment may contain one or more high-boiling point solvents. The high-boiling point solvent of this embodiment is an organic solvent having a boiling point of 150° C. or higher at 1 atmosphere (101,325 Pascals). The boiling point is preferably lower than 260° C. By including a high-boiling point solvent, effects such as improved conductivity can be obtained.

[0034] Examples of high-boiling point solvents include water-soluble organic solvents and water-insoluble organic solvents, where the definitions of water-soluble organic solvents and water-insoluble organic solvents are the same as those described above.

[0035] Examples of high-boiling water-soluble organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen-atom-containing solvents, and sulfur-atom-containing solvents. Examples of alcohol-based solvents include polyhydric alcohols such as ethylene glycol (boiling point 198°C), 1,2-propanediol (also known as propylene glycol, boiling point 188°C), 1,3-propanediol (boiling point 214°C), 1,2-butanediol (boiling point 194°C), 1,3-butanediol (boiling point 207°C), 1,4-butanediol (boiling point 228°C), dipropylene glycol (boiling point 232°C, mixture of isomers), and diethylene glycol (boiling point 245°C). Examples of ether solvents include diethylene glycol dimethyl ether (boiling point 162°C) and diethylene glycol diethyl ether (boiling point 188°C). Examples of ketone solvents include methyl amyl ketone (boiling point 151°C) and diacetone alcohol (boiling point 168°C). Examples of nitrogen atom-containing solvents include N-methylpyrrolidone (boiling point 202°C), N-methylacetamide (boiling point 206°C), dimethylacetamide (boiling point 165°C), and N,N-dimethylformamide (boiling point 153°C). An example of the sulfur atom-containing solvent is dimethyl sulfoxide (boiling point: 189° C.).

[0036] Examples of the high-boiling point water-insoluble organic solvent include hydrocarbon solvents, etc. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include nonane (boiling point 151° C.), decane (boiling point 174° C.), and dodecane (boiling point 216° C.). Examples of aromatic hydrocarbon solvents include propylbenzene (boiling point 159°C) and isopropylbenzene (boiling point 152°C).

[0037] Among the above examples, alcohol-based high-boiling point solvents are preferred because they provide a greater effect of improving conductivity. Among alcohol-based high-boiling point solvents, ethylene glycol (boiling point 198°C), 1,2-propanediol (boiling point 188°C), 1,3-propanediol (boiling point 214°C), and dimethyl sulfoxide (boiling point 189°C) are preferred because of their excellent effects in improving conductivity, and ethylene glycol, 1,2-propanediol, and 1,3-propanediol are more preferred.

[0038] The content of the high-boiling point solvent relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 1.0% by mass to 10.0% by mass, more preferably 2.0% by mass to 8.0% by mass, and even more preferably 3.0% by mass to 6.0% by mass. Within this range, the conductivity of the formed conductive layer is further improved.

[0039] <Unsaturated fatty alcohol compounds> The conductive polymer dispersion of this embodiment may contain one or more unsaturated aliphatic alcohol compounds. The unsaturated aliphatic alcohol compound is an alcohol having one or more double bonds or triple bonds between carbon atoms in the molecule and one or more hydroxyl groups (hydroxyl groups) in the molecule. The boiling point of the unsaturated aliphatic alcohol compound may be less than 150°C or may be 150°C or higher. When there are two or more hydroxyl groups in the molecule, the boiling point is likely to be 150°C or higher.

[0040] The conductive polymer dispersion of this embodiment contains an unsaturated aliphatic alcohol compound, which can further improve the conductivity and heat resistance of the conductive layer formed. From the viewpoint of further enhancing this effect, the unsaturated aliphatic alcohol compound is preferably a diol having two hydroxyl groups. From the same viewpoint, the unsaturated aliphatic alcohol compound preferably has 4 or more and 12 or less carbon atoms, more preferably 4 or more and 10 or less carbon atoms, further preferably 4 or more and 8 or less carbon atoms, and particularly preferably 4 or more and 6 or less carbon atoms. From the same viewpoint, the number of unsaturated bonds contained in the unsaturated aliphatic alcohol compound is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and even more preferably 1 or 2.

