JP7333742B2 - Conductive laminate and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a conductive laminate and its manufacturing method.

BACKGROUND ART Wiring substrates in which a transparent conductive layer is formed on the surface of a transparent base material such as glass or resin film are used in touch panels and displays. The transparent conductive layer may be formed of a metal oxide such as indium tin oxide (ITO), which has excellent conductivity. Such a conductive laminate is required to have excellent conductivity and transparency. However, due to the increase in layer thickness accompanying the improvement in the conductivity of the transparent conductive layer, when incident light passes through the conductive laminate, the wiring pattern of the transparent conductive layer becomes more visible. There is a problem called As a solution to this problem, for example, Patent Document 1 proposes a conductive laminate in which a plurality of undercoat layers having different refractive indices are laminated on a transparent conductive layer.

JP 2016-013632 A

By the way, when a conductive laminate having a resin layer such as an undercoat layer is placed in the vicinity of an electric field such as a liquid crystal panel, the resin layer is charged, thereby generating an electric field necessary for the liquid crystal panel or the like to function. I have a disturbing problem. The present inventors have considered laminating a layer containing a conductive polymer on a metal layer made of ITO or the like in order to prevent electrification of a conductive laminate. Due to the influence, the metal layer rusts and the resistance of the metal layer increases, which is a new problem.

The present invention has been made in view of the above circumstances, and includes a metal layer and a conductive polymer layer laminated on the surface thereof, wherein the conductive polymer layer increases the resistance of the metal layer. Provided is a conductive laminate and a method for manufacturing the same, in which the is suppressed.

[1] A conductive laminate comprising a metal layer and a conductive polymer layer laminated on the surface of the metal layer, wherein the conductive polymer layer contains a π-conjugated conductive polymer and A conductive complex containing a polyanion is included, and of the excess anionic groups that do not participate in the doping of the polyanion, some are modified by reaction with an epoxy group-containing compound, and another part is an amine A conductive laminate that has been modified by reaction with a compound.
[2] The conductive laminate according to [1], wherein a glass substrate or a film substrate is laminated on the surface of the metal layer opposite to the conductive polymer layer.
[3] The conductive laminate according to [1] or [2], wherein a resin layer is laminated on the surface of the conductive polymer layer opposite to the metal layer.
[4] The conductive laminate according to [3], wherein the resin layer contains an acrylic resin.
[5] The conductive laminate according to any one of [1] to [4], wherein the metal layer is made of ITO.
[6] The conductive laminate according to any one of [1] to [5], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[7] The conductive laminate according to any one of [1] to [6], wherein the polyanion is polystyrenesulfonic acid.
[8] The method for producing a conductive laminate according to any one of [1] to [7], wherein a conductive layer containing a π-conjugated conductive polymer and a polyanion is formed on the surface of the metal layer. including a lamination step of forming the conductive polymer layer by applying a conductive polymer-containing liquid containing a complex and an organic solvent, and A method for producing a conductive laminate, wherein a part is modified by reaction with an epoxy group-containing compound, and another part is modified by reaction with an amine compound.
[9] The method for producing a conductive laminate according to [8], wherein the organic solvent contains methyl ethyl ketone.
[10] The method for producing a conductive laminate according to [8] or [9], wherein the amine compound is a heterocyclic aromatic amine or a tertiary amine.
[11] The method for producing a conductive laminate according to any one of [8] to [10], wherein the amine compound is imidazole, tributylamine, or trioctylamine.
[12] The method for producing a conductive laminate according to any one of [8] to [11], wherein the conductive polymer-containing liquid further contains a binder component.
[13] The method for producing a conductive laminate according to [12], wherein the binder component is a polyester resin.
[14] including a preparation step of preparing the conductive polymer-containing liquid, wherein in the preparation step, an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion and an aqueous dispersion medium; , obtaining a first reaction solution to which an epoxy group-containing compound has been added, and reacting the epoxy group-containing compound with a part of the surplus anionic groups that do not participate in the doping of the polyanion, thereby precipitating the conductive composite. After that, the precipitate of the conductive composite is recovered from the first reaction solution, an organic solvent is added to the precipitate to obtain a preparation solution in which the precipitate is dispersed, and the preparation solution is Obtaining a second reaction liquid to which an amine compound is added, and reacting the amine compound with another part of the surplus anionic groups that do not participate in the doping of the polyanion to obtain the conductive polymer-containing liquid. [8] The method for producing a conductive laminate according to any one of [13].

In the conductive laminate of the present invention, since the polyanion of the conductive composite contained in the conductive polymer layer is chemically modified with the epoxy group-containing compound and the amine compound, the metal layer is rusted. is prevented from increasing in resistance, and has antistatic properties.
According to the method for producing the conductive laminate of the present invention, the conductive laminate of the present invention can be produced.

<<Conductive laminate>>
A first aspect of the present invention is a conductive laminate comprising a metal layer and a conductive polymer layer laminated on the surface of the metal layer, wherein the conductive polymer layer includes a π-conjugated system A conductive complex containing a conductive polymer and a polyanion is included, and of the surplus anionic groups that do not participate in the doping of the polyanion, some are modified by reaction with an epoxy group-containing compound, and another is modified by reaction with an epoxy group-containing compound. Some are conductive laminates that have been modified by reaction with amine compounds.

<Metal layer>
The metal layer of this embodiment is a conductive layer containing metal. Examples of such metals include indium, tin, titanium, zinc, tungsten, aluminum, gallium, copper, chromium, and the like. From the viewpoint of forming a transparent and highly conductive metal layer, the metal layer includes indium tin oxide (ITO), indium tin monoxide titanium monoxide (InTiTO), titanium oxide (TiO), indium oxide zinc monoxide. (IZO), indium oxide ( _In2O3 ), tungsten-doped indium oxide ( _IWO ), titanium-doped indium oxide (ITiO), zinc oxide (ZnO), tin oxide ( _SnO2 ), tin fluoride ( _SnF2 ), It is preferably a metal layer formed of a metal oxide such as aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), or gallium-aluminum-doped zinc oxide (GAZO).

The metal layer may be a metal layer that covers the entire surface of the substrate, or may be a metal layer that is patterned into wiring, electrodes, or the like, depending on the purpose of use.

The thickness of the metal layer is appropriately set according to the purpose of use of the conductive laminate. In the case of a transparent conductive layer, for example, it is preferably 1 nm or more and 1 μm or less, and 5 nm or more and 500 nm or less. is more preferable, and more preferably 10 nm or more and 100 nm or less.
If it is at least the lower limit of the above range, the conductivity will be improved, and if it is at most the upper limit of the above range, the transparency will be improved.
The thickness of the metal layer is a value obtained by measuring the thickness at arbitrary 10 points in the cross section of the conductive laminate of the present embodiment by a known method and averaging the measured values.

The metal layer preferably has a surface resistance value of, for example, 0.1 Ω/□ or more and 100 Ω/□ or less as a measure of good conductivity.

<Base material>
A glass substrate or a film substrate may be laminated on the surface of the metal layer opposite to the conductive polymer layer.

Examples of the film substrate include plastic films.
Examples of film substrate resins constituting plastic films include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio nate and the like. Among these film substrate resins, polyethylene terephthalate is preferable because it is inexpensive and has excellent mechanical strength.

Resins for film substrates may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
The film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc., in order to further improve the adhesion of the conductive polymer layer formed from the conductive polymer-containing liquid. .

The average thickness of the glass substrate is, for example, 500 μm or more and 5 mm or less.
As average thickness of a film base material, 5 micrometers or more and 500 micrometers or less are mentioned, for example.
The thickness of each base material is appropriately selected according to the application of the conductive laminate of this embodiment.
The thickness of each base material is a value obtained by measuring the thickness at arbitrary 10 points in the cross section of the conductive laminate of this embodiment by a known method and averaging the measured values.

