KR101589546B1 - Transparent conductive film having improved visual clarity and preparation method thereof - Google Patents

Abstract

The present invention relates to a transparent conductive film which is formed by using a simple exposure and cleaning process without direct etching of a conductive film to form a wiring pattern capable of electric conduction in a specific pattern form by forming a difference in electric conductivity in a local region of the conductive film, And a method for producing the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a transparent conductive film having improved visibility and a method of manufacturing the transparent conductive film.

The present invention relates to a transparent conductive film having improved visibility and a method of manufacturing the same, and more particularly, to a method of manufacturing a transparent conductive film having improved visibility by using a simple exposure and cleaning process without direct etching of the conductive film, To a transparent conductive film in which a wiring pattern capable of flowing electricity is formed and its visibility is improved, and a method for manufacturing the transparent conductive film.

Conductive thin films including metal nanowires are formed by conducting metal nanostructures in the form of wires, tubes, and ribbons in contact with each other to form a conductive film. The metal nanowire conductive thin film can be formed by coating on various substrates by a wet process and can be used as a transparent electrode and a circuit electrode in a touch panel, a surface heating element, an optical film, a display, and the like.

 The conductive thin film including the metal nanowire includes metal nanowires corresponding to conductive fillers, metal nanoribbons, metal nanoparticles, etc., and includes a dispersant for dispersing the particles, a binder for forming a conductive film by being fixed to the substrate, , Additives for securing dispersion stability of the solution, and the like.

 In order to use a conductive film composed of metal nanowires as a transparent electrode or a circuit electrode, it is necessary to control electric connection and non-connection in a local region of the conductive film to conduct electricity in a specific pattern form.

 As a conventional method of forming a conductive film pattern as the conventional art, a conductive thin film is formed by coating a coating liquid containing metal nanowires, and then a photoresist is applied to form a pattern through a photolithography process or a laser etching process To form a pattern. In the photolithography process, a photoresist is coated on a conductive film, a photoresist pattern is formed on the conductive film by exposing and developing ultraviolet rays, and then a conductive film is patterned by etching the conductive film in a specific pattern by a wet or dry method . Or a laser etching method forms a pattern of a conductive film by etching a conductive film in a specific pattern using a laser.

1, after forming a photoresist pattern, a conductive layer is directly etched by using an etching solution or a dry etching method such as a plasma treatment to form a nonconductive insulating region, and finally, by removing the photoresist, Thereby forming a pattern. This method requires a series of processes such as a conductive film formation, a photoresist coating, a photoresist pattern formation, a conductive film etching, a photoresist removal, and finally, a conductive film pattern composed of an etched region and an unetched region is formed. The conductive film thus formed may cause a problem that the conductive film pattern is visually recognized because of the difference in the distribution of the metal nanowires between the etched region and the non-etched region to form light reflectance, light transmittance, and haze difference. In addition, in the case of the photolithography process, a separate process is required to form a conductive film pattern, so that the process cost is additionally required and a large number of defects may occur.

As a method of forming a pattern of electric current, there is a method of forming a conductive film pattern by directly etching a conductive film. U.S. Patent No. 8,018,568 discloses a technique for forming a silver nano wire transparent conductive film pattern. In this patent, a silver nano wire conductive film coated on a substrate has a etched region and a non-etched region to form a conductivity difference in the localized region of the conductive film, or silver nano wires formed by oxidation or sulfide formation in the local region of the conductive film are applied, A method of forming a difference or forming a region having a different electrical conductivity by converting a silver wire existing in a conductive film local region into an oxide or a sulfide or physically damaging a silver wire in a local region to form an electrical conductivity difference .

U.S. Patent No. 8,049,333 also describes a technique for a silver nanowire conducting film patterned by the difference in silver nanowire distribution density in the region of the conducting film.

