Conductive laminate, method for manufacturing the same, and transparent electrode

Abstract

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

Description

Technical Field

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

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

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

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

Means for Solving the Problems

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

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

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

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

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

Embodiments for Carrying Out the Invention

[0010] ≪Conductive Laminate≫ The first aspect of the present invention is a conductive laminate including a glass substrate and a conductive layer in close contact with at least a part of the surface of the glass substrate. The conductive layer included in the conductive laminate of this aspect is a cured product of a conductive polymer dispersion containing a conductive composite including a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium. Hereinafter, the conductive polymer dispersion will be described.

[0011] [Conductive Composite] The conductive composite contained in the conductive polymer dispersion includes a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite dopes the π-conjugated conductive polymer to form a conductive composite having conductivity. In the polyanion, only some of the anion groups dope the π-conjugated conductive polymer, and it has surplus anion groups that do not participate in the doping. Since the surplus anion groups are hydrophilic groups, the conductive composite has water dispersibility.

[0012] (π-Conjugated Conductive Polymer) As the π-conjugated conductive polymer, any organic polymer whose main chain is composed of a π-conjugated system may be used. Examples thereof include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

[0013] Examples of polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-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), 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-didodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene). Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), and poly(3-methyl-4-hexyloxypyrrole). Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid). Among these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred because of its excellent conductivity, transparency, and heat resistance. The π-conjugated conductive polymer contained in the conductive composite may be one type or two or more types.

[0014] (Polyanion) A polyanion is a polymer having two or more monomer units having anionic groups in the molecule. The anionic groups of this polyanion function as dopants for the π-conjugated conductive polymer, 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 polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylate esters having a sulfo group, polymethacrylate esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate), polysulfoethyl methacrylate, polymethacryloyloxybenzene sulfonic acid), polymers having a sulfo group such as poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, etc., and polymers having a carboxy group such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid, etc. The polyanion may be a homopolymer in which a single monomer is polymerized, or a copolymer in which two or more monomers are polymerized. Among these polyanions, polymers having a sulfo group are preferred, and polystyrene sulfonic acid is more preferred because the conductivity can be made higher. The polyanion may be used alone or in combination of two or more. The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is the average molecular weight on a mass basis measured by gel filtration chromatography and determined in terms of pullulan.

[0015] The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less, more preferably 10 parts by mass or more and 700 parts by mass or less, and even more preferably 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer. If the content ratio of the polyanion is at least the lower limit value, the doping effect on the π-conjugated conductive polymer tends to be stronger and the conductivity becomes higher. On the other hand, if the content of the polyanion is at most the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

[0016] As the content of the conductive composite contained in the conductive polymer dispersion, 0.01% by mass or more and 5.0% by mass or less, preferably 0.10% by mass or more and 2% by mass or less, and more preferably 0.15% by mass or more and 1.0% by mass or less, based on the total mass of the conductive polymer dispersion, is preferable. When it is at least the lower limit value of the above range, the conductivity of the conductive layer formed by applying the conductive polymer dispersion can be further improved. When it is at most the upper limit value of the above range, the dispersibility of the conductive composite in the conductive polymer dispersion can be enhanced, and a uniform conductive layer can be formed.

[0017] [Alkoxysilyl group-containing acrylic resin] The alkoxysilyl group-containing acrylic resin is a homopolymer of a (meth)acrylic acid ester having an alkoxysilyl group, or a copolymer with other radically polymerizable monomers copolymerizable therewith. Here, the notation "(meth)acrylic" means "acrylic or methacrylic".

[0018] As the (meth)acrylic acid ester having an alkoxysilyl group, those represented by the following formula (Y) are preferable. (R 11 )3-Si-R 12 -O-C(=O)-C(-R 13 )=CH2···(Y) In the formula, the three Rs 11 are each independently an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and at least one of the three Rs 11 is the above alkoxy group. In the formula, R 12 is an alkylene group having 1 to 6 carbon atoms or a single bond, and R 13 is a hydrogen atom or a methyl group. In the formula, (R 11 )3-Si-R 12 - corresponds to the alkoxysilyl group.