When the conductive laminate is used for optical purposes, the glass substrate and film substrate are preferably transparent. Specifically, the total light transmittance of the substrate is preferably 65% or more, more preferably 70% or more, and even more preferably 80% or more. The total light transmittance is a value measured according to JIS K7136.

<Conductive polymer layer>
[Conductive composite]
First, an unmodified conductive composite will be described.
The conductive composite in this aspect contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite forms a conductive composite having conductivity by doping the π-conjugated conductive polymer.

(π-conjugated conductive polymer)
The π-conjugated conductive polymer may be any organic polymer having a π-conjugated main chain. molecules, polyphenylene-based conductive polymers, polyphenylene-vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, copolymers thereof, and the like. Polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable from the viewpoint of stability in air, and polythiophene-based conductive polymers are more preferable from the viewpoint of transparency.

Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), and 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-carboxy butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butyl pyrrole), 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), poly(3-methyl-4-hexyloxypyrrole).
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 from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

(polyanion)
A polyanion is a polymer having two or more monomer units having an anionic group in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves 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 polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, Polymers having carboxy groups such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, etc. A polyanion is a single monomer. may be a homopolymer obtained by polymerizing or a copolymer obtained by polymerizing two or more monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
One of the polyanions may be used alone, or two or more thereof may be used in combination.
The weight average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The mass-average molecular weight is a mass-based average molecular weight determined by gel permeation chromatography and calculated in terms of polystyrene.

The content 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 with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. and more preferably in the range of 100 parts by mass or more and 500 parts by mass or less. If the polyanion content is at least the above lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the polyanion content is equal to or less than the above upper limit, the π-conjugated conductive polymer can be sufficiently contained, and sufficient conductivity can be ensured.

In the polyanions in the conductive composite, not all anionic groups are doped into the π-conjugated conductive polymer, and there are surplus anionic groups that do not participate in doping. The surplus anionic group is a hydrophilic group, and the dispersibility of the conductive composite in which the anionic group is not modified is high in an aqueous dispersion medium and low in an organic solvent.

[Modification of conductive composite]
Next, modification of the conductive composite will be described.
The conductive composite in this aspect is modified by each reaction between an epoxy group-containing compound (epoxy compound) and an amine compound. Specifically, some of the surplus anionic groups that are not involved in the doping of the polyanion of the conductive composite have reduced hydrophilicity due to reaction with the epoxy groups of the epoxy compound. Further, another part of the surplus anionic groups (the part not reacting with the epoxy compound) has decreased hydrophilicity due to the reaction with the amine compound. As a result, the modified conductive composite is more hydrophobic than the unmodified conductive composite, and has enhanced dispersibility in organic solvents.

(Substituent A)
Substituent A that can be formed by reacting the surplus anionic group with the epoxy compound is represented by, for example, the following structural formula.
Detailed analysis of the modified conductive composite is not necessarily easy, but the substituent (A) is presumed to be a group represented by the following formula (A1) or a group represented by the following formula (A2). be.

［式（Ａ１）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４はそれぞれ独立に、水素原子、又は任意の置換基である。］

[In Formula (A1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an arbitrary substituent. ]

［式（Ａ２）中、ｍは２以上の整数であり、複数のＲ^１５、複数のＲ^１６、複数のＲ^１７、及び複数のＲ^１８はそれぞれ独立に、水素原子、又は任意の置換基であり、複数のＲ^１５は同一でも異なっていてもよく、複数のＲ^１６は同一でも異なっていてもよく、複数のＲ^１７は同一でも異なっていてもよく、複数のＲ^１８は同一でも異なっていてもよい。］

[In the formula (A2), m is an integer of 2 or more, and the plurality of R ¹⁵ , the plurality of R ¹⁶ , the plurality of R ¹⁷ , and the plurality of R ¹⁸ are each independently a hydrogen atom or an arbitrary substituent, A plurality of R ¹⁵ may be the same or different, a plurality of R ¹⁶ may be the same or different, a plurality of R ¹⁷ may be the same or different, and a plurality of R ¹⁸ may be the same or different. may ]

In the formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with the proton of the anion group. An anionic group having a substituted proton includes, for example, an anionic group having an active proton bonded to an oxygen atom such as “—SO ₃ H”.

In formula (A1), the optional substituents for R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present. R ¹¹ and R ¹³ may combine to form a ring which may have a substituent. For example, R ¹¹ and R ¹³ are the above hydrocarbon groups, and a divalent hydrocarbon group excluding any one hydrogen atom of the monovalent hydrocarbon group of R ¹¹ and a monovalent hydrocarbon of R ¹³ A case where a divalent hydrocarbon group from which any one hydrogen atom is removed from the hydrogen group is combined with the carbon atoms from which the hydrogen atom is removed to form a ring is exemplified.
Among them, in formula (A1), R ¹¹ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms, R ¹² is a hydrogen atom, and R ¹³ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms. and R ¹⁴ is preferably a hydrogen atom.

In formula (A2), the optional substituents for R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present. R ¹⁵ and R ¹⁷ may combine to form a ring which may have a substituent. Examples of ring formation are the same as above.
Among them, in formula (A2), R ¹⁵ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms, R ¹⁶ is a hydrogen atom, and R ¹⁷ is a hydrogen atom or an alkoxyalkyl group having 10 to 16 carbon atoms. and R ¹⁸ is preferably a hydrogen atom.

As used herein, the term “optionally having a substituent” refers to cases in which a hydrogen atom (—H) is substituted with a monovalent group, and cases in which a methylene group (—CH ₂ —) is substituted with a divalent group. Including both when to replace.
Monovalent groups as substituents include alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and trialkoxysilyl groups. (trimethoxysilyl group, etc.), and the like.
The divalent group as a substituent includes an oxygen atom (-O-), -C(=O)-, -C(=O)-O- and the like. However, the case where two oxygen atoms are adjacent to each other is excluded.

In formula (A2), m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. Hydrophobicity of the conductive composite becomes sufficiently high that m is at least the above lower limit. When m is equal to or less than the upper limit, it is possible to prevent the hydrophobicity from becoming too high and the conductivity from decreasing.

The epoxy group-containing compound (epoxy compound) is a compound having one or more epoxy groups in one molecule. From the viewpoint of preventing aggregation or gelation when modifying the conductive composite, the epoxy compound is preferably a compound having one epoxy group in one molecule.
An epoxy compound may be used individually by 1 type, and may use 2 or more types together.

Monofunctional epoxy compounds having one epoxy group in one molecule include, for example, ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1 ,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2- epoxy octadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, Epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2- epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H,3H, 3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy(3-glycidyloxypropyl)methylsilane, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl- 3-(3-glycidyloxypropyl)trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis(4-glycidyloxyphenyl)propane, 2 -tert-butyl-2-[2-(4-chlorophenyl)]ethyloxirane, styrene oxide, glycidyltrityl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α , 6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate, ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl) perfluoro-n-octylsulfonamide, ( 2S,3S)-1,2-epoxy-3-(tert-butoxycarbonylamino)-4-phenylbutane, (R)-glycidyl 3-nitrobenzenesulfonate, glycidyl 3-nitrobenzenesulfonate, parthenolide, N-glycidyl phthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7,7-dimethyloctanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ether having 10 to 16 carbon atoms, and the like. be done.

