JP7097832B2 - Manufacturing method of conductive laminate - Google Patents

Description

The present invention relates to a method for producing a conductive laminate using a conductive polymer dispersion liquid containing a π-conjugated conductive polymer.

As an input device for a portable electronic device such as a smartphone, an in-cell type capacitive touch panel having excellent thinness may be used (for example, Patent Document 1).
The in-cell type capacitive touch panel includes a conductive laminate in which a conductive layer is formed on the surface of a glass base material. Conductive polymers are attracting attention as conductive materials that give appropriate conductivity to the conductive layer. For example, they are based on a conductive polymer dispersion containing a conductive composite of a π-conjugated conductive polymer and a polyanion. A method of coating a material surface with a bar coater is known (for example, Patent Document 2).

International Publication No. 2014/042248 Japanese Unexamined Patent Publication No. 2018-115269

In the process of incorporating the touch panel into the product, the conductive layer on the surface of the base material may be scratched. In order to increase the hardness of the conductive layer in order to prevent this damage, the conductive polymer dispersion liquid forming the conductive layer may contain silicate.
However, when the conductive polymer dispersion liquid containing silicate is applied with a bar coater or a slit coater, a dried product containing silicate adheres to the gap between the flow paths and the edge of the discharge port. If this coating is continued, the dried product occasionally peels off and is placed on the coating film, which causes a problem that the appearance and performance of the coating film are deteriorated.

INDUSTRIAL APPLICABILITY The present invention is a method for producing a conductive laminate in which when a conductive polymer dispersion liquid is applied to the surface of a base material to form a conductive layer having sufficient hardness, the appearance and performance of the conductive layer are less likely to be deteriorated. I will provide a.

[1] A method for producing a conductive laminate, which comprises forming a conductive layer on the surface of the base material by spray-coating the base material with a conductive polymer dispersion liquid, and the above-mentioned conductive polymer dispersion. A method for producing a conductive laminate, wherein the liquid contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a silicate, and an aqueous dispersion medium containing water and an organic solvent.
[2] The method for producing a conductive laminate according to [1], wherein the conductive polymer dispersion further contains an epoxy group-containing alkoxysilane.
[3] The method for producing a conductive laminate according to [1] or [2], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[4] The method for producing a conductive laminate according to any one of [1] to [3], wherein the polyanion is polystyrene sulfonic acid.
[5] The conductivity according to any one of [1] to [4], wherein the silicate is at least one selected from tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrapropoxysilane. A method for manufacturing a sex laminate.
[6] The conductive polymer dispersion further contains an epoxy group-containing alkoxysilane, and the epoxy group-containing alkoxysilane is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-. The method for producing a conductive laminate according to any one of [1] to [5], which is glycidoxypropylmethyldimethoxysilane or 3-glycidoxypropylmethyldiethoxysilane.
[7] The method for producing a conductive laminate according to any one of [1] to [6], wherein the aqueous dispersion medium contains methanol, ethanol, isopropanol, or propylene glycol monomethyl ether.
[8] The method for producing a conductive laminate according to any one of [1] to [7], wherein the conductive polymer dispersion further contains an antioxidant.
[9] The method for producing a conductive laminate according to [8], wherein the antioxidant contains a compound having two or more hydroxy groups.
[10] The method for producing a conductive laminate according to [9], wherein the compound having two or more hydroxy groups contains at least one selected from the group consisting of gallic acid and an ester of gallic acid.
[11] The item according to any one of [1] to [10], wherein the content of the silicate with respect to the total mass of the conductive polymer dispersion is 0.25% by mass or more and 5.0% by mass. A method for manufacturing a conductive laminate.
[12] The method for producing a conductive laminate according to any one of [1] to [11], wherein the conductive polymer dispersion further contains a surfactant.
[13] The method for producing a conductive laminate according to [12], wherein the surfactant is a polyether-modified silicone.
[14] The method for producing a conductive laminate according to any one of [1] to [13], wherein the base material is a glass base material.
[15] The method for producing a conductive laminate according to [14], wherein the glass substrate is a non-alkali glass substrate.
[16] The method for producing a conductive laminate according to [14] or [15], wherein the glass substrate is a member of a liquid crystal cell.

According to the method for producing a conductive laminate of the present invention, it is possible to produce a conductive laminate containing a silicate and having a conductive layer having a good appearance and performance.

It is a schematic diagram which shows the outline of the apparatus composition about an example of a spray coating apparatus. It is a schematic partial break side view of the spray gun of the said spray coating apparatus. It is a schematic partial breakage side view which enlarged the tip part of the spray gun.

<Conductive polymer dispersion liquid>
One aspect of the conductive polymer dispersion liquid used in the present invention contains a conductive composite, a silicate, and an aqueous dispersion medium containing water and an organic solvent.

[Conductive complex]
The conductive composite in this embodiment includes a π-conjugated conductive polymer and a polyanion. The polyanion coordinates with the π-conjugated conductive polymer, and a part of the anion group of the polyanion is doped with the π-conjugated conductive polymer, so that a conductive composite having conductivity is formed.

(Pi-conjugated conductive polymer)
The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer whose main chain is composed of a π-conjugated system, as long as it has the effect of the present invention. Conductive polymer, polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophenine-based conductive polymer, and Examples thereof include these copolymers. 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.

Examples of the polythiophene-based conductive polymer 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-didodecyloxythiophene) 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-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and 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).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among the above-mentioned π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable 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)
The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic 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 anion 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, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic carboxylic acid, polymethacrylic carboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, and polyacrylic acid. May be these homopolymers or may be two or more kinds of copolymers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, 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 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight of the polyanion is the mass-based molecular weight determined based on the elution time vs. molecular weight calibration curve obtained in advance from a polystyrene standard material having a known molecular weight by measuring the elution time using gel permeation chromatography (GPC). That is.