In order to solve the problems of the prior art described above, when a pattern of an electric current flow of a conductive film is formed by a non-etching method in an exposure and a cleaning process without using an etching process in a pattern formation process, Therefore, the pressure is concentrated on the stepped portion due to the external pressure of the pattern, so that the insulating property is damaged in the insulating region, or the polymer composition is not removed in the cleaning process, and some of the thin film remains on the surface of the thin film. have. Also, if such a phenomenon is concentrated in a part of the insulating region, the pattern may cause some visibility problems due to the difference in haze. Also, since the metal nanowires of the conductive film are directly exposed to the outside, the environmental stability is poor, and due to the excessive volume change of the thin film due to the environment, the insulating property may be weak due to the change of the conductive network shape between the metal nanowires in the insulating region.

The present inventors have found that when a pattern of electric current flow of a conductive film is formed by a non-etching method in the process of exposure and washing without using an etching process in the pattern formation process, and a top coating layer is formed of a specific polymer or an inorganic material, , Visibility, environmental stability, and insulating properties can be produced. Thus, the present invention has been completed.

It is an object of the present invention to provide a method of forming a wiring pattern capable of electrically conducting electricity in a specific pattern form by forming a difference in electrical conductivity in a local region of a conductive film by using a simple exposure and cleaning process without direct etching of the conductive film, A transparent conductive film having improved visibility, and a method of manufacturing the transparent conductive film.

Another object of the present invention is to provide a transparent conductive film which is not chemically / physically etched in a specific region for forming a pattern of a conductive film, is not oxidized by a chemical method or formed with a sulfide and physically does not substantially damage the conductive nanomaterial, Method.

It is still another object of the present invention to provide a method for producing a transparent conductive film capable of improving optical characteristics, visibility, environmental stability, and insulation of a conductive film formed by an exposure and cleaning process.

In order to accomplish the above object, the present invention provides a method of manufacturing a semiconductor device, comprising: forming a coated conductive film on a substrate, which is coated with a coating solution composition containing a metal nanowire, an ultraviolet ray sensitive material and a solvent and in which an exposed region and an unexposed region are formed; And a top coating layer composed of a polymer or an inorganic material formed on the coating conductive film.

In the present invention, the top coat layer for improving the optical characteristics, visibility, environmental stability, and insulation of the transparent conductive film is selected from the group consisting of polyurethane, polyacrylate, epoxy, polyimide, polyester, polyacrylic acid, polyvinyl alcohol and polyethyleneimine A polymer selected therefrom, or an inorganic material such as silicon dioxide or titanium dioxide by a top coating method.

The coating liquid composition may further comprise a binder.

In an embodiment of the present invention, the top coating layer may further include a corrosion inhibitor or a color coordinate adjusting material.

The corrosion inhibitor may be selected from the group consisting of benzotriazole, tolytriazole, butyl benzyl triazole, dithiothiadiazole, alkyldithiothiadiazoles and alkyl dithiothiadiazoles and alkylthiols, 2-aminopyrimidine, 5,6-dimethylbenzimidazole, 2-amino-5-mercapto- 1, 3, 4-thiadiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, An organic compound selected from the group consisting of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole can be used.

In the present invention, the thickness of the top coating layer is preferably 0.001 to 1000 탆.

In one embodiment of the present invention, the photosensitive coating solution composition for preparing a coating conductive film according to the present invention comprises 0.01 to 5% by weight of metal nanowires, 0.1 to 5% by weight of ultraviolet sensitive material, and the balance of the solvent. When the binder is added, the binder is preferably added in an amount of 1% by weight or less.

In addition, the photosensitive coating composition for coating conductive film according to the present invention is selected from the group consisting of polyvinylpyrrolidone, hydroxypropylmethylcellulose, carboxymethylcellulose, 2-hydroxyethylcellulose, and 2-hydroxymethylcellulose 0.01 to 5% by weight of an additive, and 0.001 to 5% by weight of other additives selected from the group consisting of carbon nanotubes, graphene, graphene oxide, carbon nanoplates, carbon black and conductive polymers.

In one embodiment of the present invention, metal nanowires or metal nanoribbons including silver nanowires, gold nanowires and copper nanowires may be used as the metal nanowires, and it is preferable to use silver nanowires as metal nanowires Do.