[0041] The unsaturated aliphatic alcohol is preferably at least one selected from the group consisting of cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, 2-butyne-1,4-diol, and 2,4-hexadiyn-1,6-diol. Other examples include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol.

[0042] The content of the unsaturated aliphatic alcohol compound relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.1 mass % or more and 3 mass % or less, more preferably 0.4 mass % or more and 2.0 mass % or less, and even more preferably 0.7 mass % or more and 1.5 mass % or less. When the content is at least as large as the lower limit of the above range, the conductivity and heat resistance of the conductive layer can be further improved, and when the content is at most the upper limit of the above range, the drying time of the coating film of the conductive polymer dispersion can be further shortened.

[0043] <Binder components> The conductive polymer dispersion of this embodiment may further contain a binder component. The binder component is a compound other than the polythiophene-based conductive polymer, polyanion, and dye, and is a component capable of binding the polythiophene-based conductive polymer to a substrate or the like. The binder component is preferably at least one selected from the group consisting of thermoplastic resins, curable monomers, curable oligomers, and silicon oxide compounds (such as silica). The thermoplastic resin acts as a binder as it is, and the curable monomer, oligomer, and silicon oxide compound act as a binder (binding material) when they are cured to form a cured product.

[0044] Specific examples of binders derived from binder components include acrylic resins, polyester resins, polyurethane resins, polyimide resins, polyether resins, melamine resins, silicones, alkoxysilane condensates, and silicate condensates. In this specification, the alkoxysilane condensate and the silicate condensate are sometimes collectively referred to as silane compounds. The conductive polymer dispersion of this embodiment may contain one type of binder component or two or more types of binder components.

[0045] When the binder component is a thermoplastic resin, the binder resin is preferably a water-dispersible resin that can be dispersed in the conductive polymer dispersion. The water-dispersible resin is an emulsion resin or a water-soluble resin. Specific examples of emulsion resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, melamine resins, etc., which are emulsionized with an emulsifier. Specific examples of water-soluble resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, and melamine resins, which have an acid group such as a carboxy group or a sulfo group, or a salt thereof. The water-soluble resin dissolves in distilled water at 25° C. in an amount of 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more.

[0046] When the substrate to which the conductive polymer dispersion of this embodiment is applied is made of a polyester resin, the binder component preferably contains one or more types selected from the above-mentioned water-dispersible polyester resins.

[0047] When the conductive polymer dispersion of this embodiment contains the thermoplastic resin, the content of the solids (non-volatile components) is preferably 10 parts by mass or more and 5000 parts by mass or less, more preferably 50 parts by mass or more and 2000 parts by mass or less, and even more preferably 100 parts by mass or more and 1000 parts by mass or less, relative to 100 parts by mass of the conductive composite. When the content of the thermoplastic resin is at least the lower limit of the above range, the strength of the conductive layer and the adhesion to the substrate can be further improved. When the content of the thermoplastic resin is equal to or less than the upper limit of the above range, it is possible to suppress a decrease in conductivity due to a relative decrease in the content of the conductive composite.

[0048] In this specification, alkoxysilane refers to a compound having one silicon atom in the molecule, with one or more alkoxy groups bonded to the silicon atom. The alkoxysilane included in this embodiment preferably has a methoxy group or an ethoxy group because it is easily hydrolyzed. The alkoxysilane may have, as a functional group other than the alkoxy group, for example, an epoxy group, an allyl group, a vinyl group, a glycidyl group, or the like. Specific preferred alkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

[0049] The content of alkoxysilane in the conductive polymer dispersion of this embodiment is preferably 10 parts by mass or more and 10,000 parts by mass or less, more preferably 50 parts by mass or more and 5,000 parts by mass or less, and even more preferably 100 parts by mass or more and 2,000 parts by mass or less, relative to 100 parts by mass of the conductive composite. When the content of alkoxysilane is equal to or greater than the lower limit, the hardness of the conductive layer formed from the conductive polymer dispersion can be sufficiently increased, and when the content is equal to or less than the upper limit, a decrease in the conductivity of the conductive layer formed from the conductive polymer dispersion can be prevented.