Polyanions form a conductive complex by coordinating with a π-conjugated conductive polymer. However, in the polyanion, a part of the anion group is not doped in the π-conjugated conductive polymer and has an extra anion group. Since this excess anion group is a hydrophilic group, the conductive complex has water dispersibility.

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 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. It is more preferable that the amount is 100 parts by mass or more and 500 parts by mass or less. When the content ratio of the polyanion is at least the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

The content of the conductive composite with respect to the total mass of the conductive polymer dispersion is, for example, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less. More preferably, it is 1.0% by mass or more and 5.0% by mass or less.

[Sylicate]
The silicate used in this embodiment is a silicic acid ester. Preferred silicates include compounds represented by the following chemical formula (I).
Examples of the silicate represented by the following chemical formula (I) include at least one selected from the group consisting of tetraethyl orthosilicate, tetramethyl orthosilicate, and a silicic acid oligomer having at least one of a methyl group and an ethyl group. ..

In the formula (I), R ¹ , R ² , R ³ and R ⁴ are independently alkyl groups having 1 to 4 carbon atoms, and s is an integer of 1 to 100.
The alkyl group having 1 to 4 carbon atoms may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group.
The s is preferably 1 to 50, more preferably 1 to 25, and even more preferably 1 to 10.

As the silicic acid oligomer, at least one of the compound represented by the following chemical formula (II) and the compound represented by the following chemical formula (III) is more preferable from the viewpoint of stability.
Si _n On _-1 (OCH ₃ ) _{2n + 2} ... (II)
In the formula (II), n is an integer of 2 or more and 100 or less.
Si _m O _m-1 (OCH ₂ CH ₃ ) _{2m + 2} ... (III)
In the above formula (III), m is an integer of 2 or more and 100 or less.
The silicate used in this embodiment may be used alone or in combination of two or more.

The silicic acid oligomer is preferably a silicic acid ester having two or more silicon atoms in one molecule because the hardness of the conductive layer formed from the conductive polymer dispersion liquid of this embodiment becomes higher. The number of silicon atoms in one molecule in the silicic acid oligomer is more preferably 3 or more, and further preferably 4 or more. The number of silicon atoms in one molecule in the silicic acid oligomer is more preferably 30 or less, and further preferably 20 or less.
The content of ₂ units of SiO of the silicic acid oligomer is preferably 40% by mass or more and 70% by mass or less, and more preferably 50% by mass or more and 60% by mass or less with respect to the total mass of the silicate. When the content of ₂ units of SiO of the silicic acid oligomer is at least the above lower limit value, the hardness of the conductive layer formed from the conductive polymer dispersion is higher, and when it is at least the above upper limit value, the conductive polymer. It is possible to prevent a decrease in the conductivity of the conductive layer formed from the dispersion liquid.
Here, the content of ₂ units of SiO in silicate is the ratio of the mass of ₂ units of SiO (—O—Si—O— unit) contained in silicate to 100% by mass of the molecular weight of silicate, and is obtained by elemental analysis. Can be measured. The content of ₂ units of SiO when two or more kinds of silicates are used is the average value of the contents of ₂ units of SiO of each silicate.

The preferable content of the silicate in the conductive polymer dispersion liquid of this embodiment is appropriately selected according to the content of ₂ units of SiO of the silicate. When the content of ₂ units of SiO of the silicate is in the above preferable range, the content of silicate is 1 part by mass or more and 100,000 parts by mass in terms of the content of ₂ units of SiO with respect to 100 parts by mass of the conductive composite. It is preferably 10 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 1000 parts by mass or less. When the content of the silicate is at least the above lower limit value, the hardness of the conductive layer formed from the conductive polymer dispersion can be sufficiently increased, and when it is at least the above upper limit, it is formed from the conductive polymer dispersion. It is possible to prevent a decrease in the conductivity of the conductive layer.

[Epoxy group-containing alkoxysilane]
The conductive polymer dispersion liquid of this embodiment may further contain an epoxy group-containing alkoxysilane.
The epoxy group-containing alkoxysilane is a silicon compound having an epoxy group and an alkoxy group in the molecule. Here, it is preferable that the oxygen atom of the alkoxy group is bonded to the silicon atom.
Examples of the epoxy group-containing alkoxysilane include those having one epoxy group in one molecule and one or more and three or less alkoxy groups in one molecule.
The epoxy group-containing alkoxysilane is preferably a compound represented by the following formula (IV) or a compound represented by the following formula (V).

In formula (IV), R ⁵ and R ⁶ are arbitrary divalent organic groups, R ⁷ , R ⁸ and R ⁹ are arbitrary substituents, and at least one of R ⁷ , R ⁸ and R ⁹ One is an alkoxy group.
In formula (V), R ¹¹ is an arbitrary divalent organic group, R ¹² , R ¹³ and R ¹⁴ are arbitrary substituents, and at least one of R ¹² , R ¹³ and R ¹⁴ is alkoxy. It is a group. Ring A is a 3- to 8-membered cycloalkane.

Optional substituents include, for example, a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), and the like. Examples thereof include an aryl group (for example, a phenyl group, etc.). These substituents may further have a substituent (for example, a (meth) acryloyloxy group, a carboxy group, a hydroxy group, an epoxy group, an amino group, a trialkoxysilyl group, etc.). Examples of the arbitrary divalent organic group include a divalent group obtained by removing one arbitrary hydrogen atom from an arbitrary substituent.