[0019] Specific examples of the (meth)acrylate ester having an alkoxysilyl group include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and the like. The monomer having an alkoxysilyl group that constitutes the repeating unit of the alkoxysilyl group-containing acrylic resin may be only one kind or two or more kinds.

[0020] In the alkoxysilyl group-containing acrylic resin, the number of carbon atoms of the repeating unit (monomer unit) having an alkoxysilyl group is preferably 6 or more and 20 or less, more preferably 7 or more and 17 or less, and even more preferably 8 or more and 14 or less. When it is within the above range, the self-crosslinkability with the above-mentioned polyester resin is enhanced, and the adhesion of the conductive layer formed using the conductive polymer dispersion of this aspect to the substrate is further improved.

[0021] In the alkoxysilyl group-containing acrylic resin, the content ratio of the repeating unit (monomer unit) having an alkoxysilyl group is preferably 10% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and even more preferably 80% by mass or more and 100% by mass or less, based on the total mass of the monomer having an alkoxysilyl group and other radically polymerizable monomers copolymerizable with this monomer. Note that when this ratio is 100% by mass, it means a homopolymer of the monomer having an alkoxysilyl group.

[0022] Examples of the other radically polymerizable monomers include vinyl esters, unsaturated carboxylic acid esters, unsaturated carboxylic acid amides, unsaturated nitriles, unsaturated carboxylic acids, allyl compounds, nitrogen-containing vinyl monomers, hydrocarbon vinyl monomers, or vinyl silane compounds, etc. One or more of these can be used as a copolymerizable monomer.

[0023] (Manufacturing method) The manufacturing method of the alkoxysilyl group-containing acrylic resin is not particularly limited, and for example, it can be manufactured by emulsion polymerization. When applying emulsion polymerization, for example, 10 to 1000 parts by mass of ion-exchanged water, 1 to 10 parts by mass of a polymerization initiator, and 1 to 20 parts by mass of a surfactant are added to a reaction tank. On the other hand, 10 to 1000 parts by mass of ion-exchanged water and 1 to 20 parts by mass of a surfactant are added to a dropping tank, and after adding 100 parts by mass of the monomers constituting the alkoxysilyl group-containing acrylic resin to prepare an emulsion, this emulsion is dropped into the reaction tank and added to carry out emulsion radical polymerization. The reaction temperature depends on the reactivity of the monomers used, but is preferably 60 to 100 °C, and the reaction time is preferably 4 to 10 hours.

[0024] As the surfactant used in emulsion polymerization, one or more of an anionic surfactant, a nonionic reactive surfactant, and a non-reactive surfactant can be used. It is preferable to use an anionic surfactant.

[0025] As the polymerization initiator used in emulsion polymerization, general radical polymerizable initiators such as water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, or oil-soluble peroxides such as benzoyl peroxide and t-butyl hydroperoxide, or azo compounds such as azobisisobutyronitrile can be mentioned.

[0026] 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 it becomes difficult to obtain a uniform dispersion as the solid content concentration increases, the mass of the solid content (non-volatile component) of the alkoxysilyl group-containing acrylic resin is preferably 30% by mass or less based on the total mass of the dispersion.

[0027] The content of the alkoxysilyl group-containing acrylic resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50000 parts by mass or less, more preferably 100 parts by mass or more and 10000 parts by mass or less, and even more preferably 200 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the conductive composite. If it is equal to or higher than the above lower limit value, the adhesion of the conductive layer to the base material is further improved, and if it is equal to or lower than the above upper limit value, it is possible to prevent a decrease in conductivity due to a decrease in the content of the conductive composite.

