KR101620037B1 - Coating solution comprising metal nanowire, coated conductive film manufactured by using the same and preparation method thereof - Google Patents

Abstract

The present invention can form a wiring pattern capable of flowing electricity in a specific pattern form by forming a difference in electrical conductivity in a local region of the conductive film by using a simple exposure and cleaning process without direct etching of the conductive film, And a coating conductive film using the same, and a method for manufacturing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution composition containing metal nanowires,

The present invention relates to a coating liquid composition comprising metal nanowires, a coated conductive film using the same, and a method of manufacturing the same. More particularly, the present invention relates to a coating liquid composition comprising metal nanowires, A coating liquid composition including metal nanowires capable of forming wiring patterns capable of flowing electricity in a specific pattern form and capable of improving insulation stability in an insulating region of a patterned conductive film, a coating conductive film using the same, and a manufacturing method thereof ≪ / RTI >

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.

The present inventors formed a pattern of electric current with a conductive film having a difference in electrical conductivity in a local region by using an ultraviolet photosensitive material contained in a coating liquid containing a metal nanowire, an ultraviolet light sensitive material, a binder, a bulk contraction inhibitor and a solvent The metal nanowires corresponding to the conductive filler of the conductive film are not etched and exist in a similar distribution with respect to regions having different electrical conductivities and are not chemically / physically damaged due to localization in a specific region, When the coating liquid contains a bulk shrinkage inhibitor, it is exposed to ultraviolet rays to improve the insulation property by interfering with the contact property between the metal nanoparticles in the portion where insulation is formed. I know that I can A has been completed.

It is an object of the present invention to provide a method of forming an electrical conductivity difference in a localized region of a conductive film using a simple exposure and cleaning process without direct etching of the conductive film by including metal nanowires, ultraviolet sensitive materials, binders, A coating liquid composition capable of forming a wiring pattern through which electricity can flow, and a coated conductive film for a transparent electrode manufactured using the same.

Another object of the present invention is to provide a coating liquid composition which is not chemically / physically etched in a specific region for forming a pattern of a conductive film, is not oxidized or formed by a chemical method, is not formed and physically conductive nanomaterial is hardly damaged, And to provide a coated conductive film for a transparent electrode.

It is still another object of the present invention to provide a method for manufacturing a coated conductive film for a transparent electrode, which can improve insulation stability and pattern accuracy in an insulating region of a conductive film patterned by an exposure and cleaning process.

In order to accomplish the above object, the present invention provides a photosensitive coating liquid composition for the production of a coating conductive film comprising a metal nanowire, an ultraviolet ray-sensitive material, a bulk shrinkage inhibitor and a solvent.

The photosensitive coating solution composition for producing a coating conductive film may further comprise a binder.

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 an ultraviolet sensitive material, 0.001 to 30% by weight of a bulk shrinkage inhibitor, Of a solvent. When the binder is added, the content of the binder is preferably 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 volumetric shrinkage preventing agent used in the present invention may be at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyethylene glycol derivatives, polyethylene oxide, polyvinyl alcohol, poly (hydroxyethyl methacrylate) Methyl methacrylate), N-methyl-2-pyrrolidone, dimethylformamide, and water-soluble or alcohol-soluble hydrogels.

The present invention also provides a coated conductive film for a transparent electrode formed on a substrate, comprising a metal nanowire, an ultraviolet ray sensitive material, a binder, a volume contraction inhibitor, and a solvent, wherein the exposed region and the non- Thereby providing a coated conductive film for a transparent electrode.

The present invention also provides a method for forming a conductive film, comprising: coating a substrate with a photosensitive coating composition for forming a conductive film to form a conductive film; Exposing the substrate on which the conductive film is formed to ultraviolet light according to a predetermined specific pattern to form an exposed region and an unexposed region; And cleaning the substrate on which the exposed region and the non-exposed region are formed.

In the coated conductive film according to the present invention, the unexposed area is more removed in the cleaning process than the exposed area, so that the residue content is lower, so that the unexposed area is exposed Electrical conductivity is higher than in the region.

The present invention relates to a method for forming a conductive film using a photosensitive coating solution containing a metal nanowire, an ultraviolet photosensitive material, a binder, a bulk shrinkage inhibitor and a solvent, and forming a pattern of an electric current flow through an exposure and cleaning process, The pattern forming process can be greatly shortened.

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.