Examples of R5 and R6 in the formula ( ^IV ) include alkylene groups having 1 to ⁴ carbon atoms independently, and specific examples thereof include an ethylene group, a propylene group, and a butylene group.
Examples of R ⁷ , R ⁸ and R ⁹ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, respectively, among R ⁷ , R ⁸ and R ⁹ . At least one is an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a t-butoxy group and the like.
Examples of the ring A in the formula (V) include cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. R ¹¹ is bonded to ring A by substituting one of the arbitrary hydrogen atoms of the cycloalkane of ring A. Examples of R ¹¹ include an alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group having 1 to 4 carbon atoms include an ethylene group, a propylene group and a butylene group.
Examples of R ¹² , R ¹³ and R ¹⁴ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, respectively. Here, at least one of R ¹² , R ¹³ and R ¹⁴ is an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and the like. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a t-butoxy group and the like.

Specific examples of the epoxy group-containing alkoxysilane represented by the formula (IV) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxy. Examples thereof include silane and 3-glycidoxypropyltriethoxysilane.
Specific examples of the epoxy group-containing alkoxysilane represented by the formula (V) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
These alkoxysilanes may be used alone or in combination of two or more.

In the conductive polymer dispersion liquid of this embodiment, the content of the epoxy group-containing alkoxysilane is preferably defined by the mass ratio with the polyanion. Specifically, the mass ratio B represented by (mass of epoxy group-containing alkoxysilane) / (mass of polyanion) is preferably 50 or more and 300 or less, and 71.4 or more and 285.7 or less. More preferred. When the mass ratio B is within the above range, the storage stability of the conductive polymer dispersion becomes higher.

The epoxy group-containing alkoxysilane reacts with some anion groups of the polyanion. The epoxy group-containing alkoxysilane may react with some anionic groups in the conductive polymer dispersion, or the conductive polymer dispersion is used as a base material in the method for producing a conductive laminate described later. It may react with some anionic groups when heated and dried after coating.

(Dispersion medium)
The dispersion medium in the conductive polymer dispersion liquid of this embodiment is an aqueous dispersion medium for dispersing the conductive composite, and is a mixed liquid containing water and an organic solvent.
Examples of the organic solvent used in this embodiment include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, nitrogen atom-containing compound-based solvents, and the like. One type of organic solvent may be used alone, or two or more types may be used in combination.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol and propylene glycol monomethyl. Examples thereof include ether and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, propylene glycol dialkyl ether and the like.
Examples of the ketone solvent 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 and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.

In this embodiment, since the conductive composite, the silicate, and the epoxy group-containing alkoxysilane can be easily dispersed or dissolved, it is preferable to use an alcohol solvent, a ketone solvent, or an ester solvent as the organic solvent, and the alcohol solvent is preferable. Is more preferable to use.
In particular, the organic solvent preferably contains a low boiling point alcohol having a boiling point of less than 100 ° C. at standard atmosphere and a high boiling point alcohol having a boiling point of 100 ° C. or higher and 150 ° C. or lower at standard pressure. Here, the standard atmospheric pressure is 1013 hPa. If the organic solvent contains a low boiling point alcohol and a high boiling point alcohol, the storage stability of the conductive polymer dispersion can be further improved.
Examples of low boiling alcohols include methanol (boiling point 65 ° C.), ethanol (boiling point 78 ° C.), 1-propanol (boiling point 97 ° C.), 2-propanol (boiling point 82 ° C.), and 2-methyl-2-propanol (boiling point 83 ° C.). ° C.), 2-butanol (boiling point 99 ° C.), allyl alcohol (boiling point 97 ° C.) and the like.
Examples of the high boiling point alcohol include 1-butanol (boiling point 117 ° C.), 2-methyl-1-propanol (boiling point 108 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), ethylene glycol monomethyl ether (boiling point 124 ° C.), and the like. Can be mentioned.

When the dispersion medium contains low-boiling alcohol and high-boiling alcohol, the composition of the dispersion medium is 25% by mass or more and 70% by mass or less for low-boiling alcohol, 5% by mass or more and 15% by mass or less for high-boiling alcohol, and water. Is preferably 20% by mass or more and 60% by mass or less (the total of water, low-boiling alcohol and high-boiling alcohol is 100% by mass).
A more preferable composition of the dispersion medium is a composition of 30% by mass or more and 50% by mass or less of low boiling point alcohol, 5% by mass or more and 15% by mass or less of high boiling point alcohol, and 40% by mass or more and 60% by mass or less of water.
When the dispersion medium has the above composition, the wettability of the conductive polymer dispersion liquid to the base material, particularly the glass base material, becomes higher, the shrinkage of the coating film due to drying can be suppressed, and the formation of the conductive layer becomes easier. Therefore, the appearance of the conductive layer formed from the conductive polymer dispersion is improved.

The content of water in the dispersion medium is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 60% by mass or less, and 30% by mass or more with respect to the total mass of the dispersion medium. It is more preferably 50% by mass or less. When the content of water in the dispersion medium is within the above range, the storage stability of the conductive polymer dispersion liquid of this embodiment can be further improved, and the conductive polymer dispersion liquid is sprayed by spray coating. At that time, it is possible to prevent the conductive polymer dispersion liquid adhering to the periphery of the spray port from drying, and the dried product from being placed on the coating film to impair the appearance and performance of the conductive layer.

(Antioxidant)
In order to prevent oxidative deterioration of the conductive layer formed from the conductive polymer dispersion liquid of this embodiment, the conductive polymer dispersion liquid may contain an antioxidant.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like. Among these antioxidants, phenolic antioxidants are preferable because the conductive layer has high antioxidant properties. Among the phenolic antioxidants, at least one of gallic acid (gallic acid) and an ester of gallic acid is preferable. Galic acid and the ester of gallic acid have an effect of exhibiting high antioxidant performance and improving conductivity in a dispersion liquid or a conductive layer containing a conductive composite.
Examples of the gallic acid ester include an alkyl ester having 1 to 3 carbon atoms of the gallic acid, specifically, a methyl ester of the gallic acid, an ethyl ester of the gallic acid, and a propyl ester of the gallic acid.