[0028] [Polyester resin] The polyester resin contained in the conductive polymer dispersion liquid is a resin having an ester bond formed by polycondensation of a polyvalent carboxylic acid and a polyalcohol. The polyester resin used in this embodiment preferably has an acid group from the viewpoint of enhancing water dispersibility. The acid group may form a salt. Further, the polyester resin used in this embodiment is preferably a saturated polyester resin containing no reactive double bond from the viewpoint of enhancing the weather resistance of the conductive layer.

[0029] Examples of the polyester resin having an acid group include polyester resins (hereinafter referred to as "polyester resin (1)") which are polycondensates of a dicarboxylic acid component and a diglycol component and have an alkali metal salt of an acid group (such as a sulfo group, a carboxy group, a phosphoric acid group, etc.). Since this polyester resin (1) has a large polarity, it has excellent water dispersibility and can be stably dispersed in water without using an emulsifier or a stabilizer.

[0030] Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,5-dimethyl terephthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and orthophthalic acid; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The dicarboxylic acid may be used alone or in combination of two or more. The dicarboxylic acid component preferably contains a dicarboxylic acid having a sulfonic acid alkali metal salt type substituent (-SO 3- X + 、(X + is an alkali metal ion)) in which the sulfo group is neutralized by an alkali metal.

[0031] A dicarboxylic acid having a sulfonic acid alkali metal salt type substituent is a compound in which the sulfonic acid group in the dicarboxylic acid having a sulfonic acid group is converted to an alkali metal salt. Examples of the dicarboxylic acid having a sulfonic acid group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, or derivatives thereof. Examples of the alkali metal include sodium, potassium and the like. As the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent, the sodium salt of 5-sulfoisophthalic acid and its derivatives are preferable.

[0032] As the dicarboxylic acid component other than the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent in the dicarboxylic acid component, an aromatic dicarboxylic acid is preferable, and terephthalic acid and isophthalic acid are more preferable.

[0033] The content ratio of the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent is preferably 5 mol% or more and 30 mol% or less, more preferably 10 mol% or more and 25 mol% or less in all the dicarboxylic acid components. When it is in the above range, the crosslinking of the self-crosslinkable resin in the conductive layer becomes appropriate, and the adhesion of the conductive layer to the substrate is further improved.

[0034] Examples of the diglycol component for forming the polyester resin (1) include diethylene glycol, aliphatic glycols having 2 to 8 carbon atoms, or alicyclic glycols having 6 to 12 carbon atoms. Specific examples of the aliphatic glycols having 2 to 8 carbon atoms or alicyclic glycols having 6 to 12 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, neopentyl glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,6-hexanediol, p-xylene glycol, triethylene glycol, and the like. The diglycol component may be used alone or in combination of two or more.

[0035] The number average molecular weight of the polyester resin (1) is preferably 2,000 or more and 30,000 or less, and more preferably 10,000 or more and 27,000 or less. The number average molecular weight of the polyester resin (1) is the number-average molecular weight determined based on the calibration curve of elution time vs. molecular weight obtained in advance from a polystyrene standard substance with known molecular weight by measuring the elution time using gel permeation chromatography (GPC). If the number average molecular weight of the polyester resin (1) is equal to or higher than the lower limit value, the adhesion of the conductive layer becomes higher, and if it is equal to or lower than the upper limit value, the water dispersibility of the polyester resin (1) becomes higher.

[0036] The method for producing the polyester resin (1) is not particularly limited. For example, a method in which a dicarboxylic acid component and a diglycol component are subjected to an esterification or transesterification reaction at 130°C or higher and 200°C or lower, and then a polycondensation reaction is carried out at 200°C or higher and 250°C or lower under reduced pressure conditions can be mentioned. Examples of the reaction catalyst used in the method for producing the polyester resin (1) include metal acetates such as zinc acetate and manganese acetate, metal oxides such as antimony oxide and germanium oxide, and titanium compounds. The obtained polyester resin (1) may be added to water to form an aqueous dispersion. Since it becomes difficult to obtain a uniform dispersion as the solid content (non-volatile component) concentration of the aqueous dispersion of the polyester resin (1) increases, the solid content concentration is preferably 30% by mass or less.