The present invention further secures insulation stability in the insulating region of the conductive film patterned by the exposure and cleaning processes, thereby securing reliability against external impacts and environmental changes, reducing process defects during pattern formation, and improving pattern accuracy .

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 conductive substrate on which a coated conductive film including a metal nanowire according to the present invention is formed.
3 is an enlarged view of a portion " A " in Fig.
4 is a flow chart according to the method of manufacturing the coated conductive film of FIG.
FIGS. 5 to 8 are views showing each manufacturing step of the manufacturing method of FIG.
9 is a view showing a structure of an insulation test pattern according to a line width of a wiring pattern of a coated conductive film manufactured according to an embodiment of the present invention.

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 conductive substrate on which a coated conductive film including a metal nanowire 21 according to the present invention, an ultraviolet ray sensitive material, a binder, a volume contraction inhibitor, and a solvent is formed. 3 is an enlarged view of a portion " A " in Fig.

2 and 3, a conductive substrate 100 according to the present invention includes a substrate 10, and a metal nanowire 21 formed on the substrate 10. The metal nanowire 21, an ultraviolet sensitive material, a binder, And a coating conductive film 20 for a transparent electrode including a solvent and having wiring patterns 29 formed by exposure and washing.

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.

The photosensitive coating composition includes, for example, 0.01 to 5 wt% of metal nanowires, ultraviolet light sensitive material, ultraviolet light sensitive material, ultraviolet light sensitive material, binder, bulk shrinkage preventing agent and solvent. 0.1 to 5% by weight of a substance, 1% by weight or less of a binder, 0.001 to 30% by weight of a bulk shrinkage inhibitor, and a solvent such as water or an alcohol.

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

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

Further, in order to improve the conductivity of the conductive film, improve the uniformity, and improve the environmental stability, the photosensitive coating composition may further contain other additives such as carbon nanotubes, graphene, graphene oxide, and conductive polymer materials in addition to metal nanowires. 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 liquid, 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% by weight, 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 volumetric shrinkage preventing agent used in the present invention means a material capable of preventing shrinkage of a thin film while evaporating the solvent during drying after coating, or causing volume increase due to moisture absorption and temperature change. Representative materials include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyethylene glycol derivatives, polyethylene oxide, polyvinyl alcohol, poly (hydroxyethyl methacrylate), poly (hydroxymethyl methacrylate) N-methyl-2-pyrrolidone, dimethylformamide and a water-soluble or alcohol-soluble hydrogel.

If the volume contraction inhibitor is added to the coating liquid composition in an amount of less than 0.001 wt%, it is difficult to sufficiently perform the function. If the volume contraction inhibitor is added in an amount of more than 30 wt%, the volume contraction inhibitor may not be removed or removed in a non- It is not desirable.

These materials can be dissolved in water or alcohol which is a coating liquid solvent to form a coating liquid composition, but generally have a high breaking point, so that they can not be completely dried during the drying process after the thin film coating, thereby preventing shrinkage of the thin film, It is a substance that absorbs or increases in volume by temperature change. When such a material is added to a coating liquid composition to be dried on the substrate, it is possible to minimize the shrinkage of the film due to evaporation of the solvent during the drying process, to absorb ultraviolet light when washed with water or alcohol, The volume is increased. Among the specific kinds of chemicals contained in the coating liquid, those present in the exposed area increase the insulation property by opening the gap between the metal nanowire particles due to the prevention of volume contraction or increase in volume of the process. In the case of unexposed areas of the chemical, all or part of the area is removed during the cleaning process, so that the non-exposed areas maintain the conductive properties.

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 sensitive material, a binder, a bulk shrinkage preventing agent, and a solvent, or may have a structure in which a photosensitive material layer is formed on the 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 light sensitive material, the binder, and the volume contraction inhibitor before being formed into the coating conductive film 20, that is, before the ultraviolet light exposure and the cleaning is cleaned is formed by the photosensitive material and the binder with very low electrical conductivity .

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.

A method of manufacturing the coated conductive film 20 according to the present invention will now be described with reference to FIGS. 2 to 8. FIG. Here, FIG. 4 is a flow chart according to the method of manufacturing the coating conductive film 20 of FIG. And FIGS. 5 to 8 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. The photosensitive coating composition may include 0.01 to 5 wt% of metal nanowires, 0.1 to 5 wt% of an ultraviolet ray sensitive material, 1 wt% or less of a binder, and 0.001 to 30 wt% of a volumetric shrinkage inhibitor.