[0050] In this specification, silicate refers to a compound having two or more silicon atoms in one molecule, with at least one pair of silicon atoms being ether-bonded via an oxygen atom. The number of silicon atoms in one molecule of the silicate is preferably four or more, more preferably six or more, and even more preferably eight or more, since this increases the hardness of the conductive layer formed from the conductive polymer dispersion of this embodiment. Furthermore, from the viewpoint of increasing the solubility of the silicate in the conductive polymer dispersion of this embodiment, the number of silicon atoms in one molecule of the silicate is preferably 40 or less, more preferably 30 or less. The content of SiO2 units in the silicate is preferably 15% by mass or more and 70% by mass or less, and more preferably 25% by mass or more and 50% by mass or less, relative to the total mass of the silicate. If the content of SiO2 units in the silicate is equal to or more than the lower limit, the hardness of the conductive layer formed from the conductive polymer dispersion of this embodiment will be higher, and if it is equal to or less than the upper limit, a decrease in the conductivity of the conductive layer can be prevented. Here, the content of SiO2 units in silicate refers to the mass ratio of SiO2 units (-O-Si-O- units) contained in the silicate relative to 100% by mass of the molecular weight of the silicate, and can be measured by elemental analysis.

[0051] The silicate is preferably a compound represented by the following chemical formula (X). (X)… R 3 O-[(R 4 O-)(R 5 O-)Si-O-] s -R 6

[0052] In formula (X), R 3 , R 4 , R 5 , and R 6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and s is an integer of 2 to 100. The alkyl group having 1 to 4 carbon atoms may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. s is preferably 2-50, more preferably 3-25, and further preferably 4-10.

[0053] The silicate is more preferably at least one of a compound represented by the following chemical formula (x1) and a compound represented by the following chemical formula (x2). (x1)… Si m O m-1 (OCH3) 2m+2 (x2)…Si n O n-1 (OCH2CH3) 2n+2 In the above formulas (x1) and (x2), m is 2 or more and 100 or less, and n is 2 or more and 100 or less. In the above formulae (x1) and (x2), Si and O are bonded, and Si and O are not adjacent to each other and are not adjacent to each other.

[0054] The preferred content of silicate in the conductive polymer dispersion is appropriately selected depending on the content of SiO units in the silicate. When the content of SiO units in the silicate is within the preferred range described above, the content of silicate is preferably 1 part by mass or more and 100,000 parts by mass or less, more preferably 10 parts by mass or more and 10,000 parts by mass or less, and even more preferably 100 parts by mass or more and 2,000 parts by mass or less, relative to 100 parts by mass of the conductive composite. When the silicate content is equal to or greater than the lower limit, the hardness of the conductive layer formed from the conductive polymer dispersion can be sufficiently increased, and when the silicate content is equal to or less than the upper limit, a decrease in the conductivity of the conductive layer formed from the conductive polymer dispersion can be prevented.

[0055] When the substrate to which the conductive polymer dispersion of this embodiment is applied is made of glass, the binder component preferably contains one or more selected from the above-mentioned alkoxysilanes or silicates.

[0056] As the silica, colloidal silica is preferred from the viewpoint of dispersibility, and colloidal silica dispersible in an organic solvent (hereinafter also referred to as "organosilica sol") is more preferred. Examples of commercially available organosilica sol products include methanol silica sol, MA-ST-M, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, EG-ST-ZL, DMAC-ST, DMAC-ST-ZL, NPC-ST-30, PGM-ST, MEK-ST, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-SD, PMA-ST, EAC-ST, NBAC-ST, XBA-ST, TOL-ST, MEK-AC-2101, MEK-AC-4101 (trade names, manufactured by Nissan Chemical Industries, Ltd.); OSCAL-1432, OSCAL-1132, OSCAL-1632, OSCAL-1421 (trade names, manufactured by Nikki Catalysts and Chemicals Co., Ltd.), and Snowtex ST-OS (trade name, manufactured by Nissan Chemical Industries, Ltd.).