In the conductive polymer dispersion liquid of this embodiment, the content of the antioxidant is preferably 10 parts by mass or more and 10,000 parts by mass or less, and 20 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive composite. Is more preferable. When the content of the antioxidant is not less than the lower limit value, the antioxidant property of the conductive layer formed from the conductive polymer dispersion liquid becomes higher, and when it is not more than the upper limit value, the conductive polymer dispersion liquid is used. It is possible to prevent a decrease in the conductivity of the conductive layer formed from the above.

(Surfactant)
The conductive polymer dispersion used in the present invention may contain a surfactant. By including the surfactant, spray coating can be facilitated, the appearance of the formed conductive layer can be improved, and the performance can be improved. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and the like. Of these, nonionic surfactants are preferable, and polyether-modified silicones, which are excellent in suppressing foaming due to spray coating, are more preferable.

The polyether-modified silicone used in this embodiment is a polymer in which a polyether chain is bonded to a silicone chain. Note that the polyether-modified silicone does not have an epoxy group in the molecule. The polyether-modified silicone is preferably one in which a polyether chain is bonded to a side chain of the silicone chain. The polyether chain preferably has a polyoxyalkylene group, and examples of the polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group. Specifically, a compound in which the hydroxyl group of polyethylene glycol (PEG) or polypropylene glycol (PPG) forms an ether bond with the hydroxyl group of the side chain of the silicone chain is preferable. The polyether-modified silicone has lipophilicity due to the silicone chain and hydrophilicity due to the polyether chain, and thus functions as a surfactant. The silicone may be linear or branched. The silicone chain may have an alkyl chain in addition to the polyether chain.
The mass average molecular weight of the polyether-modified silicone is preferably 100 or more and 100,000 or less, more preferably 200 or more and 50,000 or less, and further preferably 300 or more and 30,000 or less. When the mass average molecular weight of the polyether-modified silicone is within the above range, foaming due to spray coating can be further suppressed, and the substrate can be further prevented from repelling the conductive polymer dispersion. The mass average molecular weight of the polyether-modified silicone was determined by measuring the elution time using gel permeation chromatography (GPC) and based on a calibration curve of elution time vs. molecular weight obtained in advance from a polystyrene standard material having a known molecular weight. It is the standard molecular weight.
Specific examples of the polyether-modified silicone include, for example, PEG-11 methyl ether dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, PEG-9 dimethicone, PEG-3 dimethicone, PEG-9 methyl ether dimethicone, and PEG-10 dimethicone. , PEG-32 methyl ether dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone and the like.
One type of surfactant may be used alone, or two or more types may be used in combination.

The solid content concentration of the surfactant with respect to the total mass of the conductive polymer dispersion liquid of this embodiment is preferably 0.001% by mass or more and 1% by mass or less, preferably 0.005% by mass or more and 0.5% by mass or less. It is more preferably 0.005% by mass or more and 0.1% by mass or less. When the solid content concentration of the surfactant in the conductive polymer dispersion is at least the above lower limit, the generation of bubbles can be sufficiently prevented when the conductive polymer dispersion is spray-coated, and the conductivity is also conductive. It is possible to further suppress the polymer dispersion liquid from being repelled by the base material, particularly the glass base material. This makes it possible to further prevent the appearance of the conductive layer from being deteriorated. When the solid content concentration of the surfactant in the conductive polymer dispersion is not more than the upper limit, it is possible to prevent the conductive layer from being lowered in conductivity. Here, the "solid content" is a residual content (nonvolatile content) remaining after distilling off the dispersion medium or the solvent.

(Highly conductive agent)
The conductive polymer dispersion liquid may contain a highly conductive agent in order to further improve the conductivity.
Here, the above-mentioned π-conjugated conductive polymer, polyanion, silicate, epoxy group-containing alkoxysilane, surfactant, antioxidant and organic solvent are not classified as high conductivity agents.
The highly conductive agent is a saccharide, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having one or more hydroxy groups and one or more carboxy groups, a compound having an amide group, and the like. It is preferably at least one compound selected from the group consisting of a compound having an imide group and a lactam compound.
The highly conductive agent contained in the conductive polymer dispersion may be one kind or two or more kinds.
The content ratio of the highly conductive 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, and 20 parts by mass with respect to 100 parts by mass of the conductive composite. It is more preferably 2 parts or more and 2500 parts by mass or less. When the content ratio of the high conductive agent is at least the above lower limit value, the effect of improving the conductivity by adding the high conductivity agent is sufficiently exhibited, and when it is at least the above upper limit value, the concentration of the π-conjugated conductive polymer is lowered. It is possible to prevent a decrease in conductivity due to the above.

(Other additives)
The conductive polymer dispersion may contain other known additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and for example, an inorganic conductive agent, a defoaming agent, a coupling agent, an ultraviolet absorber, or the like can be used. However, the additive comprises a compound other than the above-mentioned π-conjugated conductive polymer, polyanion, silicate, epoxy group-containing alkoxysilane, surfactant, antioxidant, organic solvent and high conductivity agent.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
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. Can be mentioned.
When the conductive polymer dispersion liquid contains the above additive, the content ratio thereof is appropriately determined depending on the type of the additive. For example, 0. The range may be 001 parts by mass or more and 5 parts by mass or less. Here, the "solid content" is a residual content (nonvolatile content) remaining after distilling off the dispersion medium or the solvent.