As the higher alcohol glycidyl ether, one or more higher alcohol glycidyl ethers having 10 to 16 carbon atoms are preferable, and one or more higher alcohol glycidyl ethers having 12 to 14 carbon atoms are more preferable. At least one of alcohol glycidyl ether and C13 (13 carbon atoms) higher alcohol glycidyl ether is more preferred, and C12 and C13 mixed higher alcohol glycidyl ether is particularly preferred.

Examples of polyfunctional epoxy compounds having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. Diglycidyl ether, 1,2:3,4-diepoxybutane, diglycidyl 1,2-cyclohexanedicarboxylate, triglycidyl neopentyl glycol isocyanurate diglycidyl ether, 1,2:3,4-diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, tri Methylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and the like.

The epoxy compound preferably has a molecular weight of 50 or more and 2,000 or less because it is highly dispersible in an organic solvent. In addition, since the dispersibility in low-polar organic solvents increases, the epoxy compound preferably has 2 or more and 100 or less carbon atoms, more preferably 5 or more and 80 or less, and 10 or more and 50 or less. More preferred.

(Substituent B)
Substituent B that can be formed by reacting the surplus anionic group with the amine compound is represented by, for example, the following structural formula.
Detailed analysis of the conductive composite is not necessarily easy, but it is presumed that the substituent (B) is a group represented by the following formula (B).

-HN ⁺ R ²¹ R ²² R ²³ (B)
[In formula (B), R ²¹ to R ²³ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that at least one of R ²¹ to R ²³ is a substituent is a hydrocarbon group which may have ]

In the substituent (B), the leftmost bond represents that the negative charge of the anion group and the positive charge of the amine compound are bonded. An anionic group that can be negatively charged includes an anionic group having an oxygen atom to which an active proton can bind, such as “—SO ₃ ⁻ ”.

R ²¹ to R ²³ in formula (B) are hydrogen atoms or hydrocarbon groups which may have a substituent. R ²¹ to R ²³ in formula (B) are substituents derived from an amine compound.
The hydrocarbon group in the formula (B) is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. groups.
Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
A phenyl group, a hydroxyl group, etc. are mentioned as a substituent which may substitute hydrogen of an aliphatic hydrocarbon group.
A phenyl group, a naphthyl group, etc. are mentioned as an aromatic-hydrocarbon group.
Substituents which may substitute hydrogen in the aromatic hydrocarbon group include alkyl groups having 1 to 5 carbon atoms and hydroxyl groups.

The amine compound is at least one selected from the group consisting of primary amines (primary amines), secondary amines (secondary amines) and tertiary amines (tertiary amines). An amine compound may be used individually by 1 type, and may use 2 or more types together.
Examples of primary amines include aniline, toluidine, benzylamine, ethanolamine and the like.
Secondary amines include, for example, diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Tertiary amines include, for example, triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Among the amine compounds, tertiary amines are preferable, and at least one of trioctylamine and tributylamine is more preferable, since the conductive composite can be easily hydrophobized.

Since the dispersibility in low-polarity organic solvents increases, the amine compound preferably has a substituent having 4 or more carbon atoms on the nitrogen atom, and a substituent having 6 or more carbon atoms on the nitrogen atom. It is more preferable to have

(Substituent C)
When the amine compound reacted with the surplus anionic group is a heterocyclic aromatic amine, the substituent C formed by the reaction with this is represented by the following structural formula, for example.

−HN ⁺ R ²⁴ (C)
[In formula (C), N ⁺ R ²⁴ represents a heterocyclic aromatic amine containing a positively charged nitrogen atom due to addition of a proton. ]
Here, the heterocyclic aromatic amine means a cyclic amine compound containing a nitrogen atom that constitutes an aromatic ring, and hydrogen atoms bonded to the amine compound may optionally be substituted.

In formula (C), the bond on the left end represents that the negative charge of the anion group and the positive charge of the heterocyclic aromatic amine are bonded. An anionic group that can be negatively charged includes an anionic group having an oxygen atom to which an active proton can bind, such as “—SO ₃ ⁻ ”.

If the heteroaromatic amine is too basic, the conductivity of the modified conductive composite may decrease. preferable. Here, the imidazole-based amine means a compound having an imidazole ring, and the hydrogen atoms bonded to the imidazole ring may optionally be substituted.

Examples of substituents that may optionally substitute hydrogen atoms of the imidazole ring include hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms. be done. A hydrogen atom constituting these substituents may be substituted with a hydroxyl group or a cyano group. In addition, the divalent or trivalent groups constituting these substituents may be substituted with -C(=O)-, -C(=O)-O-, -N=, and the like. Moreover, when it has two or more substituents which substitute the hydrogen atom of an imidazole ring, these substituents may couple|bond together and form the ring.

Examples of the imidazole-based amine include imidazole, 2-methylimidazole, 2-propylimidazole, N-methylimidazole, 1-(2-hydroxyethyl)imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethyl imidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2-(2-pyridyl)benzimidazole and the like.
Among these, imidazole is preferable because it has good reactivity with the anionic group of the conductive composite and is inexpensive.

(Regarding the reaction ratio of the anion group)
In this embodiment, of the surplus anionic groups that do not participate in the doping of the polyanion of the conductive composite, the proportion of anionic groups that have reacted with the epoxy compound is considered to be 10 to 90%, and about 20 to 60% is appropriate. It is considered to be In addition, among the surplus anion groups that do not participate in the doping of the polyanion of the conductive composite, the proportion of the anion groups that reacted with the amine compound is considered to be 0.1 to 50%, and about 1 to 30% is appropriate. It is considered to be
As will be described in the production method described later, first, the unmodified conductive composite is reacted with an epoxy compound to make it hydrophobic enough to precipitate from the aqueous solvent. It is considered that a modification reaction is taking place. In addition, when an amine compound is reacted with a conductive composite that has been hydrophobized by reacting an epoxy compound, the anionic group that remains without reacting with the epoxy compound reacts with the amine compound. If the ratio is large, the reaction ratio with the amine compound will inevitably decrease. Therefore, in the conductive composite contained in the conductive polymer layer of the conductive laminate manufactured by the manufacturing method described later, the anionic group that reacted with the epoxy compound is higher than the anionic group that reacts with the amine compound. It is easy to become many.

The content of the conductive composite contained in the conductive polymer layer of the conductive laminate of the present embodiment is preferably, for example, 1% by mass or more and 90% by mass or less with respect to the total mass of the conductive polymer layer. , more preferably 5% by mass or more and 50% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less.
When it is at least the lower limit of the above range, the antistatic property of the conductive polymer layer can be further enhanced, and rusting of the metal layer due to the conductive polymer layer can be more reliably prevented.
If it is equal to or less than the upper limit of the above range, the conductive polymer layer can contain an optional component such as a binder resin.

[Binder resin]
The conductive polymer layer of the conductive laminate of this aspect may contain a binder resin. The binder resin is a resin other than the π-conjugated conductive polymer and the polyanion, and examples thereof include thermoplastic resins and curable resins cured during formation of the conductive polymer layer.
Specific examples of binder resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, polyether resins, epoxy resins, oxetane resins, vinyl acetate resins, melamine resins, and silicone resins.
Binder resin may be used individually by 1 type, and may use 2 or more types together.

The binder resin contained in the conductive polymer layer is preferably the same type of resin as the resin contained in the film substrate. For example, when the film substrate contains a polyester resin, the binder resin contained in the conductive polymer layer preferably contains a polyester resin. Thus, when the conductive polymer layer and the film substrate contain the same type of resin, the adhesion between the conductive polymer layer and the film substrate can be improved.