[0057] [Antioxidants] The conductive polymer dispersion of this embodiment may contain an antioxidant (stabilizer). Among antioxidants, phenol-based antioxidants are preferred. Among phenol-based antioxidants, at least one of gallic acid (gallic acid) and esters of gallic acid is preferred. Gallic acid and esters of gallic acid exhibit high antioxidant performance and also have the effect of improving electrical conductivity. Examples of esters of gallic acid include methyl gallate, ethyl gallate, and propyl gallate. As other phenolic antioxidants, bisphenol compounds having a sulfide group or a sulfone group can also be suitably used. Examples of bisphenol compounds having a sulfide group or a sulfone group include bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) disulfide, bis(4-hydroxyphenyl) sulfone, and bis(2,4-dihydroxyphenyl) sulfide.

[0058] The content of the antioxidant is preferably 5 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less, and even more preferably 20 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the conductive composite. When the content is equal to or more than the lower limit of the above range, oxidation of the conductive composite can be further prevented. When the content is equal to or less than the upper limit of the above range, a decrease in the conductivity of the conductive composite can be prevented.

[0059] <Acetylene-based surfactants> The conductive polymer dispersion of this embodiment preferably contains one or more acetylene-based surfactants, which enhances wettability to the surface of the glass substrate and allows the formation of a conductive layer with a uniform thickness.

[0060] The acetylene surfactant is a nonionic compound having at least one triple bond between carbon atoms in the molecule. Suitable examples of the acetylene surfactant include wetting agents manufactured by Nissin Chemical Industry Co., Ltd., such as Olfine EXP4200, Dynol 604, Dynol 607, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104PA, Surfynol 104S, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol SE, Surfynol SE-F, Surfynol PSA-336, and Surfynol 2502.

[0061] The number of carbon atoms in the molecule of the acetylene surfactant is preferably 11 to 100, more preferably 12 to 70, even more preferably 13 to 50, and most preferably 14 to 40. When the number of carbon atoms is within these suitable ranges, the wettability is further improved. The acetylene surfactant preferably has a hydroxyl group or an oxygen atom forming an ether bond in the molecule, which further improves wettability.

[0062] The content of the acetylene surfactant relative to the total mass of the conductive polymer dispersion of this embodiment is preferably 0.0001 mass% or more and 0.50 mass% or less, more preferably 0.001 mass% or more and 0.10 mass% or less, and even more preferably 0.005 mass% or more and 0.05 mass% or less. When the content is within the above range, the wettability to the surface of the glass substrate is further increased, and a conductive layer with a uniform thickness can be more easily formed.

[0063] <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. However, the additives are other than the polythiophene-based conductive polymer, dye, polyanion, unsaturated aliphatic alcohol compound, solvent, binder component, and antioxidant. 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 antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil. 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.

[0064] 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.

[0065] <Method of manufacturing conductive polymer dispersion> The conductive polymer dispersion of the first embodiment can be produced by blending the materials in a solvent, and then mixing and stirring the blended materials. From the viewpoint of blending the dye stably, it is preferable to add the dye last after blending the materials other than the dye.

[0066] Known methods can be used to form the conductive composite. For example, when a thiophene-based compound is polymerized in the presence of a polyanion to synthesize a polythiophene-based conductive polymer, the polyanion spontaneously dopes the polythiophene-based conductive polymer formed by the polymerization reaction. Since water is usually used as the solvent for the reaction solution, the conductive composite is obtained in a water-dispersed state. In this specification and claims, no distinction is made between a dispersed state and a dissolved state unless otherwise specified.

[0067] The content ratio (by mass) of polythiophene-based conductive polymer to polyanion constituting the conductive composite formed by polymerization is approximately the same as the ratio of thiophene-based compound to polyanion blended in the reaction solution. In other words, the content ratio of monomer to polyanion blended in the reaction solution is reflected in the content ratio of polythiophene-based conductive polymer to polyanion in the conductive composite contained in the conductive polymer dispersion.

[0068] <Conductive laminate> A second aspect of the present invention is a conductive laminate comprising a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer comprising a cured product of the conductive polymer dispersion of the first aspect.