[0037] The content of the polyester resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50000 parts by mass or less, more preferably 100 parts by mass or more and 10000 parts by mass or less, and still more preferably 200 parts by mass or more and 2000 parts by mass or less with respect to 100 parts by mass of the conductive composite. If it is above the above lower limit value, the adhesion of the conductive layer to the substrate is further improved, and if it is below the above upper limit value, it is possible to prevent a decrease in conductivity due to a decrease in the content of the conductive composite.

[0038] [Self-crosslinkable resin] The alkoxysilyl group-containing acrylic resin, when combined with the polyester resin (1) and contained together with the conductive composite, self-crosslinks during the formation of the conductive layer to become a self-crosslinkable resin. The excess anion groups that do not participate in the doping of the polyanion of the conductive composite can function as a catalyst for promoting the above self-crosslinking.

[0039] In order to obtain appropriate self-crosslinking, the content ratio represented by (alkoxysilyl group-containing acrylic resin / polyester resin (1)) is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, and still more preferably 20 / 80 to 80 / 20 on a mass basis of the solid content. When it is in the above range, the mechanical strength of the formed conductive layer is further improved, and the adhesion of the conductive layer to the substrate is further improved.

[0040] [Aqueous dispersion medium] The aqueous dispersion medium contained in the conductive polymer dispersion is water or a mixture of water and an organic solvent.

[0041] Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, and the like. Examples of alcohol solvents include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc.; and dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc. Examples of ether solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, etc. 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, diacetone alcohol, etc. Examples of ester solvents include ethyl acetate, propyl acetate, butyl acetate, etc. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, etc. Examples of solvents not classified above include dimethyl sulfoxide. The organic solvent may be used alone or in combination of two or more.

[0042] From the viewpoint of enhancing the dispersibility of the conductive composite, the dispersion medium of the conductive polymer dispersion preferably has a high water content, and preferably contains an organic solvent from the viewpoint of enhancing the dispersibility of the alkoxysilyl group-containing acrylic resin. The organic solvent is preferably a water-soluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a solubility of 1 g or more in 100 g of water at 20°C, and the water-insoluble organic solvent is an organic solvent having a solubility of less than 1 g in 100 g of water at 20°C. As the water-soluble organic solvent, one or more selected from alcohol solvents are preferred.

[0043] The dispersion medium of the conductive polymer dispersion is preferably an aqueous dispersion medium containing water. The content ratio of water to the total mass of the aqueous dispersion medium is preferably, for example, 20% by mass or more and 50% by mass or less, more preferably 30% by mass or more and 40% by mass or less.

[0044] [Other Additives] The conductive polymer dispersion may contain other additives. The additives are not particularly limited as long as the effects of the present invention can be obtained. For example, surfactants, inorganic conductive agents, defoamers, coupling agents, antioxidants, ultraviolet absorbers, etc. can be used. Examples of the surfactant include nonionic, anionic, and cationic surfactants. From the viewpoint of storage stability, nonionic surfactants are preferred. Also, polymer surfactants such as polyvinylpyrrolidone may be added. Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ions can be generated by dissolving a metal salt in water. Examples of the coupling agent include silane coupling agents having an epoxy group, a vinyl group, or an amino group. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars, etc. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc.

[0045] When the conductive polymer dispersion contains the above additives, the content ratio can be appropriately determined according to the type of the additive. For example, it can be in the range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the conductive composite.