The total solid content concentration of the silicate component with respect to the total mass of the conductive polymer dispersion liquid of this embodiment is preferably 0.25% by mass or more and 5% by mass or less, and 0.5% by mass or more and 4.0% by mass or less. It is more preferably 1.0% by mass or more and 3.0% by mass or less. Here, the "solid content" is a residual content (nonvolatile content) remaining after distilling off the aqueous dispersion medium.
When the total solid content concentration of each component in the conductive polymer dispersion is within the above range, it is easy to apply the conductive polymer dispersion uniformly to the substrate when spray-coating. Therefore, it is possible to more easily form a conductive layer having a good appearance and conductivity.

(Manufacturing method of conductive polymer dispersion liquid)
Examples of the method for producing the conductive polymer dispersion liquid of this embodiment include the following methods.
First, an aqueous dispersion of a conductive composite is prepared by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in a solution containing a polyanion and a dispersion medium. Then, an organic solvent, a silicate, an epoxy group-containing alkoxysilane, a surfactant, an antioxidant, a high conductivity agent and other additives are added to the aqueous dispersion, and the conductive polymer dispersion is added. To get.
A known catalyst may be applied to the chemical oxidative polymerization. For example, catalysts and oxidizing agents can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and ferric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.
The order in which the organic solvent, silicate, epoxy group-containing alkoxysilane, surfactant, antioxidant, high conductivity agent and other additives are added to the aqueous dispersion is not particularly limited.

<Manufacturing method of conductive laminate>
The method for producing a conductive laminate of the present invention includes forming a conductive layer on the surface of the substrate by spray-coating the substrate with a conductive polymer dispersion. As described above, the conductive polymer dispersion liquid is an aqueous system containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a silicate, an epoxy group-containing alkoxysilane, and water and an organic solvent. Contains a dispersion medium. Hereinafter, one aspect of the method for manufacturing the conductive laminate of the present invention will be described.

The shape of the base material is not particularly limited, and may be a plate shape or a film shape, or may be a three-dimensional arbitrary shape in which a flat surface or a curved surface is arbitrarily combined.
When the shape of the base material is plate-like or film-like, a conductive layer is formed on at least one surface of the base material.

The spray coating of the present invention can be performed by a known device. For example, as shown in FIG. 1, a spray coating apparatus including a coating liquid supply means 2 for supplying a conductive polymer dispersion liquid (coating liquid), an atomized air supply means 3, and a spray gun 4. 1 is mentioned. The spray gun 4 is connected to the coating liquid supply means 2 and the atomizing air supply means 3, respectively, and is configured to supply the coating liquid 2A and the atomizing air 3A from these, respectively. The spray gun 4 surrounds the coating liquid nozzle 5 for discharging the coating liquid 2A supplied from the coating liquid supply means 2 from the discharge port and the outer peripheral surface of the coating liquid nozzle 5, and the outer periphery of the coating liquid nozzle 5. It is composed of an air cap 6 as a flow path forming member that forms an air flow path 9 through which the atomized air 3A supplied by the atomized air supply means 3 passes between the surface and the surface.

The coating liquid 2A, which is a conductive polymer dispersion liquid, is supplied from the coating liquid supply means 2, and atomized air whose pressure is adjusted is supplied from the atomized air supply means 3. As a result, from the spray gun 4, a coating liquid in which the coating liquid 2A discharged from the coating liquid nozzle 5 is made into a mist by atomizing air is placed on the atomizing air and is a base to be coated. Spray on the surface of the material.

FIG. 2 is a schematic diagram showing an example of the spray gun 4 in the present embodiment.
The spray gun 4 of the present embodiment includes a truncated cone-shaped coating liquid nozzle 5 and a hollow cone-shaped air cap 6. The coating liquid nozzle 5 is provided inside with a coating liquid flow path 7 for supplying the coating liquid 2A, and the coating liquid flow path 7 communicates with a discharge port 8 opened on the tip surface of the coating liquid nozzle 5. is doing. Further, the outlet 10 of the air flow path 9 for supplying the atomized air 3A formed between the air cap 6 and the coating liquid nozzle 5 is open in the vicinity of the tip surface of the coating liquid nozzle 5. ..

FIG. 3 is an enlarged view showing a schematic configuration of a tip portion of the spray gun 4.
As shown in FIG. 3, a needle 5p is provided inside the coating liquid flow path 7 of the coating liquid nozzle 5. The needle 5p is configured to be able to move forward and backward with respect to the discharge port 8 of the coating liquid flow path 7 by a needle moving means (not shown). When the needle 5p is located at the retracted position as shown in FIG. 3, a gap is formed between the discharge port 8 of the coating liquid flow path 7 and the needle 5p, and the coating liquid 2A in the coating liquid flow path 7 is formed. It is discharged from the discharge port 8. On the other hand, when the needle 5p is located in the forward position (not shown), the discharge port 8 of the coating liquid flow path 7 is blocked by the needle 5p, and the coating liquid 2A in the coating liquid flow path 7 is discharged from the discharge port 8. It becomes impossible.

The pressure of the atomized air 3A to be supplied is preferably 0.01 MPa or more and 0.2 MPa or less, more preferably 0.02 MPa or more and 0.1 MPa or less immediately before being introduced into the spray gun 4. When the pressure of the atomized air is 0.01 MPa or more, the coating liquid 2A is sufficiently atomized, and a uniform coating film can be easily formed. Further, when the pressure is 0.2 MPa or less, it is possible to prevent the force of spraying the mist-like coating liquid 2A on the surface of the base material from becoming excessively strong, and to easily form a uniform coating film. .. The pressure of the atomized air 3A can be controlled by adjusting the flow rate.