[0069] [Conductive layer] The conductive layer may be formed over the entire surface of the substrate or over only a portion of the surface. In a conductive film, it is preferable that a conductive layer of substantially uniform thickness is formed over substantially the entire surface of one or the other of the film substrate. When a conductive layer is formed over only a portion of the surface of the substrate, the conductive layer may be, for example, a fine conductive pattern such as a circuit or electrode, or may be simply a roughly divided area where a conductive layer is provided and an area where a conductive layer is not provided exist on the same surface.

[0070] The average thickness of the conductive layer is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and even more preferably 30 nm or more and 30 μm or less. When the average thickness of the conductive layer is equal to or greater than the lower limit, the conductive layer can exhibit sufficiently high conductivity, and when the average thickness is equal to or less than the upper limit, the adhesiveness of the conductive layer to the substrate is further improved.

[0071] As an indicator of good conductivity of the conductive layer of this embodiment, for example, it is preferable that the conductive layer has a surface resistance value of 10 Ω / sq. or more and 10,000 Ω / sq. or less, more preferably a surface resistance value of 10 Ω / sq. or more and 5,000 Ω / sq. or less, even more preferably a surface resistance value of 10 Ω / sq. or more and 2,500 Ω / sq. or less, and particularly preferably a surface resistance value of 10 Ω / sq. or more and 1,000 Ω / sq. or less.

[0072] The chromaticity of the conductive layer of this embodiment can be evaluated by a* and b*, which are measured and calculated based on JIS Z8722:2009 and JIS Z 8781-4:2013 Colorimetry - Part 4: CIE 1976 L*a*b* color space. The a* value of the conductive layer in this embodiment is preferably in the range of −1.1 to 0.7. The b* value of the conductive layer in this embodiment is preferably −0.2 or more, more preferably −0.1 or more, even more preferably 0.0 or more, and particularly preferably 0.1 or more. The upper limit of the b* value is usually 0.5 or less, and may be 0.4 or less.

[0073] [Base material] The substrate constituting the conductive laminate of this embodiment may be a substrate made of an insulating material or a substrate made of a conductive material. The shape of the substrate is not particularly limited, and examples thereof include shapes 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.

[0074] (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 layer, the synthetic resin for the film substrate is preferably the same type of resin as the binder resin, and among these, polyester resins such as polyethylene terephthalate are preferred.

[0075] 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 adhesiveness of the conductive layer formed from the conductive polymer dispersion.

[0076] 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.

[0077] (glass substrate) Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, and a quartz glass substrate. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease. Therefore, among the glass substrates, an alkali-free glass is preferred. Here, alkali-free glass refers to a glass composition having an alkali component content of 0.1% by mass or less relative to the total mass of the glass composition.

[0078] 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.

[0079] <Method for manufacturing conductive laminate> A third aspect of the present invention is a method for producing a conductive laminate, which includes applying the conductive polymer dispersion of the first aspect to at least a part of the surface of a substrate. By the production method of this aspect, the conductive laminate of the second aspect can be produced.

[0080] Examples of a method for coating (applying) the conductive polymer dispersion of the first embodiment onto any surface of a substrate include a method using a coater such as a gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, or screen coater; a method using a sprayer such as an air spray, airless spray, or rotor dampening; and an immersion method such as dipping.

[0081] The amount of conductive polymer dispersion to be applied to the film substrate is not particularly limited, but taking into consideration 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:

[0082] The coating film made of the conductive polymer dispersion applied onto the substrate is dried to remove the solvent, thereby obtaining a conductive laminate in which a conductive layer (conductive film) is formed by curing the coating film. Methods for drying the coating film include heat drying, vacuum drying, etc. Heat drying can be performed using, for example, hot air heating or infrared heating. When heat drying is applied, the heating temperature is set appropriately depending on the solvent used, but is usually within the range of 50°C to 150°C. Here, the heating temperature is the temperature set in the drying device. The suitable drying time within the above heating temperature range is preferably 1 minute to 30 minutes, more preferably 5 minutes to 15 minutes.