[0046] <Method for Producing Conductive Polymer Dispersion>[ As a method for producing the conductive polymer dispersion of the present aspect, for example, a method of adding a polyester resin, an acrylic resin containing an alkoxysilyl group, and, if necessary, other additives to an aqueous dispersion of a conductive composite can be mentioned. The aqueous dispersion of the conductive composite may be obtained by chemically oxidatively polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous solution of a polyanion by a known method, or a commercially available product may be used. In the prepared conductive polymer dispersion, since the conductive composite functions as a catalyst for promoting the self-crosslinking of the self-crosslinkable resin, it is prepared as a self-crosslinking resin in which the polyester resin and the acrylic resin containing an alkoxysilyl group are previously mixed, and immediately before coating, it is preferable to mix the conductive composite with the self-crosslinkable resin to obtain a conductive polymer dispersion.

[0047] [Conductive layer] The formation range of the conductive layer provided in the conductive laminate of the present aspect may be the entire surface or a part of any surface of the glass substrate. When the conductive layer is formed only on a part of the surface of the glass substrate, for example, the conductive layer may be a fine conductive pattern such as a circuit or an electrode, or the region where the conductive layer is provided and the region where it is not provided may exist on the same surface and may be roughly divided.

[0048] As the average thickness of the conductive layer, for example, 10 nm or more and 100 μm or less is preferable, 20 nm or more and 50 μm or less is more preferable, and 30 nm or more and 30 μm or less is further preferable. If the average thickness of the conductive layer is equal to or greater than the lower limit value, high conductivity can be exhibited, and if it is equal to or less than the upper limit value, the adhesion of the conductive layer to the substrate is further improved.

[0049] [Glass substrate] Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, a fused silica glass substrate, etc. When the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease. Therefore, among the above glass substrates, an alkali-free glass is preferred. Here, the alkali-free glass is a glass composition in which the content of the alkali component is 0.1% by mass or less based on the total mass of the glass composition.

[0050] The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is equal to or greater than the lower limit value, it is less likely to be damaged, and if it is equal to or less than the upper limit value, it can contribute to thinning of the conductive laminate. The average thickness of the glass substrate is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

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

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

[0053] The coating amount of the conductive polymer dispersion liquid on the substrate is not particularly limited, but considering uniform coating without unevenness and conductivity and film strength, as a solid content, 0.01 g / m2 10.0 g / m or less 2 is preferably in the following range.

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

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

[0056] ≪Transparent Electrode≫ If the glass substrate and the conductive layer constituting the conductive laminate of the first aspect are each transparent, the conductive laminate of the first aspect can be used as a transparent electrode or a transparent wiring board. Here, being transparent means having the property of allowing visible light to pass through. The total light transmittance at the location where the glass substrate and the conductive layer are laminated is preferably 65% or more, more preferably 70% or more, and even more preferably 80% or more. Here, the total light transmittance is a value measured in accordance with JIS K7136.

Examples

[0057] (Production Example 1) Production of Polystyrene Sulfonic Acid Dissolve 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water, and while stirring at 80°C, dropwise add a solution of 1.14 g of ammonium persulfate oxidant dissolved in 10 ml of water in advance over 20 minutes, and stir this solution for 12 hours. Add 1000 ml of sulfuric acid diluted to 10% by mass to the obtained sodium polystyrene sulfonate-containing solution to obtain a polystyrene sulfonic acid-containing solution. Next, remove approximately 1000 ml of the solvent of the polystyrene sulfonic acid-containing solution by ultrafiltration, add 2000 ml of ion-exchanged water to the residue, and remove approximately 2000 ml of the solvent by ultrafiltration to wash the polystyrene sulfonic acid with water. This water washing operation was repeated 3 times. Remove the water in the obtained solution under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

[0058] (Production Example 2) Preparation of PEDOT-PSS Aqueous Dispersion A solution obtained by dissolving 0.5 g of 3,4-ethylenedioxythiophene and 1.5 g of polystyrene sulfonic acid in 15.0 g of ion-exchanged water was mixed at 20°C. Next, 89.5 g of ion-exchanged water was added. Keep the obtained mixed solution at 20°C, and while stirring, slowly add 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, and stir the obtained reaction solution for 24 hours to react. By the above reaction, an aqueous dispersion of PEDOT-PSS containing a conductive composite (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene), which is a π-conjugated conductive polymer, and polystyrene sulfonic acid, and water as a dispersion medium was obtained. Add 13.2 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) and 13.2 g of Duolite A368S (manufactured by Sumika Chemtex Co., Ltd., anion exchange resin) to this dispersion, filter to remove the ion exchange resin, and obtain a PEDOT-PSS aqueous dispersion (solid content 1.3% by mass) from which the oxidant and the catalyst have been removed.