In one embodiment of the present invention, a polyvinyl alcohol having a photosensitive functional group may be used as the ultraviolet sensitive material, and a water dispersible polyurethane or a cationic polymer electrolyte may be used as the binder. As the solvent, water or an alcohol Can be used.

The present invention also provides a method for manufacturing a coated conductive film, comprising the steps of: applying a photosensitive coating solution composition for preparing a coated conductive film to a substrate to form a coated conductive film; Exposing to ultraviolet light in accordance with a predetermined specific pattern and exposing and cleaning to form an exposed area and an unexposed area; And forming a top coating layer on the coated conductive film in which the exposed region and the unexposed region are formed.

The haze of the transparent electrode film produced according to the present invention is 1.4 or less.

The present invention relates to a process for producing a conductive film and a pattern forming process as compared with the prior art by forming a conductive film using a photosensitive coating solution containing a metal nanowire, an ultraviolet photosensitive material, a binder and a solvent, and forming an electric current flow pattern through an exposure and washing process It is possible to provide a transparent conductive film which can be greatly shortened and a method for producing the same. In addition, by providing a conductive film forming technique capable of controlling electrical flow characteristics of a conductive film including metal nanowires without etching the conductive film directly, it is possible to solve the pattern visibility problem of the conductive film, which has been pointed out as a serious problem in the conventional art, The factors can be reduced.

It is another object of the present invention to provide a patterned conductive film formed by an exposure and a cleaning process, in which the haze of the film is reduced, the problem of pattern visibility is improved, the step of the insulating region is reduced so that the pressure due to external contact is not concentrated in the insulating region, It is possible to provide a method of manufacturing a transparent conductive film capable of ensuring environmental stability of silver nano wire particles and further securing insulation stability by preventing volume change in an insulating region due to environmental changes.

FIG. 1 is a schematic view illustrating a process of forming a specific pattern on a conductive film using a photoresist method according to the prior art.
2 is a perspective view showing a transparent conductive film having a coated conductive film formed by the metal nanowires according to the present invention.
3 is an enlarged view of a portion " A " in Fig.
FIG. 4 is a flowchart illustrating a method of manufacturing a transparent conductive film according to the present invention shown in FIG.
5 to 9 are views showing respective steps according to the manufacturing method of FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

The embodiments and drawings described in the present specification are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be substituted for them at the time of application of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

2 is a perspective view showing a coated conductive film including a metal nanowire 21, an ultraviolet sensitive material, a binder and a solvent in a transparent conductive film according to the present invention. 3 is an enlarged view of a portion " A " in Fig.

2 and 3, a coated conductive film according to the present invention is formed on a substrate 10, coated with a coating liquid composition comprising metal nanowires 21, an ultraviolet sensitive material, a binder and a solvent, The wiring pattern 29 is formed.

Here, the substrate 10 may be made of a transparent material having light transmittance. For example, as the material of the substrate 10, any one of glass, quartz, transparent plastic substrate, and transparent polymer film may be used. As the material of the transparent polymer film, PET, PC, PEN, PES, PMMA, PI, PEEK and the like can be used, but the present invention is not limited thereto. The substrate 10 of the transparent polymeric film material may have a thickness of 1 to 100,000 mu m.

For example, the photosensitive coating composition may contain 0.01 to 5% by weight of metal nanowires, 0.1 to 5% by weight of ultraviolet sensitive material, and 5 to 10% by weight of an ultraviolet light sensitive material. The photosensitive coating composition for forming the coating conductive film 20 includes metal nanowires, ultraviolet sensitive materials, binders and solvents. % By weight of the binder, 1% by weight or less of the binder, and the solvent, for example, water or alcohol, is added to the remaining 100% by weight.

The photosensitive coating composition may further contain additives selected from the group consisting of polyvinylpyrrolidone, hydroxypropylmethylcellulose, carboxymethylcellulose, 2-hydroxyethylcellulose, and 2-hydroxymethylcellulose.