[0083] When the applied conductive polymer dispersion contains the above-mentioned silicon oxide-containing compound such as alkoxysilane, silicate, or silica as a binder component, the coating film can be heated to cause the binder components to react with each other, thereby forming a cured conductive layer. [Example]

[0084] (Production Example 1) Synthesis of Polyanion 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 resulting sodium polystyrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and approximately 1000 ml of the solvent from the resulting polystyrene sulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the remaining solution, and approximately 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This water washing procedure was repeated three times. Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

[0085] (Production Example 2) Synthesis of conductive composite 14.2 g of 3,4-ethylenedioxythiophene and a solution prepared by dissolving 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 in 2000 ml of ion-exchanged water were mixed at 20° C. The resulting mixed solution was kept at 20° C., and while stirring, an oxidation catalyst solution of 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate dissolved in 200 ml of ion-exchanged water was slowly added, followed by stirring for 3 hours to allow the reaction to proceed. After the reaction, 2000 ml of ion-exchanged water was added to the reaction solution, and about 2000 ml of the solvent was removed by ultrafiltration. This procedure was repeated three times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2,000 ml of ion-exchanged water were added to the resulting solution, and about 2,000 ml of the solvent was removed by ultrafiltration. 2,000 ml of ion-exchanged water was added to the remaining liquid, and about 2,000 ml of the solvent was removed by ultrafiltration. This procedure was repeated three times. 2000 ml of ion-exchanged water was added to the resulting solution, and approximately 2000 ml of the solvent was removed by ultrafiltration. This procedure was repeated five times to obtain an aqueous dispersion of polystyrene sulfonate-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) with a solids concentration of 1.2% by mass.

[0086] (Coating composition) Preparation of coating composition C1: 40 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 (solid content 0.48 g) was mixed with 10 g of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 10 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 30.9 g of ion-exchanged water, 5 g of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.05 g of bis(4-hydroxyphenyl) sulfide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.05 g of an acetylene-based surfactant (manufactured by Nissin Chemical Industry Co., Ltd., Olfin EXP4200) at room temperature and thoroughly mixed. Then, 3 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) and 1 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-13) were added as binder components and mixed at room temperature for 48 hours to prepare coating composition C1.

[0087] C2: To 60 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 (solid content 0.72 g), 15 g of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 13.9 g of ion-exchanged water, 1 g of 2-butyne-1,4-diol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.05 g of gallic acid monohydrate (manufactured by Junsei Chemical Co., Ltd.), and 0.05 g of an acetylene-based surfactant (manufactured by Nissin Chemical Industry Co., Ltd., Dynol 604) were added and mixed thoroughly at room temperature, and then 10 g of a water-dispersible polyester resin (manufactured by Takamatsu Oil & Fats Co., Ltd., PES Resin A125S) was added as a binder component and mixed at room temperature for 48 hours to prepare coating composition C2.

[0088] C3: 40 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 29.9 g of ion-exchanged water, 4 g of 1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.05 g of bis(4-hydroxyphenyl) sulfide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.05 g of an acetylene-based surfactant (manufactured by Nissin Chemical Industry Co., Ltd., Olfine EXP4200) were added to 20 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 (solid content 0.24 g), and the mixture was thoroughly mixed at room temperature. After that, 6 g of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04) was added as a binder component, and the mixture was mixed at room temperature for 48 hours to prepare coating composition C3.

[0089] (dye) D1: Carminic acid (CAS number 1260-17-9), an anthraquinone dye, maximum absorption wavelength 490 nm (solvent: water), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. D2: Chrome Yellow (CAS number 6054-97-3), azo dye, maximum absorption wavelength 450 nm (solvent: water), manufactured by Tokyo Chemical Industry Co., Ltd. D3: Alizarin Red S (CAS number 130-22-3), an anthraquinone dye, maximum absorption wavelength 510 nm (solvent: water), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. D4: Tropaeolin O (CAS number 547-57-9), azo dye, maximum absorption wavelength 430 nm (solvent: water), Fujifilm Wako Pure Chemical Industries, Ltd. D5: Rutin (CAS number 153-18-4), a flavonoid pigment with a maximum absorption wavelength of 360 nm (solvent: water), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. The solubility of each of D1 to D5 in 100 g of water at 20° C. is 0.1 g or more. D2P: A 2.00 wt% aqueous solution of dye D2 was prepared and purified using Duolite C255LHF (manufactured by Sumika Chemitech Co., Ltd.), a cation exchange resin, to remove sodium ions. The aqueous solution concentration after purification was 1.84 wt%. D3P: A 2.00 wt% aqueous solution of dye D3 was prepared and purified using Duolite C255LHF, a cation exchange resin, to remove sodium ions. The aqueous solution concentration after purification was 1.75 wt%.