The content of the binder resin contained in the conductive polymer layer is, for example, preferably 1% by mass or more and 99% by mass or less, and 10% by mass or more and 90% by mass, based on the total mass of the conductive polymer layer. The following are more preferable, and 20% by mass or more and 70% by mass or less are even more preferable.
When it is at least the lower limit of the above range, the adhesion of the conductive polymer layer to the substrate, the metal layer and the resin layer described below can be improved. When it is at most the upper limit of the above range, the relative content of the conductive composite contained in the conductive polymer layer can be increased, and the antistatic properties of the conductive polymer layer can be enhanced.

[High conductivity agent]
The conductive polymer layer of the conductive laminate of this embodiment may contain a highly conductive agent in order to further improve its antistatic property. Here, the π-conjugated conductive polymer, the polyanion, the amine compound, and the binder resin are not classified as high-conductivity agents.
Conductivity enhancing agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having one or more hydroxy groups and one or more carboxy groups, compounds having an amide group, It is preferably at least one compound selected from the group consisting of compounds having an imide group, lactam compounds, and compounds having a glycidyl group.
As the conductivity enhancer, a compound (diol) having two or more hydroxy groups is preferable, and propylene glycol is more preferable.
The conductivity enhancing agent contained in the conductive polymer layer of the conductive laminate of this embodiment may be one type or two or more types.

The content ratio of the high-conductivity agent in the conductive polymer layer of this aspect can be, for example, 1 part by mass or more and 100,000 parts by mass or less with respect to 100 parts by mass of the conductive composite, and 100 parts by mass. More than 1000 parts by mass or less is preferable. If the content ratio of the high-conductivity agent is at least the above lower limit, the effect of improving conductivity by adding the high-conductivity agent is sufficiently exhibited, and if it is at or below the above upper limit, the concentration of the π-conjugated conductive polymer decreases. It is possible to prevent a decrease in conductivity caused by

[Refractive index adjuster]
The conductive laminate of this aspect may contain a refractive index adjuster in the conductive polymer layer in order to reduce the visibility (bone appearance) of the metal layer. Here, the π-conjugated conductive polymer, the polyanion, the amine compound, and the binder resin are not classified as refractive index modifiers.
Examples of the refractive index adjuster include inorganic fine particles made of oxides of metals such as titanium, aluminum, zirconium, silicon, tin, and niobium, having a particle diameter of about several tens of nanometers. When these inorganic fine particles are contained, the refractive index of the conductive polymer layer increases. In addition, a known refractive index adjuster such as a fluorine-based organic resin material, a silicon oxide-based sol-gel material, a silicon oxide-based organic resin material, a silicon oxide-based or fluorine-based microporous material may be added to the conductive polymer layer of this embodiment. may be included.
A conductive polymer layer containing a refractive index modifier can function as an undercoat layer as described in Patent Document 1. From the viewpoint of reducing the visibility of the metal layer, the refractive index of the conductive polymer layer is preferably adjusted to 1.61 or more and 1.80 or less.
The content of the refractive index modifier in the conductive polymer layer of this embodiment is adjusted according to the desired refractive index in the same manner as the content of the refractive index modifier in the known undercoat layer.

[Other additives]
The conductive polymer layer of the conductive laminate of this embodiment may contain other additives.
Additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers and the like can be used. However, the additive is composed of a compound other than the π-conjugated conductive polymer, polyanion, binder resin, and high-conductivity agent described above.
Examples of surfactants include nonionic, anionic, and cationic surfactants, with nonionic surfactants being preferred from the standpoint of storage stability. A polymeric surfactant such as polyvinylpyrrolidone may also be added.
Examples of inorganic conductive agents include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Antifoaming agents include silicone resins, polydimethylsiloxane, silicone oils and the like.
Examples of coupling agents include silane coupling agents having an epoxy group, a vinyl group, or an amino group.
Antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars and the like.
UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. is mentioned.
When the conductive polymer layer of the conductive laminate of this embodiment contains the above additive, the content ratio thereof is appropriately determined according to the type of the additive. 0.001 parts by mass or more and 5 parts by mass or less.

The thickness of the conductive polymer layer is 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 10 μm or less.
If it is at least the lower limit of the above range, sufficient antistatic properties can be exhibited, and if it is at most the upper limit of the above range, the conductive polymer layer can be easily formed.
The thickness of the conductive polymer layer is a value obtained by measuring the thickness at arbitrary 10 points in the cross section of the conductive laminate of this embodiment by a known method and averaging the measured values.

The conductive polymer layer preferably has a surface resistance value of, for example, 1×10 ³ Ω/□ or more and 1×10 ¹⁰ Ω/□ or less as a measure of good antistatic property, and 1×10 ⁴ Ω. It more preferably has a surface resistance value of 1×10 ⁹ Ω/□ or more and 1×10 8 Ω/□ or less, preferably 1×10 ⁵ Ω/□ or more and 1×10 ⁸ Ω/□ or less.

In the conductive laminate of this aspect, the conductive polymer layer may be thinner or thicker than the metal layer. The thickness ratio represented by (the thickness of the conductive polymer layer/the thickness of the metal layer) is, for example, preferably 0.01 or more and 1000 or less, more preferably 0.05 or more and 500 or less, and 0.05 or more. 1 or more and 100 or less is more preferable.
When it is at least the lower limit of the above range, the antistatic property of the conductive polymer layer can be further enhanced, and rusting of the metal layer due to the conductive polymer layer can be more reliably prevented.
When it is equal to or less than the upper limit of the above range, the adhesion of the conductive polymer layer to the metal layer is improved.

<Resin layer>
In the conductive laminate of this aspect, a resin layer may be laminated on the surface of the conductive polymer layer opposite to the metal layer.

The resin layer contains a binder resin and does not contain a conductive composite. Examples of binder resins include acrylic resins, polyester resins, polyurethane resins, polyimide resins, polyether resins, epoxy resins, oxetane resins, vinyl acetate resins, melamine resins, and silicone resins.
Binder resin may be used individually by 1 type, and may use 2 or more types together.
Among them, an acrylic resin is preferable because it is easy to form a resin layer with high hardness.

Specific examples of acrylic monomers forming acrylic resins include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and ditrimethylol. Propane tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A/ethylene oxide-modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, tri methylolpropane triacrylate, glycerin propoxy triacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate acrylates, acrylates such as tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate; tetraethylene glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, allyl methacrylate, 1,3 -butylene glycol dimethacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate , tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, and other methacrylates; (Meth)acrylamides such as -methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, and 2-hydroxyethylacrylamide. One of these acrylic monomers may be used alone, or two or more thereof may be used in combination.

The binder resin contained in the resin layer may be the same type of binder resin as the binder resin contained in the conductive polymer layer, or may be a different binder resin. When the same kind of binder resin is contained in the resin layer and the conductive polymer layer, the adhesion between the resin layer and the conductive polymer layer can be improved.

The content of the binder resin contained in the resin layer can be, for example, 80% by mass or more and 100% by mass or less with respect to the total mass of the resin layer.

The resin layer may contain other additives.
Examples of additives that can be used include surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, and ultraviolet absorbers. However, the additive is composed of a compound other than the π-conjugated conductive polymer, polyanion, and binder resin described above.
Examples of specific additives are the same as the specific examples of the additives that may be contained in the conductive polymer layer, so the examples are omitted here.
When the resin layer contains an additive, the content is appropriately determined according to the type of the additive.

The resin layer may contain the refractive index adjuster described above. In this case, the resin layer containing the refractive index adjuster can function as an undercoat layer as described in Patent Document 1. From the viewpoint of reducing the visibility of the metal layer, the refractive index of the layer is preferably adjusted to 1.61 or more and 1.80 or less.
The content of the refractive index modifier in the resin layer of this embodiment is adjusted in accordance with the desired refractive index in the same manner as the content of the refractive index modifier in the known undercoat layer.