[0059] (Production Example 3) Preparation of Polyester Resin A Into a four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a thermometer, and a stirrer, 854 g of dimethyl terephthalate, 355 g of 5-sodium sulfoisophthalic acid, 186 g of ethylene glycol, 742 g of diethylene glycol, and 1 g of zinc acetate as a reaction catalyst were charged. Then, the temperature inside the flask was raised from 130 °C to 170 °C over 2 hours for transesterification reaction. After that, 730 g of isophthalic acid and 1 g of antimony trioxide were added, and the temperature was raised from 170 °C to 200 °C over 2 hours for esterification reaction. Next, the temperature was gradually raised and the pressure was reduced, and finally a polycondensation reaction was carried out at a reaction temperature of 250 °C and a vacuum degree of 5 mmHg or less for 1 hour. Then, it was cooled, and ion-exchanged water was added under normal pressure to obtain Polyester Resin A with a non-volatile content (solid content) of 25% by mass.

[0060] (Production Example 4) Preparation of Alkoxysilyl Group-Containing Acrylic Resin B 18 g of ion-exchanged water and 3 g of Eleminol RS-3000 (manufactured by Sanyo Chemical Industries, Ltd., anionic surfactant, active ingredient 50% by mass) as a surfactant were charged into a beaker. Then, while stirring the inside of the beaker, 40 g of 3-methacryloyloxypropyltrimethoxysilane was added to prepare a monomer emulsion. Next, 37.5 g of ion-exchanged water, 1 g of surfactant (Eleminol RS-3000), and 0.5 g of potassium persulfate were charged into a four-necked flask equipped with a condenser, a monomer dropping funnel, a thermometer, and a stirrer. Then, after nitrogen substitution while stirring the inside of the flask, heating was started, and the monomer emulsion was added dropwise at 75 °C over 4 hours. After the dropping was completed, the reaction was advanced by maintaining the liquid temperature at 75 - 85 °C, and it was cooled 4 hours after the dropping was completed. After cooling, ion-exchanged water was further added to obtain an alkoxysilyl group-containing acrylic resin B with a non-volatile content (solid content) of 25% by mass.

[0061] (Production Example 5) Preparation of Alkoxysilyl Group-Containing Acrylic Resin C Except for changing 40 g of 3-methacryloyloxypropyltrimethoxysilane to 40 g of 3-acryloyloxypropyltrimethoxysilane, an alkoxysilyl group-containing acrylic resin C with a nonvolatile content of 25% by mass was obtained in the same manner as in Production Example 4.

[0062] (Production Example 6) Preparation of alkoxysilyl group-containing acrylic resin D Except for changing 40 g of 3-methacryloyloxypropyltrimethoxysilane to 40 g of 3-methacryloyloxypropyltriethoxysilane, an alkoxysilyl group-containing acrylic resin D with a nonvolatile content of 25% by mass was obtained in the same manner as in Production Example 4.

[0063] (Production Example 7) Preparation of alkoxysilyl group-containing acrylic resin E Except for changing 40 g of 3-methacryloyloxypropyltrimethoxysilane to 40 g of 3-acryloyloxypropyltriethoxysilane, an alkoxysilyl group-containing acrylic resin E with a nonvolatile content of 25% by mass was obtained in the same manner as in Production Example 4.

[0064] (Production Example 8) Preparation of self-crosslinkable resin F The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended at a solid content mass ratio of 50 / 50 to obtain a self-crosslinkable resin F with a nonvolatile content (solid content) of 25% by mass.