The discharge rate of the coating liquid 2A discharged from the discharge port 8 of the coating liquid nozzle 5 is, for example, preferably 0.1 cc / min or more and 30 cc / min or less, and more preferably 0.2 cc / min or more and 15 cc / min or less. Within the above range, a uniform coating film can be easily formed, and the conductive polymer dispersion liquid (coating liquid 2A) adheres around the tip of the spray gun 4, and the dried product becomes dry. It can be sufficiently prevented from being formed.

The distance from the tip of the spray gun 4 to the coated surface (surface) of the base material is, for example, preferably 10 mm or more and 200 mm or less, and more preferably 30 mm or more and 150 mm or less. Within the above range, a uniform coating film can be easily formed, and a dried product in which a conductive polymer dispersion liquid (coating liquid 2A) adheres around the tip of the spray gun 4 is dried. Even if it is formed, it is possible to prevent the dried material from reaching the coated surface.

It is preferable that the tip of the spray gun 4 is arranged so that the coated surface (surface) of the base material does not exist vertically below the tip of the spray gun 4 at the time of spraying. It is preferable that the tip of the spray gun 4 sprays the coating liquid 2A onto the coated surface of the base material from the side or vertically below the coated surface of the base material. When the relative arrangement between the tip of the spray gun 4 and the coated surface of the base material is as described above, the conductive polymer dispersion liquid (coating liquid 2A) adheres around the tip of the spray gun 4. Even if the dried dried product is formed and then dropped off, it is possible to prevent the dried product from being placed on the coated surface.

As the average thickness of the coating film formed on the surface of the base material by spray coating, for example, the thickness of the conductive layer to be formed is preferably 10 nm or more and 2 μm or less, more preferably 10 nm or more and 500 nm or less, still more preferably 10 nm. A thickness of 200 nm or less can be mentioned.

In the method for producing a conductive laminate according to this embodiment, after spray coating, a coating film made of a conductive polymer dispersion is dried and the coating film is cured to form a conductive layer.
Examples of the drying method include heat drying and vacuum drying. As the heat drying, for example, a usual method such as hot air heating or infrared heating can be adopted.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, but is usually in the range of 50 ° C. or higher and 150 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower, more preferably 100. It is in the range of ° C. or higher and 130 ° C. or lower. Here, the heating temperature is a set temperature of the drying device. The drying time is preferably 5 minutes or more.

The base material used in the method for producing the conductive laminate of this embodiment is preferably a glass base material or a plastic base material. The above-mentioned conductive polymer dispersion is particularly suitable for a glass substrate. Examples of the glass substrate include a non-alkali glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, a quartz glass substrate and the like. If the base material contains an alkaline component, the conductivity of the conductive layer may decrease. Therefore, among the glass base materials, non-alkali glass is preferable. Here, the non-alkali glass is a glass composition in which the content of the alkali oxide is 0.1% by mass or less with respect to the total mass of the glass composition.
The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, and more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is at least the lower limit value, it is less likely to be damaged, and if it is at least the upper limit value, it can sufficiently contribute to the thinning of the member using the conductive laminate.
The average thickness in the present specification is a value obtained by measuring the thickness at any 10 points using a micrometer and averaging the measured values.
The base material may be a liquid crystal cell or a member such as a glass plate constituting the liquid crystal cell. Here, the liquid crystal cell preferably includes a pair of glass plates, a pair of electrode layers provided between the pair of glass plates, and a liquid crystal layer provided between the pair of electrode layers. The liquid crystal layer is preferably a layer in which liquid crystal molecules are enclosed between a pair of oriented layers.

The conductive layer of the conductive laminate is a layer obtained by curing the coating film of the conductive polymer dispersion liquid formed by spray coating. The conductive layer contains a conductive composite, silica derived from a silicate, and a reactant derived from an epoxy group-containing alkoxysilane. Since the conductive layer contains silica, the hardness of the conductive layer is increased. Here, silica is a compound produced by hydrolysis of silicate when the conductive polymer dispersion is cured. Generally, silica has a silanol group. Further, since the conductive layer contains a reactant derived from the epoxy group-containing alkoxysilane, the adhesion of the conductive layer to the surface of the base material is enhanced.

The average thickness of the conductive layer is preferably 10 nm or more and 2 μm or less, more preferably 10 nm or more and 500 nm or less, and further preferably 10 nm or more and 200 nm or less. When the average thickness of the conductive layer is not less than the lower limit value, sufficiently high conductivity and sufficiently high hardness can be exhibited, and when it is not more than the upper limit value, the conductive layer can be easily formed.

(Action effect)
In the method for producing a conductive laminate of the present invention, since the conductive polymer dispersion is applied to the surface of the base material by spray coating, the coater is applied to the surface of the coating film such as a bar coater or a slit coater. Compared to the coating method in which the coating film is in contact with the coating film, dry matter containing a silicate is less likely to be generated on the coated portion of the coater. As a result, it is possible to prevent the appearance and performance of the conductive layer from being impaired.

In the conductive polymer dispersion used in the present invention, the silicate hydrolyzes to form a silanol group, which can be bonded to the hydroxy group on the surface of the substrate. The formation of silica from the silicate occurs when the coating film of the conductive polymer dispersion is dried to form the conductive layer.
The hardness of the conductive layer can be increased by including silica in the conductive layer. Therefore, according to the present invention, a conductive layer having high hardness can be easily formed on the base material.