The thickness of the resin layer is preferably 0.05 μm or more and 100 μm or less, more preferably 0.01 μm or more and 50 μm or less, and even more preferably 0.5 μm or more and 10 μm or less.
When the thickness of the resin layer is at least the lower limit, the conductive polymer layer can be sufficiently protected from the outside. When it is equal to or less than the upper limit, the adhesion of the resin layer to the conductive polymer layer is improved.
The thickness of the resin layer is a value obtained by measuring the thickness at arbitrary 10 points in the cross section of the conductive laminate of this embodiment by a known method and averaging the measured values.

In the conductive laminate of this aspect, the resin layer may be thicker or thinner than the conductive polymer layer. The thickness ratio represented by (thickness of the resin layer/thickness of the conductive polymer layer) is, for example, preferably 0.1 to 3000, more preferably 0.2 to 2000, and 0.3 to 1000 is more preferred.
When it is at least the lower limit of the above range, the conductive polymer layer can be sufficiently protected from the outside. When it is equal to or less than the upper limit, the adhesion of the resin layer to the conductive polymer layer is improved.

<Effect>
In the conductive laminate of the present invention, the conductive polymer layer is laminated on the surface of the metal layer, and the excess polyanion of the conductive composite contained in the conductive polymer layer is the epoxy group-containing compound and the Since the metal layer is chemically modified with an amine compound, an increase in resistance of the metal layer due to rusting of the metal layer is prevented. Therefore, it does not easily rust even if it is heated in the operating environment. As a mechanism for preventing the metal layer from rusting due to the influence of the polyanion, the active protons (acids) bound to the anion groups of the polyanion are substituted and neutralized by chemical modification. considered as a factor.

In the electroconductive laminate of the present invention, since the electroconductive polymer layer has antistatic properties, even when the electroconductive laminate receives an electric field from the outside, it is prevented from being charged. Moreover, even when a resin layer is formed on the surface of the conductive polymer layer, charging of the resin layer is suppressed by the conductive polymer layer.

In the conductive laminate of the present invention, the metal layer may be patterned into wiring, electrodes, etc. (may be formed in a pattern). In this case, the conductive polymer layer may be patterned in the same manner as the metal layer, or may be solidly coated over the entire surface. From the viewpoint of enhancing the antistatic property of the entire conductive laminate, it is preferable that the coating is formed on the entire surface by solid coating. In this case, the conductive polymer layer formed on the entire surface by solid coating is in contact with the surface (exposed surface) including the side surface of the patterned metal layer and the surface of the substrate on which the metal layer is formed.
In addition, since the surface resistance value of the conductive polymer layer is larger than that of the metal layer, even if the conductive polymer layer is laminated on the entire surface of the patterned metal layer by solid coating, the metal layer patterning is canceled by the conductive polymer layer.

<<Method for manufacturing conductive laminate>>
A second aspect of the present invention is a method for producing a conductive laminate according to the first aspect, wherein a conductive composite containing a π-conjugated conductive polymer and a polyanion and an organic solvent are provided on the surface of the metal layer. and a lamination step of forming the conductive polymer layer by applying a conductive polymer-containing liquid containing Here, of the surplus anionic groups that do not participate in the doping of the polyanion that constitutes the conductive composite, some are modified by reaction with an epoxy group-containing compound, and another part is an amine compound. modified by reaction with
In the following description of the modified conductive composite, description overlapping with the first aspect will be omitted.

Since the organic solvent contained in the conductive polymer-containing liquid can disperse or dissolve the conductive composite, it can be called a dispersion medium or a solvent. In the present specification, the term "dispersion" may be used without distinguishing between dispersing and dissolving, and the term "dispersion medium" may be used without distinguishing between a dispersion medium and a solvent.
Since the conductive composite contained in the conductive polymer-containing liquid is modified and made hydrophobic as described above, an organic solvent is used as the dispersion medium.

(Organic solvent)
The organic solvent in this embodiment 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. 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.

Examples of water-soluble organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, and nitrogen atom-containing solvents.
Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, Ethylene glycol, propylene glycol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether and the like can be mentioned.
Examples of ether solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, diethylene glycol diethyl ether and the like.
Ketone solvents include, for example, 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 and the like.
Examples of nitrogen atom-containing solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination. Organic solvents mixed with one or more water-insoluble organic solvents may also be used.
As the water-soluble organic solvent, an alcohol-based solvent or a ketone-based solvent is preferable because the conductive polymer-containing liquid has good coating properties. A ketone-based solvent is more preferable because of its excellent compatibility with the water-insoluble organic solvent described below. Among the ketone solvents, methyl ethyl ketone is particularly preferred.

Examples of water-insoluble organic solvents include hydrocarbon-based solvents. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents.
Examples of aliphatic hydrocarbon solvents include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane and the like.
Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
One of the water-insoluble organic solvents may be used alone, or two or more thereof may be used in combination.
Among the water-insoluble organic solvents, aromatic hydrocarbon-based solvents are preferable, and toluene is more preferable, from the viewpoint of improving the dispersibility of the binder component.

The content of the organic solvent with respect to the total mass of the conductive polymer-containing liquid is preferably 50% by mass or more, more preferably 70% by mass or more and 99% by mass or less, and 80% by mass or more and 95% by mass. More preferably: When the content of the organic solvent is within the above range, the conductive composite can be easily dispersed, and there is room for containing the binder component.

(Content of conductive composite)
The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or less, and 0.3% by mass. % by mass or more and 2 mass % or less is more preferable.
When it is at least the lower limit of the above range, the antistatic properties of the conductive polymer layer to be formed can be further enhanced.
When it is equal to or less than the upper limit of the above range, the dispersibility of the conductive composite can be enhanced.

(binder component)
The conductive polymer-containing liquid may contain a binder component. The binder component is a resin other than the π-conjugated conductive polymer and the polyanion or a precursor thereof, and is a thermoplastic resin or a curable monomer or oligomer that cures when the conductive polymer layer is formed. The thermoplastic resin becomes the binder resin as it is, and the resin formed by curing the curable monomer or oligomer becomes the binder resin.
A binder component may be used individually by 1 type, and may use 2 or more types together.

Specific examples of binder resins derived from binder components include acrylic resins, polyester resins, polyurethane resins, polyimide resins, polyether resins, melamine resins, and silicones.
Among them, the polyester resin is preferable because the antistatic properties of the conductive polymer layer to be formed hardly deteriorate and the film strength increases. Moreover, when a polyester film substrate is used, if the binder component is a polyester resin, the adhesion of the conductive polymer layer to the film substrate can be increased.

The curable monomers or oligomers may be thermosetting monomers or oligomers or photocurable monomers or oligomers. Here, an oligomer is a polymer having a mass average molecular weight of less than 10,000. A polymer having a weight average molecular weight of more than 10,000 does not have curability.
Examples of curable monomers include acrylic monomers (acrylic compounds), epoxy monomers, and organosiloxanes. Examples of curable oligomers include acrylic oligomers (acrylic compounds), epoxy oligomers, and silicone oligomers (curable silicone).
When an acrylic monomer or acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation. When an organosiloxane or silicone oligomer is used as the binder component, it is possible to impart releasability (easy peelability) to the conductive polymer layer.

When curable monomers or oligomers are included, it is preferable to further include a curing catalyst. For example, if it contains a thermosetting monomer or oligomer, it preferably contains a thermal polymerization initiator that generates radicals by heating, and if it contains a photocurable monomer or oligomer, it generates radicals by light irradiation. It preferably contains a photopolymerization initiator that causes the Also, if it contains an organosiloxane or silicone oligomer, it preferably contains a platinum catalyst for curing.