The additives may be selectively used for the purpose of improving the coating property of the photosensitive coating liquid composition, improving dispersibility, preventing corrosion of the metal nano wire, and improving the durability of the coated conductive film 20. For example, the additive can facilitate the stability of the photosensitive coating composition (e.g., an oil treatment), help wettability and coating properties (e.g., surfactant, solvent additive, etc.) And may help prevent formation of a phase separation structure in forming the coating conductive film 20, and may help promote drying.

In addition, in order to improve the conductivity of the conductive film, improve the uniformity, and improve the environmental stability, the photosensitive coating composition may contain other additives such as carbon nanotubes, graphene, graphene oxide, carbon nanoplates, carbon black, May be further included. These materials can improve the physical properties of the conductive thin film including metal nanowires by forming an auxiliary conductive film or acting as a binder.

The additives and other additives may be contained in an amount of 0.01 to 5 wt% and 0.001 to 5 wt%, respectively.

In the present invention, metal nanowires or metal nanoribbons are used as materials for forming the conductive network. For example, silver nanowires, copper nanowires, gold nanowires, and the like can be used as the metal nanowires. no. As the metal nanowires, metal nanowires having a diameter of 300 nm or less and a length of 1 mu m or more may be used.

The higher the composition ratio of the metal nanowires included in the photosensitive coating solution composition, the more the electric conductivity increases and the resistance of the coated conductive film 20 can be lowered. However, when the concentration is too high, that is, when the concentration is more than 5 wt%, it is difficult to disperse the metal nanowires in solution.

In the present invention, the ultraviolet ray-sensitive material is a material which undergoes crosslinking by ultraviolet ray exposure, and has a low solubility in a solvent during a post-exposure washing process, thereby forming a relatively low electric conductivity region. Typical water-soluble photosensitive polyvinyl alcohols include poly (vinyl alcohol), N-methyl-4 (4-formylstyryl) pyridinium methosulfate acetal and the like. In addition, chemical bonds are formed by exposure to water- Materials may be applied. In addition to the photosensitive resin, a material including both a non-photosensitive material and a light-sensitive initiator and capable of causing a chemical reaction by ultraviolet exposure is also included.

The ultraviolet sensitive material may have a different concentration depending on the target resistance difference between the exposed region 25 and the unexposed region 27. [ For example, 0.1 to 5% by weight is suitable for forming the pattern of the transparent electrode. However, if too much ultraviolet sensitive material is added, the photosensitive material in the unexposed area 27 may be removed during the post-exposure cleaning process, and the metal nanowires may be removed as well, thereby damaging the transparent electrode or increasing the resistance.

In the photosensitive coating composition according to the present invention, the binder serves to fix the metal nanowires or the carbon nanotubes not to be removed during the washing process. And additives for improving coating properties, improving environmental durability, improving adhesion, and improving corrosion resistance.

As the binder, a water-dispersible polyurethane or a cationic polyelectrolyte may be used. Examples of the cationic polymer electrolyte include poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), poly (3,4-ethylenedioxythiophene) (PEDOT), poly (2-vinylpyridine), poly (ethylenenimine), poly (acrylamide-co-diallylmethylammonium chloride, cationic polythiophene, polyaniline, poly (vinylalcohol), or derivatives thereof.

The reason for using such a binder is that the polyvinyl alcohol used as the photosensitive material forms a positive charge in the aqueous solution and therefore when the water dispersible polyurethane or the cationic polymer electrolyte is used as the binder, This is because the photosensitive polyvinyl alcohol material in the unexposed area 27 in the cleaning process does not form an electrical or chemical bonding force with the binder and is easily removed by washing.

In addition, the binder functions to fix the metal nanowires 21 corresponding to the conductive fillers so that they do not fall off the coated conductive film 20 from which the coated conductive film 20 is manufactured. That is, if the binder is not included in the photosensitive coating solution, the metal nanowires 21 are removed as the photosensitive material, the coating conductive film 20 is not formed, or the resistance uniformity is greatly reduced in the solvent cleaning process of the coated conductive film 20 .