When the conductive polymer dispersion used in the present invention contains an epoxy group-containing alkoxysilane, the epoxy group of the epoxy group-containing alkoxysilane reacts with the anionic group of the polyanion, and the alkoxysilane moiety is the group. By binding to the surface of the material, the adhesion between the conductive composite and the base material is improved.
Further, the epoxy group of the epoxy group-containing alkoxysilane can react with some anionic groups of the polyanion to reduce the acidity of the conductive polymer dispersion. This makes it possible to suppress the hydrolysis of the silicate and improve the storage stability of the conductive polymer dispersion. By improving the storage stability of the conductive polymer dispersion, the conductive composite can be uniformly contained in the conductive layer formed from the conductive polymer dispersion after storage, so that the conductivity is low. Or the problem of excessively high conductivity is less likely to occur.

When the conductive polymer dispersion used in the present invention contains a surfactant, it is possible to prevent the generation of bubbles during spray coating, and the conductive polymer dispersion is repelled by the substrate. Can be prevented. Therefore, the conductive layer formed from the conductive polymer dispersion liquid containing the surfactant is less likely to cause poor appearance and has an excellent appearance.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

(Manufacturing Example 1)
206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was added dropwise to the solution at 80 ° C. for 20 minutes. Stir for hours.
To the obtained sodium styrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, 1000 ml of the polystyrene sulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the residual liquid. Was added, and about 2000 ml of the solution was removed using an ultrafiltration method. The above ultrafiltration operation was repeated 3 times. About 2000 ml of ion-exchanged water was added to the obtained polystyrene sulfonic acid solution, and about 2000 ml of the solution was removed by using an ultrafiltration method. This ultrafiltration operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Manufacturing Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 in 2000 ml of ion-exchanged water were mixed at 20 ° C. While keeping the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added. The mixture was stirred for 3 hours and reacted.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solution was removed by using an ultrafiltration method. This operation was repeated 3 times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was removed. Was added, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by using an ultrafiltration method. This operation was repeated 5 times to obtain a polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion (PEDOT-PSS aqueous dispersion) having a solid content concentration of 1.2% by mass.

(Example 1)
7.5 g of PEDOT-PSS aqueous dispersion produced in Production Example 2 (solid content concentration 1.2% by mass, PEDOT: PSS = 1: 2.5 (mass ratio)) and tetraethyl orthosilicate (hereinafter referred to as "TEOS"). 0.25 g, 0.15 g of 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.02 g of methyl gallicate are added, and 27.06 g of ion-exchanged water is added. 55.02 g of ethanol and 10 g of propylene glycol monomethyl ether were added. The concentration of silicate added in the conductive polymer dispersion of Example 1 was 0.25% by mass.

(Example 2)
Adjustments were made in the same manner as in Example 1 except that the addition amounts of tetraethyl orthosilicate (0.5 g) and ethanol were changed to 54.77 g. The concentration of the silicate added in the conductive polymer dispersion of Example 2 is 0.5% by mass.

(Example 3)
The adjustment was carried out in the same manner as in Example 1 except that 1.0 g of tetraethyl orthosilicate and 54.27 g of ethanol were added. The concentration of the silicate added in the conductive polymer dispersion of Example 3 is 1.0% by mass.

(Example 4)
Adjustments were made in the same manner as in Example 1 except that the addition amounts of tetraethyl orthosilicate (3.0 g) and ethanol were changed to 52.27 g. The concentration of the silicate added in the conductive polymer dispersion of Example 4 is 3.0% by mass.

(Example 5)
Adjustments were made in the same manner as in Example 1 except that the addition amounts of tetraethyl orthosilicate 5.0 g and ethanol were changed to 50.27 g. The concentration of the silicate added in the conductive polymer dispersion of Example 5 is 5.0% by mass.

(Example 6)
The adjustment was carried out in the same manner as in Example 3 except that 0.01 g of SJM002 (manufactured by Nissin Chemical Industry Co., Ltd.) was added. The concentration of the silicate added in the conductive polymer dispersion of Example 6 is 1.0% by mass.

(Example 7)
Adjustments were made in the same manner as in Example 1 except that the addition amounts of tetraethyl orthosilicate 7.0 g and ethanol were changed to 48.27 g. The concentration of the silicate added in the conductive polymer dispersion of Example 7 is 7.0% by mass.

(Example 8)
The adjustment was carried out in the same manner as in Example 3 except that ethanol was changed to 54.31 g without adding methyl gallicate. The concentration of the silicate added in the conductive polymer dispersion of Example 8 is 1.0% by mass.

(Comparative Example 1)
The adjustment was carried out in the same manner as in Example 1 except that ethanol was changed to 55.27 g without adding tetraethyl orthosilicate. The concentration of silicate added in the conductive polymer dispersion of Comparative Example 1 is 0% by mass.

Using the same spray coating apparatus as in FIGS. 1 to 3, the conductive polymer dispersions of Examples 1 to 8 and Comparative Example 1 were coated on the surface of the glass substrate. The coating discharge rate is 0.35CC / min, the distance from the tip of the spray gun 4 to the coating surface (surface) of the glass substrate is 100 mm, and the pressure of the atomized air 3A supplied is 0.07 MPa. Formed. Then, it dried at 120 degreeC for 30 minutes, and obtained the conductive laminated body provided with the conductive layer. Under the same conditions, a conductive coating film was continuously applied to 10 glass substrates to obtain a conductive laminate.

(Comparative Example 2)
Using a slit coater, the conductive polymer dispersion liquid of Example 3 was applied to the surface of the glass substrate. A coating film was prepared at a discharge rate (thickness) of 8 μm and a coating speed of 100 mm / min, and dried at 120 ° C. for 30 minutes to obtain a conductive laminate having a conductive layer. Under the same conditions, a conductive coating film was continuously applied to 10 glass substrates to obtain a conductive laminate.