The content of the binder component in the conductive polymer-containing liquid is preferably 10 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. Part or more and 1000 parts by mass or less is more preferable. When the content of the binder component is at least the above lower limit, it is possible to improve film formability and film strength when the conductive polymer-containing liquid is applied to the surface of the metal layer. When the content of the binder component is equal to or less than the above upper limit, it is possible to suppress deterioration of the antistatic properties due to a decrease in the content of the conductive composite.

(high conductivity agent)
The conductive polymer-containing liquid may contain a highly conductive agent in order to further improve antistatic properties.
Conductive agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having two or more carboxyl groups, one or more hydroxy groups and one or more carboxyl groups. , compounds having an amide group, compounds having an imide group, lactam compounds, and compounds having a glycidyl group.
However, the conductivity enhancing agent is a compound other than the π-conjugated conductive polymer, polyanion, dispersion medium, amine compound, and binder component described above.
Among the highly conductive agents, glycol, which is a linear compound having two hydroxy groups, is preferable, and propylene glycol is more preferable, because the antistatic property is further improved.
The conductive polymer-containing liquid may contain one or more conductive agents.

The content of the high conductivity agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. It is more preferable that the amount is from 1 part to 2500 parts by mass. If the content of the high-conductivity agent is at least the lower limit, the antistatic property is sufficiently improved by the addition of the high-conductivity agent. It is possible to prevent deterioration of antistatic properties caused by.

(Other additives)
The conductive polymer-containing liquid may contain other additives.
Additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers and the like can be used.
However, the additive is anything other than the π-conjugated conductive polymer, polyanion, dispersion medium, amine compound, binder component, and high-conductivity agent described above.
Examples of specific additives are the same as the specific examples of the additives that may be contained in the conductive polymer layer, so the examples are omitted here.

Further, the conductive polymer-containing liquid may contain the above-described refractive index adjuster.

When the conductive polymer-containing liquid contains an additive, the content ratio is appropriately determined according to the type of the additive. It can be in the range of 5 parts by mass or less.

The conductive polymer-containing liquid described above is prepared by dispersing the modified conductive composite in an organic solvent, adding a binder component, a high conductivity agent, and other additives as necessary, and using a conventional method. It can be prepared by dispersing the ingredients.
In addition, in the method for producing a conductive laminate of this aspect, a preparation step for obtaining a modified conductive composite may be performed. The preparation step is performed before the lamination step.

[Preparation process]
A conductive polymer-containing liquid containing a modified conductive composite is preferably obtained by the following method.
That is, an aqueous dispersion containing an unmodified conductive composite containing a π-conjugated conductive polymer and a polyanion and an aqueous dispersion medium is added with an epoxy compound to obtain a first reaction solution, and the polyanion is doped. After precipitating the conductive composite by reacting the epoxy compound with a part of the surplus anionic groups that do not participate in the first reaction solution, the precipitate of the conductive composite is recovered, An organic solvent is added to the precipitate to obtain a preparation solution in which the precipitate is dispersed, to obtain a second reaction solution in which an amine compound is added to the preparation solution, and surplus that does not participate in the doping of the polyanion is obtained. By reacting another portion of the anionic group with the amine compound, the conductive polymer-containing liquid can be obtained.

(First reaction solution)
Descriptions of the π-conjugated conductive polymer and the polyanion that constitute the unmodified conductive composite are omitted since they are the same as those of the first embodiment.

The aqueous dispersion medium in which the unmodified conductive composite is dispersed is water or a mixture of water and a water-soluble organic solvent. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents, as described above. One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
The water content relative to the total mass of the aqueous dispersion medium is more than 50% by mass, preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

The content of the conductive composite is preferably 0.01% by mass or more and 4% by mass or less with respect to the total mass of the aqueous dispersion containing the unmodified conductive composite (aqueous conductive polymer dispersion). 05% by mass or more and 3% by mass or less is more preferable, and 0.1% by mass or more and 2% by mass or less is even more preferable.
Within the above range, the deposition of the conductive composite hydrophobized by the reaction with the epoxy compound is favorable.

An unmodified conductive composite can be obtained, for example, by chemically oxidatively polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous polyanion solution. A commercially available conductive polymer aqueous dispersion may also be used.

The explanation of the epoxy compound added to the aqueous dispersion is the same as the explanation of the first embodiment, so redundant explanation is omitted. One type of epoxy compound may be added to the aqueous dispersion, or two or more types may be used.

The amount of the epoxy compound added to the aqueous dispersion is preferably 100 parts by mass or more and 10000 parts by mass or less, and is preferably 200 parts by mass or more and 6000 parts by mass or less with respect to 100 parts by mass of the conductive composite. More preferably, it is 300 parts by mass or more and 3000 parts by mass or less. When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite can be sufficiently improved, and the precipitated conductive composite can be recovered with good yield. When it is at most the upper limit of the above range, a part of the surplus anionic groups possessed by the conductive composite can remain, and the amine compound can be sufficiently reacted in the latter stage.

An organic solvent may be added before, at the same time as, or after adding the epoxy compound to the conductive polymer aqueous dispersion. As the organic solvent, a water-soluble organic solvent is preferable. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The water-soluble organic solvent to be added may be one kind, or two or more kinds.

In the first reaction liquid obtained by adding the epoxy compound to the aqueous dispersion, a part of the surplus anion groups that do not participate in the doping of the polyanion that constitutes the conductive composite undergoes a ring-opening reaction with the epoxy group of the epoxy compound. By doing so, the negative charge of some of the anionic groups disappears. Thereby, the conductive composite is hydrophobized. In order to promote this hydrophobization, the conductive polymer aqueous dispersion may be heated. The heating temperature is, for example, 40 to 80°C.
A hydrophobized electrically conductive composite cannot be dispersed in an aqueous dispersion medium, and precipitates to form a deposit.

A method for collecting the conductive composite precipitated in the first reaction liquid is not particularly limited, and examples thereof include filtration, decantation, centrifugation, vacuum drying, freeze drying, spray drying and the like.
Among them, filtration or decantation is preferable because it is easy to separate components other than the hydrophobized conductive composite contained in the first reaction solution from the hydrophobized conductive composite. Here, filtration is an operation of trapping deposits of the conductive composite on a filter through which the first reaction liquid has passed. Also, decantation is an operation of allowing the precipitated conductive composite to settle and removing the supernatant.
When fractionating by filtration, it is necessary to deal with clogging of the filter, so decantation can fractionate more easily. In addition, since the solid matter of the conductive composite is compressed by the filtration pressure on the filter, the conductive composite isolated by filtration tends to be in a harder state than when separated by decantation. Since the conductive composite obtained by decantation is obtained in a relatively soft powder state, it can be easily dispersed in a dispersion medium later. Therefore, it is more preferable to recover the conductive composite by decantation.

As a filter used for filtration, filter paper used in the field of chemical analysis is preferable. As this filter paper, for example, a filter paper manufactured by Advantech Co., Ltd., a retention particle size of 7 μm, or the like can be used. Here, the retained particle size of the filter paper is a measure of the coarseness of the mesh, and is determined from the leaked particle size when barium sulfate or the like is naturally filtered as specified in JIS P 3801 [filter paper (for chemical analysis)]. The retained particle size of the filter paper can be, for example, 2 μm or more and 10 μm or less. The retained particle size is preferably 5 μm or more and 10 μm or less, since excess polyanion or the like can be permeated and easily separated.