The reason for not using an anionic polymer electrolyte as a binder is that when an anionic polymer electrolyte is used as a binder, precipitation occurs in a photosensitive coating solution, and a photosensitive material at a non-exposed portion is not removed when the conductive film is washed after the exposure, The electric conductivity of the region is lowered.

As described above, the binder is added to the photosensitive coating solution at 1 wt% or less to prevent the metal nanowires 21 from falling off the substrate 10 during cleaning after exposure. At this time, if the content of the binder is high, the adhesion of the metal nanowires 21 to the substrate 10 is improved, but the resistance of the coated conductive film 20 may increase. Also, if the binder is absent or is too small, the metal nanowires 21 may be detached from the substrate 10 during cleaning, and the characteristics of the coated conductive film 20 may deteriorate. On the other hand, when the content of the photosensitive material is as low as 0.5% by weight or less, the adhesion of the metal nanowires 21 to the substrate 10 is maintained without the binder, and the production of the coated conductive film 20 according to the present invention is performed You may.

The coated conductive film 20 according to the present invention includes the metal nanowires 21 uniformly formed on the substrate 10. The coated conductive film 20 may include an exposed area 25 and an unexposed area 27 and the unexposed area 27 may form a wiring pattern 29. [ The unexposed area 27 has a higher electrical conductivity than the exposed area 25.

The coated conductive film 20 may be formed of one layer including a metal nanowire, an ultraviolet ray sensitive material, a binder and a solvent, or may have a structure in which a photosensitive material layer is formed on a conductive nanomaterial layer.

As described above, in the coated conductive film 20 according to the present invention, the difference in electrical conductivity between the exposed region 25 and the unexposed region 27 is as follows. The photosensitive thin film including the metal nanowires 21, the ultraviolet sensitive material and the binder before being formed into the coating conductive film 20, that is, before ultraviolet exposure and cleaning, has a very low electrical conductivity by the photosensitive material and the binder.

However, when the photosensitive thin film is exposed to ultraviolet rays, physical or chemical bonds between the photosensitive materials or between the photosensitive material and other compositions are formed or broken to form a difference in solubility with respect to a specific solvent. On the other hand, there is little change in the chemical or physical properties of the metal nanowires 21 during the exposure process. Where a particular solvent can be a solvent with high solubility selectively for the photosensitive material. For example, when a water-soluble photosensitive material is used as a photosensitive material, a difference in solubility with respect to water is formed.

That is, the photosensitive material has a high solubility characteristic with respect to a specific solvent before being exposed, but may have a property of being insoluble in the solvent because it is cured upon exposure. Accordingly, the present invention forms the wiring pattern 29 using the difference in solubility of the photosensitive material with respect to a specific solvent.

Therefore, in the photosensitive thin film, the exposed region 25 and the unexposed region 27 form a solubility difference with respect to a specific solvent. Particularly, when the photosensitive thin film contains a large amount of other composition, a difference in electric conductivity between the two regions is greatly formed, and a difference in electric conductivity is large enough to form a pattern of a transparent electrode and a circuit electrode. A region in which a photosensitive material and other compositions are largely removed when exposed to a solvent usually exhibits a high electrical conductivity and a region in which a photosensitive material and other compositions are less removed exhibits a low electrical conductivity.

For example, if the unexposed area 27 is more soluble in solvent than the exposed area 25, the unexposed area 27 is formed in the wiring pattern 29.

The transparent conductive film according to the present invention is provided with a top coating layer 40 on the coated conductive film 20 on which the exposed region 25 and the unexposed region 27 are formed as described above.

A method of manufacturing a transparent conductive film according to the present invention will now be described with reference to FIGS. 2 to 9. FIG. Here, FIG. 4 is a flow chart according to the method of manufacturing the transparent conductive film of FIG. And FIGS. 5 to 9 are views showing respective steps according to the manufacturing method of FIG.