[0065] (Production Example 9) Preparation of self-crosslinkable resin G The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin C obtained in Production Example 5 were blended at a solid content mass ratio of 50 / 50 to obtain a self-crosslinkable resin G with a nonvolatile content (solid content) of 25% by mass.

[0066] (Production Example 10) Preparation of self-crosslinkable resin H The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin D obtained in Production Example 6 were blended at a solid content mass ratio of 50 / 50 to obtain a self-crosslinkable resin H with a nonvolatile content (solid content) of 25% by mass.

[0067] (Production Example 11) Preparation of Self-crosslinking Resin I The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin E obtained in Production Example 7 were blended at a solid content mass ratio of 50 / 50 to obtain a self-crosslinking resin I with a non-volatile content (solid content) of 25% by mass.

[0068] (Production Example 12) Preparation of Self-crosslinking Resin J The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended at a solid content mass ratio of 25 / 75 to obtain a self-crosslinking resin J with a non-volatile content (solid content) of 25% by mass.

[0069] (Production Example 13) Preparation of Self-crosslinking Resin K The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended at a solid content mass ratio of 75 / 25 to obtain a self-crosslinking resin K with a non-volatile content (solid content) of 25% by mass.

[0070] (Production Example 14) Preparation of Self-crosslinking Resin L The polyester resin A obtained in Production Example 3 and the alkoxysilyl group-containing acrylic resin B obtained in Production Example 4 were blended at a solid content mass ratio of 10 / 90 to obtain a self-crosslinking resin L with a non-volatile content (solid content) of 25% by mass.

[0071] (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 at a solid content mass ratio of 90 / 10 to obtain a self-crosslinking resin M with a non-volatile content (solid content) of 25% by mass.

[0072] (Example 1) 60 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 40 g of the self-crosslinking resin F, and 100 g of methanol were mixed to prepare a conductive polymer dispersion. Next, it was coated on an alkali-free glass using a #8 bar coater and dried at 150 °C for 10 minutes to obtain a conductive laminate provided with a conductive layer. The results of measuring the surface resistance value and the adhesion of the conductive layer are shown in Table 1.

[0073] (Example 2) A conductive laminate was produced and measured in the same manner as in Example 1, except that the PEDOT-PSS aqueous dispersion was changed to 20 g and the self-crosslinkable resin F was changed to 80 g. The results are shown in Table 1.

[0074] (Example 3) A conductive laminate was produced and measured in the same manner as in Example 1, except that the PEDOT-PSS aqueous dispersion was changed to 80 g and the self-crosslinkable resin F was changed to 20 g. The results are shown in Table 1.

[0075] (Example 4) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin G. The results are shown in Table 1.

[0076] (Example 5) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin H. The results are shown in Table 1.

[0077] (Example 6) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin I. The results are shown in Table 1.

[0078] (Example 7) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin J. The results are shown in Table 1.

[0079] (Example 8) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinkable resin F was changed to the self-crosslinkable resin K. The results are shown in Table 1.

[0080] (Example 9) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F was changed to the self-crosslinking resin L in Example 1. The results are shown in Table 1.

[0081] (Example 10) A conductive laminate was produced and measured in the same manner as in Example 1, except that the self-crosslinking resin F was changed to the self-crosslinking resin M in Example 1. The results are shown in Table 1.

[0082] (Comparative Example 1) A conductive laminate was produced and measured in the same manner as in Example 1, except that 40 g of the self-crosslinking resin F was changed to 40 g of water in Example 1. The results are shown in Table 1.

[0083] (Comparative Example 2) A conductive laminate was produced and measured in the same manner as in Example 1, except that 60 g of the PEDOT-PSS aqueous dispersion was changed to 60 g of water in Example 1. The results are shown in Table 1.