(Second reaction liquid)
An organic solvent is added to the precipitate to obtain a prepared liquid in which the precipitate is dispersed, and a second reaction liquid is obtained by adding an amine compound to the prepared liquid.
Examples of the organic solvent to be added to the precipitate include the organic solvents constituting the conductive polymer-containing liquid exemplified in the second embodiment. Among them, ketone-based solvents are preferred, and methyl ethyl ketone is more preferred, from the viewpoint of good dispersibility of the precipitate.

It is preferable to sufficiently disperse the hydrophobized conductive composite by stirring the prepared liquid obtained by adding an organic solvent to the precipitate using a high-pressure homogenizer or the like while applying a high shearing force.

The content of the hydrophobized conductive composite with respect to the total mass of the preparation liquid is, for example, 0.1% by mass or more and 20% by mass or less from the viewpoint of increasing dispersibility and increasing reactivity with the amine compound. It is preferably 0.2% by mass or more and 10% by mass or less, and even more preferably 0.3% by mass or more and 5.0% by mass or less.

The description of the amine compound added to the preparation liquid is the same as the description of the first embodiment, so redundant description is omitted. One type of amine compound may be added to the preparation liquid, or two or more types may be used.

When the amine compound is an imidazole-based amine (for example, imidazole), the amount of the amine compound added to the preparation solution is preferably 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive composite. 20 parts by mass or more and 200 parts by mass or less is more preferable, and 50 parts by mass or more and 150 parts by mass or less is even more preferable. When it is at least the lower limit of the above range, the amine compound can be sufficiently reacted with the conductive composite. When it is equal to or less than the upper limit of the above range, it is possible to prevent an excess amine compound from remaining in the target conductive polymer-containing liquid.

When the amine compound is a non-imidazole-based amine (e.g., a tertiary amine), the amount of the amine compound added to the preparation solution is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the conductive composite. , more preferably 5 parts by mass or more and 50 parts by mass or less, and even more preferably 10 parts by mass or more and 30 parts by mass or less. When it is at least the lower limit of the above range, the amine compound can be sufficiently reacted with the conductive composite. When it is equal to or less than the upper limit of the above range, it is possible to prevent an excess amine compound from remaining in the target conductive polymer-containing liquid.

In the second reaction solution obtained by adding an amine compound to the preparation solution, among the surplus anion groups that do not participate in the doping of the polyanion that constitutes the conductive composite, the anion groups remaining without reacting with the epoxy compound The amine compound reacts and binds to at least a portion of. The reaction proceeds at room temperature and is complete in seconds.
By the above method, the reaction in the second reaction liquid is completed, and the target conductive polymer-containing liquid is obtained.
If necessary, the above-described binder component, conductivity enhancing agent, and other additives may be added to the conductive polymer-containing liquid by a conventional method.

[Lamination process]
The metal layer to which the conductive polymer-containing liquid is applied is preferably formed in advance on the surface of the substrate.
The method of applying the conductive polymer-containing liquid to the surface of the metal layer is not particularly limited, and examples thereof include gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, and rods. Coating methods using coaters such as coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, and screen coaters; spraying methods using atomizers such as air spray, airless spray, and rotor dampening; and immersion methods such as dipping. etc. can be applied.

The amount of the conductive polymer-containing liquid applied to the surface of the metal layer is appropriately set according to the thickness of the conductive polymer layer to be formed. From the viewpoint of obtaining good antistatic properties, the solid content is preferably in the range of 0.1 g/m ² or more and 10.0 g/m ² or less.

Examples of the method for drying the coating film made of the conductive polymer-containing liquid applied to the surface of the metal layer include heat drying and vacuum drying. As heat drying, for example, a normal method such as hot air heating or infrared heating can be used. When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, and can be set to, for example, 50° C. or higher and 150° C. or lower. Here, the heating temperature is the set temperature of the drying device. The drying time for drying at the above temperature can be, for example, 30 seconds or more and 3 minutes or less.
When the coating film contains an active energy ray-curable binder component, it may further include an active energy ray irradiation step of irradiating the dried coating film with an active energy ray. If the active energy ray irradiation step is included, the forming speed of the conductive polymer layer can be increased, and the productivity of the conductive laminate is improved.
Examples of active energy rays include ultraviolet rays, electron beams, visible rays, and the like. Ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, and the like can be used as the ultraviolet light source.
The illuminance in ultraviolet irradiation is preferably 100 mW/cm ² or more from the viewpoint of sufficiently curing the conductive polymer layer. From the viewpoint of sufficiently curing the conductive polymer layer, the integrated amount of light is preferably 50 mJ/cm ² or more. In addition, the illuminance and the integrated amount of light in this specification are measured using Topcon UVR-T1 (industrial UV checker, light receiver; UD-T36, measurement wavelength range: 300 nm or more and 390 nm or less, peak sensitivity wavelength: about 355 nm). It is a measured value.

[Lamination of resin layers]
The method of forming the resin layer on the surface of the conductive polymer layer is not particularly limited, and the resin layer is formed by applying a resin composition containing the above-described binder resin, its monomer component, etc. by a conventional method. be able to.
Further, the resin composition may contain the above-described refractive index adjuster.

(Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of an ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was added while stirring at 80°C. After adding dropwise for 20 minutes, the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting sodium polystyrenesulfonate-containing solution, and about 1000 ml of the solvent in the obtained polystyrenesulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This washing operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Production Example 2) Production of conductive polymer aqueous dispersion medium A solution of 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of deionized water was heated at 20°C. Mixed.
The resulting mixed solution was kept at 20° C., and while stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were slowly added, and the mixture was stirred for 3 hours. The mixture was stirred and reacted.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three times.
Next, 200 ml of 10 mass % diluted sulfuric acid and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by ultrafiltration. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated five times to obtain a conductive polymer aqueous dispersion medium in which polystyrenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) with a concentration of 1.2% by mass was dispersed in the aqueous dispersion medium. Ta.

(Production Example 3) Production of conductive polymer-containing liquid containing hydrophobized conductive composite 25 g of Epolite M-1230 (C12, C13 mixed higher alcohol glycidyl ether) was added, and the mixture was heated and stirred at 60° C. for 4 hours. At this time, the epoxy groups of the epoxy compound were reacted and bonded to some of the surplus sulfonic acid groups of PEDOT-PSS that were not bonded to the PEDOT of the PSS. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive composite containing a reaction product of PEDOT-PSS and an epoxy compound was deposited. This precipitate was collected by filtration to obtain 1.575 g of the conductive composite.
Next, 1.575 g of the above conductive composite was added to 315 g of methyl ethyl ketone and dispersed using a high-pressure homogenizer to obtain a preparation liquid.

(Production example 4)
300 g of methanol and 25 g of butylene oxide were added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and the mixture was heated and stirred at 60° C. for 4 hours. At this time, the epoxy groups of the epoxy compound were reacted and bonded to some of the surplus sulfonic acid groups of PEDOT-PSS that were not bonded to the PEDOT of the PSS. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive composite containing a reaction product of PEDOT-PSS and an epoxy compound was deposited. This precipitate was collected by filtration to obtain 1.3 g of the conductive composite.
Next, 1.3 g of the conductive composite was added to 315 g of methyl ethyl ketone and dispersed using a high-pressure homogenizer to obtain a preparation liquid.