First, as shown in FIG. 5, a substrate 10 on which a coated conductive film is to be formed is prepared.

Next, as shown in FIG. 6, a photosensitive coating liquid composition for coating conductive film formation is applied on the substrate 10 to form a photosensitive thin film 23 in step S1. Wherein the photosensitive coating composition comprises 0.01 to 5% by weight of metal nanowires, 0.1 to 5% by weight of an ultraviolet sensitive material, and 1% by weight or less of a binder, and the solvent may be occupied by others.

Meanwhile, the photosensitive thin film 23 may be formed of one layer including a metal nanowire, an ultraviolet ray sensitive material, a binder and a solvent, or may have a structure in which a photosensitive material layer is formed on a metal nanowire layer.

Subsequently, as shown in Fig. 7, in step S2, a part of the photosensitive thin film 23 is exposed. That is, the photosensitive thin film 23 is exposed to ultraviolet rays by using a mask 30 having a pattern hole 31 corresponding to an area to be exposed.

The ultraviolet exposure time in the exposure process is generally within a few minutes, preferably within a few seconds. There is little change in the chemical and physical properties of metal nanowires during the exposure process.

8, the coated conductive film 20 having the wiring pattern 29 can be manufactured by washing and drying the photosensitive thin film exposed in the step S2 with a solvent. The removal of the photosensitive material and other composition in the unexposed area 27 is more likely because the unexposed area 27 is relatively more soluble in solvent than the exposed area 25.

The conductive substrate 100 manufactured by the manufacturing method of the present invention is free from the direct etching of the coating conductive film 20 and can be applied to the conductive nano- It is possible to form the coated conductive film 20 having the wiring pattern 29 capable of regulating the electric conductivity in a specific region to form an electric current without damage and chemical conversion of the wire.

The photosensitive thin film according to the present invention includes metal nanowires, ultraviolet sensitive materials, binders, and other composition materials such as dispersants, additives, and the like.

When the photosensitive thin film is exposed to ultraviolet rays, a physical or chemical bond between the photosensitive material or between the photosensitive material and the other composition is formed or broken to form a difference in solubility with respect to a specific solvent such as water. The area where the photosensitive material and other compositions are removed much when exposed to the solvent exhibits high electrical conductivity and the area where the photosensitive material and other compositions are less removed shows a low electrical conductivity. For example, washing with a post-exposure solvent for the photosensitive film results in a relatively high removal of photosensitive materials and other compositions in the unexposed areas 27 relative to the exposed areas 25, The region 27 has a difference in electric conductivity so as to form a pattern of electric current.

Thus, the present invention provides a method of forming an electrical conductivity difference in a localized region of a coated conductive film 20 using a simple exposure method without direct etching of the coated conductive film 20 comprising the conductive nanomaterial, It is possible to form the wiring pattern 29 which can flow.

The present invention also relates to a transparent conductive film comprising a conductive nanomaterial that is not chemically and physically etched in a particular region of the coated conductive film 20, is not oxidized or sulfide formed by a chemical method, and is not physically damaged by the conductive nanomaterial The film 100 can be provided.

The coated conductive film 20 according to the present invention has a problem that a pattern visibility problem occurs because the exposed region 25 and the unexposed region 27 similarly exist in the metal nanowires even when the exposure and cleaning are performed .

The transparent conductive film according to the present invention is provided with a top coating layer 40 on the coated conductive film 20 on which the exposed region 25 and the unexposed region 27 are formed as described above.

The top coating layer 40 may be a polymer selected from the group consisting of polyurethane, polyacrylate, epoxy, polyimide, polyester, polyacrylic acid, polyvinyl alcohol, and polyethylene imine or silicon dioxide, titanium dioxide- ) Solution by a top coating method.

In the present invention, when the top coating material for forming the top coating layer 40 is coated using polyvinyl alcohol or polyacrylic acid having excellent water-absorbing property, moisture adsorption is induced and the drying speed of adsorbed moisture of the existing pattern film is slowed down, It is possible to minimize the occurrence of shrinkage of the conductive film due to moisture drying and thereby deterioration of the insulating property.