[0084] (Comparative Example 3) A conductive laminate was produced and measured in the same manner as in Example 1, except that 40 g of the self-crosslinking resin F was changed to 40 g of the polyester resin A in Example 1. The results are shown in Table 1.

[0085] (Comparative Example 4) An attempt was made to produce a conductive laminate in the same manner as in Example 1, except that 40 g of the self-crosslinking resin F was changed to 40 g of the alkoxysilyl group-containing acrylic resin B in Example 1. However, the coating film did not conform to the glass surface, was highly elastic, and it was difficult to form a conductive layer, so the test was aborted.

[0086] [Evaluation] [Surface Resistance Value] For the conductive laminate of each example, the surface resistance value of the conductive layer was measured using a resistivity meter (manufactured by Nitto Seiko Analytic Co., Ltd., High Resista) under the condition of an applied voltage of 10 V. The measurement results of the surface resistance value are shown in Table 1. In the table, "Ω / □" means ohm per square. "1.0E+05" means "1.0 × 105 It is represented by "」", and the same applies to others.

[0087] [Adhesion] The adhesion of the formed conductive layer to each glass was evaluated by measuring the number of squares that did not peel off for a total of 100 squares of 1 mm square in accordance with the cross-cut tape peeling test in JIS K 5600:1999. The results are shown in Table 1. In the results of Table 1, the larger the number of molecules (the number of squares that did not peel off), the greater the adhesion of the conductive layer to the glass substrate.

[0088]

Table 1

[0089] Since the conductive layers of Examples 1 to 10 are cured products of a paint composed of a conductive composite, an alkoxysilyl group-containing acrylic resin, and a polyester resin, they have good conductivity and excellent adhesion to the surface of the glass substrate. Since the conductive layer of Comparative Example 1 is a cured product of a paint that does not contain an alkoxysilyl group-containing acrylic resin and a polyester resin, its adhesion to the surface of the glass substrate is poor. Since the conductive layer of Comparative Example 2 is a cured product of a paint that does not contain a conductive composite, its conductivity is poor, and furthermore, its adhesion to the surface of the glass substrate is also poor. The reason for the poor adhesion is considered to be that the polyanion constituting the conductive composite does not exist, so the above-mentioned self-crosslinking did not proceed. Since the conductive layer of Comparative Example 3 is a cured product of a paint that does not contain an alkoxysilyl group-containing acrylic resin, its conductivity is poor, and furthermore, its adhesion to the surface of the glass substrate is also poor. The reason for the poor adhesion is considered to be that the alkoxysilyl group-containing acrylic resin does not exist, so the above-mentioned self-crosslinking did not proceed.

Claims

1. A conductive laminate comprising a glass substrate and a conductive layer in close contact with at least a part of the surface of the glass substrate, wherein the conductive layer is a cured product of a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium.

2. The conductive laminate according to Claim 1, wherein the carbon number of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less.

3. The conductive laminate according to Claim 2, wherein the polyester resin has one or more selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxy group.

4. The conductive laminate according to Claim 3, wherein the polyanion is polystyrene sulfonic acid.

5. The conductive laminate according to Claim 4, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).

6. The conductive laminate according to Claim 5, wherein the glass substrate is non-alkali glass.

7. A transparent electrode comprising the conductive laminate according to any one of Claims 1 to 6.

8. A method for manufacturing a conductive laminate, comprising a step of applying a paint to at least a part of a glass substrate, drying and curing a coating film made of the paint to form a conductive layer, wherein the paint is a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an alkoxysilyl group-containing acrylic resin, a polyester resin, and an aqueous dispersion medium.

9. The method for manufacturing a conductive laminate according to Claim 8, wherein the carbon number of the repeating unit having an alkoxysilyl group in the alkoxysilyl group-containing acrylic resin is 6 or more and 20 or less.

10. The method for manufacturing a conductive laminate according to Claim 9, wherein the polyester resin has one or more selected from a sulfo group or a salt thereof, a carboxy group or a salt thereof, and a hydroxy group.

Images