<Evaluation>
The appearance, conductivity (initial surface resistance value), hardness and heat resistance of the conductive layer in the conductive laminate of each example were evaluated by the following methods. The evaluation results are shown in Table 1.

(exterior)
Observing at a magnification of 100 times with an optical microscope, those with a large amount of coating unevenness were marked with x, those with a little coating unevenness were marked with Δ, and those with very little coating unevenness were marked with ◯. Further, the conductive polymer dispersion liquid was dried and crystallized at the discharge port, and the dried product was peeled off and mixed in the coating film, which was marked with x.

(Surface resistance value)
The measurement was performed using a resistivity meter (High Restor manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under the conditions of an applied voltage of 10 V and an applied time of 10 seconds. This surface resistance is used as the initial surface resistance. The unit of surface resistance is (Ω / sq.), And “1.00E + 06” in Table 1 means “1.00 × ¹⁰⁶ ”.

(Hardness of conductive layer)
The surface of the conductive layer was tested using a pencil scratch tester under the condition of a load of 750 g, and the scratch marks were observed with a microscope at a magnification of 100 times to measure the pencil hardness.

(Heat-resistant)
After the conductive layer of the conductive laminate of each example was left in a high thermal environment with a temperature of 85 ° C. and no humidity adjustment for 240 hours, the surface resistance of the conductive layer was measured in the same manner as described above.
The rate of change in surface resistance after being left in a high thermal environment with respect to the initial surface resistance was calculated by the following formula.
Heat resistance change rate (%) =
"Surface resistance value after 240 hours at 85 ° C" ÷ "Initial surface resistance value" x 100

<Result>
The conductive layers of Examples 1 to 6 had very little coating unevenness and were excellent in conductivity, pencil hardness and heat resistance. In Example 6, the appearance was particularly excellent due to the addition of the surfactant.
In Example 7, since the amount of silicate was larger than that in the other examples, coating unevenness appeared a little, but there was no defect due to peeling or mixing of the dried product, and excellent hardness was exhibited.
In Example 8, since gallic acid was not added, the heat resistance was inferior, but there was no uneven coating, and there was no defect due to peeling or mixing of the dried product.
In Comparative Example 1, the hardness was low because TEOS was not added.
In Comparative Example 2, since the coating was performed using a slit coater instead of spray coating, the conductive polymer dispersion liquid adhering to the periphery of the discharge port dries and crystallizes, peels off during coating, and the coated surface is coated. The problem that the dried product was mixed into the coating film was noticeably observed. In particular, in continuous coating, the amount of dried matter mixed in increased in the latter half.
In addition, Example 7 is a comparative example.

1 ... Spray coating device, 2 ... Coating liquid supply means, 2A ... Coating liquid (conductive polymer dispersion liquid), 3 ... Atomized air supply means, 3A ... Atomized air, 4 ... Spray gun, 5 ... Coating liquid nozzle, 5p ... Needle, 6 ... Air cap, 7 ... Coating liquid flow path, 8 ... Discharge port, 9 ... Air flow path, 10 ... Outlet

Claims (13)

A method for producing a conductive laminate, which comprises forming a conductive layer on the surface of the base material by spray-coating the base material with a conductive polymer dispersion liquid.
The conductive polymer dispersion liquid contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a silicate, an aqueous dispersion medium containing water and an organic solvent, and a polyether-modified silicone .
The content of the polyether-modified silicone with respect to the total mass of the conductive polymer dispersion is 0.005% by mass or more and 0.1% by mass or less.
The content of the silicate with respect to the total mass of the conductive polymer dispersion is 0.25% by mass or more and 5.0% by mass.
A low boiling point alcohol having a boiling point of less than 100 ° C. at a standard pressure of 25% by mass or more and 70% by mass or less and a high boiling point alcohol having a boiling point of 100 ° C. or more at a standard pressure are contained in the total mass of the aqueous dispersion medium. A conductive laminate containing 5% by mass or more and 15% by mass or less, containing 30% by mass or more and 50% by mass or less of water, and the total of the low boiling point alcohol, the high boiling point alcohol and the water is 100% by mass . Manufacturing method. The method for producing a conductive laminate according to claim 1, wherein the conductive polymer dispersion further contains an epoxy group-containing alkoxysilane. The method for producing a conductive laminate according to claim 1 or 2, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The method for producing a conductive laminate according to any one of claims 1 to 3, wherein the polyanion is polystyrene sulfonic acid. The production of the conductive laminate according to any one of claims 1 to 4, wherein the silicate is at least one selected from tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrapropoxysilane. Method. The conductive polymer dispersion further contains an epoxy group-containing alkoxysilane, and the epoxy group-containing alkoxysilane is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy. The method for producing a conductive laminate according to any one of claims 1 to 5, which is propylmethyldimethoxysilane or 3-glycidoxypropylmethyldiethoxysilane. The method for producing a conductive laminate according to any one of claims 1 to 6, wherein the aqueous dispersion medium contains methanol, ethanol, isopropanol, or propylene glycol monomethyl ether. The method for producing a conductive laminate according to any one of claims 1 to 7, wherein the conductive polymer dispersion further contains an antioxidant. The method for producing a conductive laminate according to claim 8, wherein the antioxidant contains a compound having two or more hydroxy groups. The method for producing a conductive laminate according to claim 9, wherein the compound having two or more hydroxy groups contains at least one selected from the group consisting of gallic acid and an ester of gallic acid. The method for producing a conductive laminate according to any one of claims 1 to 10 , wherein the base material is a glass base material. The method for producing a conductive laminate according to claim 11 , wherein the glass substrate is a non-alkali glass substrate. The method for producing a conductive laminate according to claim 11 or 12 , wherein the glass substrate is a member of a liquid crystal cell.

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