When silver nano wire is used as the metal nanowire in the present invention, since the amine functional group has a corrosion inhibiting effect on the silver material when the top coating material is formed of polyethyleneimine as the top coating material for forming the top coating layer 40, It is possible to prevent the corrosion of the silver nano wire caused by the carbon nanotube

In the present invention, the top coat layer 40 is formed on the coated conductive film 20, thereby coating the conductive film patterned in a non-etching manner, thereby eliminating steps in the insulating / non-insulating region and reducing the surface roughness And it is coated on the metal nanowire to prevent oxidation of the metal nanowire by outside air contact and to prevent rapid moisture adsorption and sudden moisture drying due to environmental changes and to minimize insulation damage due to variation of the insulation region volume.

In the present invention, the top coating layer may further include a corrosion inhibitor or a color coordinate modifier.

The corrosion inhibitor may be, for example, benzotriazole, tolytriazole, butyl benzyl triazole, dithiothiadiazole, alkyldithiothiadiazoles and alkylthiols alkyl dithiothiadiazoles and alkylthiols, 2-aminopyrimidine, 5,6-dimethylbenzimidazole, 2-amino-5-mercapto- mercaptopyridine, 2-mercaptobenzoxazole, 2-mercaptopyridine, 3,4-thiadiazole, 2-mercaptopyrimidine, An organic compound selected from the group consisting of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used.

In the present invention, the thickness of the top coating layer is preferably 0.001 to 1000 탆, and if the thickness of the top coating layer is out of the above range, the effect of improving the visibility may be insignificant.

The above-mentioned transparent conductive film produced according to the present invention exhibits very excellent characteristics with a haze of about 0.4 to 1.4.

The characteristics of the transparent conductive film according to the present invention will be described as follows.

Example  One

The transparent conductive film according to Example 1 of the present invention uses a PET film as the substrate and silver nano wire as the conductive nanostructure.

That is, in the first embodiment, a silver nano wire coating liquid containing a silver nanowire, a photosensitive polyvinyl alcohol as a water-soluble photosensitive material, and a water-dispersible polyurethane binder is coated on a substrate and exposed and washed to form a high conductivity region and a low conductivity region To form a pattern. The silver wire was 20 to 40 nm in diameter and 10 to 20 탆 in length. At this time, silver nano wire (0.15 wt%), photosensitive polyvinyl alcohol (0.5 wt%) as a water-soluble photosensitive material, dispersant HPMC (0.3 wt%) and water dispersible polyurethane binder (0.04 wt%) were contained in the silver nano wire coating solution.

A transparent conductive film was formed by forming a top coating layer by coating a conductive film formed by coating a silver nano wire coating liquid on a substrate as described above to a thickness of 0.1 m.

Comparative Example  One

A conductive film was formed in the same manner as in Example 1, except that a polyacrylate was not used to form a top coating layer.

The haze of the transparent conductive film prepared in Example 1 was 1.3 to 1.4, but the haze of the conductive film prepared in Comparative Example 1 was 1.6 to 1.7. In addition, the transparent conductive film prepared in Example 1 was hardly visible in the exposed region, whereas the transparent conductive film prepared in Comparative Example 1 was visually observed with a slightly opaque line in the exposed region, It was not so good. In Comparative Example 1, the non-etching pattern film formed on the PET film had a shape in which the insulating property was destroyed when the opposite side of the coating was strongly rubbed. However, when the transparent conductive film prepared in Example 1 was rubbed under the same pressure, I could confirm that it was still maintained. This is because the step coverage of the insulating region is reduced by the top coating, and concentration of pressure in the insulating region is prevented. In addition, the transparent conductive film of Example 1 was superior to Comparative Example 1 in resistance and insulation stability when exposed to the atmosphere. For example, in the case of measuring the resistance after one month in the general atmospheric environment, the resistance change rate in Example 1 was less than 5% and the insulation property remained unchanged. In Comparative Example 1, the resistance change rate was measured at 9% Insulation was damaged.