[0090] [Example 1] 76 mg of dye D1 was added to 100 g of coating composition C1 and thoroughly mixed at room temperature to obtain a dye-added coating composition. The amount of dye was 15.8 g per 100 g of solids in the conductive composite (total of polythiophene-based conductive polymer and polyanion). This coating composition was applied to alkali-free glass (Corning Eagle XG, 75 mm x 75 mm x 0.7 mm) using a spin coater (Mikasa MS-B100, 400 rpm) to form a coating film. The coating film was then dried at 120°C for 10 minutes to produce a conductive laminate. The surface resistance of this conductive laminate was measured using a resistivity meter (Loresta manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under the condition of an applied voltage of 10 V and was found to be 360 ​​Ω / sq. Furthermore, the chromaticity of the conductive laminate measured using a spectrophotometer (CM-5 manufactured by Konica Minolta) under the condition of a D65 light source and a viewing angle of 2 degrees was a*=0.6 and b*=-0.1. Here, the chromaticity is a value measured and calculated based on JIS Z8722:2009 and JIS Z 8781-4:2013 Colorimetry - Part 4: CIE 1976 L*a*b* color space.

[0091] [Example 2] Except for changing dye D1 to dye D2, a conductive laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1. [Example 3] Except for changing dye D1 to dye D3, a conductive laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1. [Example 4] A conductive laminate was produced and evaluated in the same manner as in Example 1, except that dye D1 was changed to dye D4 and the amount added was changed to 90 mg. The amount of dye was 18.8 g per 100 g of solid content of the conductive composite. The results are shown in Table 1. [Example 5] A conductive laminate was produced and evaluated in the same manner as in Example 1, except that dye D1 was changed to dye D5 and the amount added was changed to 380 mg. The amount of dye was 79.2 g per 100 g of solid content of the conductive composite. The results are shown in Table 1. [Example 6] A conductive laminate was produced and evaluated in the same manner as in Example 1, except that dye D1 was replaced with a dye D2P aqueous solution and the amount added was changed to 4.00 g (amount of dye added: 74 mg). The amount of dye was 15.3 g per 100 g of solid content of the conductive composite. The results are shown in Table 1. [Example 7] A conductive laminate was produced and evaluated in the same manner as in Example 1, except that dye D1 was replaced with a dye D3P aqueous solution and the amount added was changed to 4.00 g (amount of dye added: 70 mg). The amount of dye was 14.6 g per 100 g of solid content of the conductive composite. The results are shown in Table 1. [Example 8] A conductive laminate was prepared and evaluated in the same manner as in Example 1, except that 38 mg of dye D1 and 38 mg of dye D2 were used in combination. The total amount of dyes was 15.8 g per 100 g of solid content of the conductive composite. The results are shown in Table 1.

[0092] [Example 9] 120 mg of dye D2 was added to 100 g of coating composition C2 and thoroughly mixed at room temperature to obtain a dye-added coating composition. The amount of dye was 16.7 g per 100 g of solids in the conductive composite. This coating composition was applied to a polyethylene terephthalate film (Cosmoshine A4360, manufactured by Toyobo Co., Ltd.) using a bar coater (wet film thickness 52 μm) to form a coating film. The coating film was then dried by heating at a drying temperature of 100°C for 10 minutes to produce a conductive laminate. The surface resistance and chromaticity of this conductive laminate were evaluated, and the results are shown in Table 1.

[0093] [Example 10] A conductive laminate was prepared and evaluated in the same manner as in Example 9, except that 60 mg of dye D1 and 60 mg of dye D2 were used in combination. The total amount of dyes was 16.7 g per 100 g of solid content of the conductive composite. The results are shown in Table 1. [Example 11] A conductive laminate was prepared and evaluated in the same manner as in Example 9, except that 60 mg of dye D2 and 48 mg of dye D3 were used in combination. The total amount of dyes was 15.0 g per 100 g of solid content of the conductive composite. The results are shown in Table 1.