(Example 1)
An ITO glass (thickness of ITO layer: 50 nm) was prepared by sputtering ITO on glass of 75 mm×75 mm, and 5 mm portions of both lateral ends of the ITO layer were masked with sellotape (registered trademark).
Next, 0.3 g of imidazole was added to 100 g of the preparation liquid of Production Example 3, and 10 g of an amorphous polyester resin (Vylon 240, manufactured by Toyobo Co., Ltd., solid content 30%, toluene solution) was added to obtain a paint. .
The paint was applied on masked ITO glass using a #4 bar coater and dried at 100° C. for 1 minute to form a conductive polymer layer on the ITO layer.
By the above method, a conductive laminate was obtained in which glass/ITO layer/conductive polymer layer were laminated in this order.

(Example 2)
A conductive laminate was produced in the same manner as in Example 1, except that 0.6 g of imidazole was used.

(Example 3)
A conductive laminate was produced in the same manner as in Example 1, except that 0.15 g of imidazole was used.

(Example 4)
A conductive laminate was produced in the same manner as in Example 1, except that 0.05 g of trioctylamine was used in place of 0.3 g of imidazole.

(Example 5)
A conductive laminate was produced in the same manner as in Example 1, except that 0.026 g of tributylamine was used in place of 0.3 g of imidazole.

(Example 6)
A conductive laminate was produced in the same manner as in Example 1, except that 100 g of the preparation liquid of Production Example 3 was changed to 100 g of the preparation liquid of Production Example 4.

(Example 7)
A conductive laminate was produced in the same manner as in Example 1, except that the ITO glass was an ITO film (ITO layer thickness: 20 nm) obtained by sputtering ITO on a 75 mm×75 mm PET film.

(Example 8)
ITO was sputtered on glass of 75 mm×75 mm to prepare an ITO glass, and a 5 mm end portion on both sides of the ITO layer was masked with sellotape.
Next, 0.3 g of imidazole was added to 100 g of the preparation liquid of Production Example 3, and 10 g of an amorphous polyester resin (Vylon 240, manufactured by Toyobo Co., Ltd., solid content 30%, toluene solution) was added to prepare paint (A). Obtained. Further, 50 g of pentaerythritol triacrylate, 50 g of isopropanol, and 2 g of Irgacure 184 (manufactured by BASF, photopolymerization initiator) were added to obtain paint (B).
The paint (A) was applied on masked ITO glass using a #4 bar coater and dried at 100° C. for 1 minute to form a conductive polymer layer on the ITO layer. Subsequently, the coating material (B) was applied on the conductive polymer layer using a #4 bar coater and irradiated with 400 mJ ultraviolet rays to form a hard coat layer.
By the above method, a conductive laminate was obtained in which glass/ITO layer/conductive polymer layer/hard coat layer were laminated in this order.

(Comparative example 1)
A conductive laminate was obtained in the same manner as in Example 1, except that imidazole was not added.

(Comparative example 2)
A conductive laminate was obtained in the same manner as in Example 1, except that 100 g of the preparation liquid of Production Example 3 was changed to 100 g of methyl ethyl ketone.

<Evaluation>
(Measurement of surface resistance)
The surface resistance value of the conductive polymer layer of the conductive laminate produced in each example was measured using a resistivity meter (Mitsubishi Chemical Analytic Tech, Hiresta) under the condition of an applied voltage of 10V. Table 1 shows the measurement results. "Ω/□" in the table means ohms per square. Also, "1.0E+08" represents "1.0×10 ⁸ ".
The surface resistance of the conductive laminate of Example 7 was measured by placing a probe of a resistivity meter on the hard coat layer.

(heating test)
A heating test was conducted as follows to accelerate the rusting of the ITO layer by heating the conductive laminate produced in each example.
Peel off the mask at both ends of the conductive laminate prepared in each example, expose the ITO layer (contact), use a digital multimeter (manufactured by CUTTOM, CDM-17D), bring the terminal into contact with the contact, initial A resistance value _R0 was measured. Subsequently, the same conductive laminate was heated at 40° C. for 240 hours, and then the post-heating resistance value _R1 was measured. The rate of increase in resistance value before and after heating was calculated by R ₁ /R ₀ . These results are shown in Table 1.

From the results in Table 1, in Examples 1 to 8 according to the present invention, the conductive composite contained in the conductive polymer layer laminated on the surface of the ITO layer was modified with an epoxy compound and an amine compound. ing. It is clear that this suppresses rusting of the ITO layer and suppresses an increase in resistance after the heating test.
On the other hand, in Comparative Example 1, since the conductive composite was modified only with the epoxy compound, rusting of the ITO layer was not sufficiently suppressed, and the resistance after the heating test increased significantly.
In Comparative Example 2, since the resin layer laminated on the ITO layer does not contain the conductive composite, the surface resistance value is high and the resin layer does not have antistatic properties.

Claims (14)

A conductive laminate comprising a conductive layer containing a metal element and a conductive polymer layer laminated on the surface of the conductive layer containing the metal element,
The conductive polymer layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion,
Of the surplus anionic groups that do not participate in the doping of the polyanion, a portion is modified by reaction with an epoxy group-containing compound, and another portion is modified by reaction with an amine compound,
A conductive laminate , wherein the epoxy group-containing compound is a higher alcohol glycidyl ether having 10 to 16 carbon atoms . 2. The conductive laminate according to claim 1, wherein a glass substrate or a film substrate is laminated on the surface of the conductive layer containing the metal element opposite to the conductive polymer layer. 3. The conductive laminate according to claim 1, wherein a resin layer is laminated on the surface of the conductive polymer layer opposite to the conductive layer containing the metal element . The conductive laminate according to claim 3, wherein the resin layer contains an acrylic resin. The conductive laminate according to any one of claims 1 to 4, wherein the conductive layer containing the metal element is made of ITO. The conductive laminate according to any one of claims 1 to 5, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The conductive laminate according to any one of claims 1 to 6, wherein said polyanion is polystyrene sulfonic acid. A conductive layer containing a metal element, and a conductive polymer layer laminated on the surface of the conductive layer containing the metal element,
The conductive polymer layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and some of the excess anionic groups that do not participate in the doping of the polyanion contain epoxy groups. A method for producing a conductive laminate modified by reaction with a compound, another part by reaction with an amine compound, comprising:
A preparation step of preparing a conductive polymer-containing liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion and an organic solvent;
a laminating step of forming the conductive polymer layer by applying the conductive polymer-containing liquid to the surface of the conductive layer containing the metal element ;
In the preparation step,
obtaining a first reaction liquid obtained by adding an epoxy group-containing compound to an aqueous dispersion containing the conductive composite and an aqueous dispersion medium,
After depositing the conductive composite by reacting the epoxy group-containing compound with a part of the surplus anionic groups that do not participate in the doping of the polyanion,
recovering the deposit of the conductive composite from the first reaction solution;
adding an organic solvent to the precipitate to obtain a preparation solution in which the precipitate is dispersed,
Obtaining a second reaction solution by adding an amine compound to the prepared solution,
A method for producing a conductive laminate, wherein the conductive polymer-containing liquid is obtained by reacting another part of the surplus anionic groups that do not participate in the doping of the polyanion with the amine compound. 9. The method for producing a conductive laminate according to claim 8, wherein the organic solvent contains methyl ethyl ketone. 10. The method for producing a conductive laminate according to claim 8, wherein said amine compound is a heterocyclic aromatic amine or a tertiary amine. The method for producing a conductive laminate according to any one of claims 8 to 10, wherein the amine compound is imidazole, tributylamine or trioctylamine. The method for producing a conductive laminate according to any one of claims 8 to 11, wherein the conductive polymer-containing liquid further contains a binder component. 13. The method for producing a conductive laminate according to claim 12, wherein the binder component is a polyester resin. The method for producing a conductive laminate according to any one of claims 8 to 13, wherein the epoxy group-containing compound is a higher alcohol glycidyl ether having 10 to 16 carbon atoms.