The foregoing description is merely illustrative of the technical idea of the present invention and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

Description of the Related Art [0002]
10: substrate
20: Coated conductive film
21: metal nanowire
23: Photosensitive thin film
25: exposed area
27: unexposed area
29: wiring pattern
30: Mask
31: pattern hole
40: Top coating layer
100: transparent conductive film

Claims (17)

Coated with a coating liquid composition comprising a metal nanowire, a UV light-sensitive material, a binder which is a water-dispersible polyurethane or a cationic polymer electrolyte, and a solvent on the substrate, and a coating on which an exposed area and a non- Conductive film; And
And a top coating layer coated on the coating conductive film with a polymer or an inorganic material, wherein the non-exposed region has a higher electrical conductivity than the exposed region.
The method according to claim 1,
Wherein the top coating layer comprises a polymer selected from the group consisting of polyurethane, polyacrylate, epoxy, polyimide, polyester, polyacrylic acid, polyvinyl alcohol, and polyethyleneimine, or an inorganic material selected from silicon dioxide and titanium dioxide .
delete The method according to claim 1,
0.01 to 5 wt% of a metal nanowire, 0.1 to 5 wt% of an ultraviolet sensitive material, and 1 wt% or less of a binder.
The method according to claim 1,
0.01 to 5% by weight of an additive selected from the group consisting of polyvinylpyrrolidone, hydroxypropylmethylcellulose, carboxymethylcellulose, 2-hydroxyethylcellulose and 2-hydroxymethylcellulose, and carbon nanotubes, graphene, Wherein the transparent conductive film further comprises 0.001 to 5 wt% of other additives selected from the group consisting of graphene, carbon nanoplate, carbon black, and conductive polymer.
The method according to claim 1,
Wherein the metal nanowires are metal nanowires or metal nanoribbons including silver nanowires, gold nanowires, and copper nanowires.
The method according to claim 6,
Wherein the metal nanowires are silver nanowires.
The method according to claim 1,
Wherein the ultraviolet sensitive material is a polyvinyl alcohol having a photosensitive functional group.
delete The method according to claim 1,
Wherein the solvent is water or an alcohol.
delete The method according to claim 1,
Wherein the top coating layer further comprises a corrosion inhibitor or a color coordinate control material.
13. The method of claim 12,
The corrosion inhibitors benzotriazole, tolytriazole, butyl benzyl triazole, dithiothiadiazole, alkyl dithiothiadiazoles and alkyl dithiothiadiazoles, alkylthiols, 2-aminopyrimidine, 5,6-dimethylbenzimidazole, 2-amino-5-mercapto-1 ), 3,4-thiadiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole ( 2-mercaptobenzothiazole, and 2-mercaptobenzimidazole. 2. A transparent conductive film according to claim 1, wherein the transparent conductive film is an organic compound selected from the group consisting of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole.
The method according to claim 1,
Wherein the top coating layer has a thickness of 0.001 to 1000 mu m.
Applying a coating liquid composition comprising a metal nanowire, an ultraviolet light sensitive material, a water dispersible polyurethane or a binder which is a cationic polymer electrolyte and a solvent to a substrate to form a coating conductive film;
Exposing to ultraviolet light in accordance with a predetermined specific pattern and exposing and cleaning to form an exposed area and an unexposed area; And
And forming a top coating layer on the coated conductive film formed with the exposed region and the unexposed region.
16. The method of claim 15,
The top coat layer may be formed of a polymer selected from the group consisting of polyurethane, polyacrylate, epoxy, polyimide, polyester, polyacrylic acid, polyvinyl alcohol, and polyethyleneimine, or an inorganic material including silicon dioxide and titanium dioxide, Wherein the transparent conductive film is formed by coating.
16. The method of claim 15,
Wherein the top coating layer further comprises a corrosion inhibitor or a color coordinate adjusting material.

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