[0094] [Example 12] 15 mg of dye D1 and 15 mg of dye D4 were added to 100 g of coating composition C3 and thoroughly mixed at room temperature to obtain a dye-added coating composition. The total amount of dye was 12.5 g per 100 g of solids in the conductive composite. This coating composition was applied to alkali-free glass (Corning Eagle XG, 75 mm x 75 mm x 0.7 mm) using a spray coater (Musashi Engineering Co., Ltd.) to form a coating film. The coating film was then dried at 120°C for 30 minutes to produce a conductive laminate. The surface resistance and chromaticity of this conductive laminate were evaluated, and the results are shown in Table 1.

[0095] [Example 13] A conductive laminate was produced and evaluated in the same manner as in Example 12, except that 55 mg of dye D2 was used. The total amount of dye was 22.9 g per 100 g of solid content of the conductive composite. The results are shown in Table 1.

[0096] [Table 1]

[0097] [Comparative Example 1] Except for not adding the dye, a conductive laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2. Comparative Example 2 Except for not adding the dye, a conductive laminate was produced and evaluated in the same manner as in Example 9. The results are shown in Table 2. Comparative Example 3 Except for not adding the dye, a conductive laminate was produced and evaluated in the same manner as in Example 12. The results are shown in Table 2.

[0098] [Table 2]

[0099] [Examples 14 to 19, Comparative Example 4] The conductive laminates obtained in Examples 1 to 8 and Comparative Example 1 were evaluated for thermal stability of color tone by the following method. The conductive laminate thus produced was kept at 85°C for 500 hours with the surface of the conductive layer exposed, and then kept at 24°C and 40% humidity for 24 hours. The surface resistance and chromaticity were measured, and the changes in chromaticity (Δa*, Δb*) are shown in Table 3.

[0100] [Table 3]

[0101] From the above, it was confirmed that the blue tint originating from polythiophene in the conductive layer of the conductive laminate produced using the conductive polymer dispersion of the example according to the present invention was alleviated (the color coordinate b* shifted positively). In addition, the heat resistance of the conductive layer was good, and the azo-based dye and quinone-based dye were resistant to fading and stable in the conductive polymer dispersion.

Claims

1. A conductive polymer dispersion containing a polythiophene-based conductive polymer, a solvent, and at least one dye whose aqueous solution has a maximum absorption wavelength in the range of 350 to 550 nm.

2. 2. The conductive polymer dispersion according to claim 1, wherein the polythiophene-based conductive polymer is poly(3,4-ethylenedioxythiophene) or a derivative of poly(3,4-ethylenedioxythiophene).

3. 3. The conductive polymer dispersion according to claim 2, further comprising a polyanion, wherein the polyanion forms a conductive complex together with the polythiophene-based conductive polymer.

4. The conductive polymer dispersion according to claim 3 , wherein the polyanion is polystyrene sulfonic acid.

5. 5. The conductive polymer dispersion according to claim 4, wherein the dye is a water-soluble dye having a solubility of 0.1 g or more in 100 g of water.

6. The conductive polymer dispersion according to claim 5 , wherein the water-soluble dye is at least one selected from the group consisting of azo dyes and anthraquinone dyes.

7. 7. The conductive polymer dispersion according to claim 6, wherein the total content of the dyes is 1 to 100 parts by mass per 100 parts by mass of the solid content of the conductive complex.

8. The conductive polymer dispersion according to claim 7 , comprising at least one binder component selected from the group consisting of a thermoplastic resin, a curable monomer, a curable oligomer, and a silicon oxide compound.

9. A method for producing a conductive laminate, comprising applying the conductive polymer dispersion according to any one of claims 1 to 8 to at least a part of a surface of a substrate.

10. A conductive laminate comprising: a substrate; and a conductive layer formed on at least a part of the surface of the substrate, the conductive layer comprising a cured product of the conductive polymer dispersion according to any one of claims 1 to 8.

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