Meanwhile, the photosensitive thin film 23 may have a structure including a metal nanowire, an ultraviolet ray sensitive material, a binder, a bulk shrinkage preventing agent, 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.

Then, as shown in FIG. 8, the conductive thin film, which has been exposed in step S2, is washed with a solvent and dried to produce the conductive substrate 100 having the coating conductive film 20 having the wiring pattern 29 formed thereon. 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 a metal nanowire, an ultraviolet ray sensitive material, a binder and a bulk shrinkage preventing agent, and may include other composition materials such as additives such as a dispersing agent.

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 conductive substrate 20 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 (100).

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 .

In addition, since the coating conductive film 20 according to the present invention includes a volumetric shrinkage inhibitor, when it is added to a coating liquid composition and coated on a substrate and dried at a high temperature, shrinkage of the thin film due to evaporation of the solvent during the drying process is minimized, When washed with water or alcohol, and when exposed to the atmosphere, the volume increases by absorbing moisture. Those of the volumetric shrinkage inhibitor contained in the coating solution, which are present in the exposed region 25, increase the insulating property by spreading the space between the metal nanowires due to the increase in the volume of the process. In the case of the non-exposed region 27 of the bulk shrinkage preventing agent, all or part of the unbaked region 27 is removed during the cleaning process, so that the conductive characteristics of the unexposed region 27 are maintained.

The characteristics of the coated conductive film will be described below with reference to the conductive substrate according to the present invention.

Example  One

The conductive substrate according to Example 1 of the present invention used a PET film as a substrate and silver nano wire as a 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, a silver nano wire (0.15 wt%), a photosensitive polyvinyl alcohol (0.5 wt%) as a water-soluble photosensitive material, a dispersant HPMC (0.3 wt%), a water dispersible polyurethane binder (0.04 wt% 0.5% by weight).

The silver nano wire aqueous dispersion was coated on the substrate by a bar coating method, and the coated substrate was dried at a temperature of 130 DEG C for 5 minutes. The sheet resistivity of the dried photosensitive composite conductive film was high (not less than 10 MΩ / sq) so as not to be measured by a sheet resistance meter. The photosensitive composite conductive film was irradiated with ultraviolet rays in a specific pattern form for 3 seconds using a chromium photomask. And washed with water as a solvent and dried. The ultraviolet ray exposure area was a straight line of various line width as shown in the figure below, and the insulation property according to the exposure line width was examined.

As a result, a transparent conductive film was formed in which the ultraviolet exposure line was visually recognized with a slight opaque line, and the opaque line of the exposure line was not visually recognized when another polymer material was over-coated thereon or another film was bonded. The exposure line has a linear shape with different linewidths as shown in FIG. 9, and the resistance is measured with respect to each exposure line.

The AB resistance, the BC resistance, the CD resistance, and the DE resistance value in FIG. 9 were all 10 MΩ / sq or more, and the insulation resistance of the exposure line was high enough to make resistance measurement impossible with the resistance measuring instrument. The EF resistance was 50 to 60 kΩ and the FG resistance was 10 to 20 kΩ Level resistance was measured. The areas A, B C, D, E, F, and G are areas with high electrical conductivity to areas where photosensitive materials, chemicals, and other compositions have been removed by washing into respective non-exposed areas. In this region, the sheet resistance value was 110 ~ 140? / Sq, the light transmittance was 90%, and the haze was 1.6.

 A, B, C, D, E, F, and F were exposed to the ultraviolet rays of the same condition for 5 seconds in order to check the damage of the silver wire itself by the ultraviolet ray exposure, The sheet resistance of each region was measured. The sheet resistances of A, B, C, D, E, F and G before UV exposure were 110 ~ 140 Ω / sq and the light transmittance was 90% and haze was 1.6. , The surface resistances of the F and G regions were 110 ~ 140 Ω / sq, and the light transmittance was 90% and the haze was 1.6. Within 5 seconds, the ultraviolet exposure showed almost no damage to the silver nano wire.

In order to confirm the insulation stability at a high temperature, the film of FIG. 9 was stored in an oven at 130 ° C for 1 hour and AB resistance, BC resistance, CD resistance, DE resistance, EF resistance and FG resistance value were measured. As a result, AB resistance, BC resistance, CD resistance and DE resistance exceed 10MΩ / sq, and the resistance of the resistance measuring device is out of the range of 40 ~ 60kΩ and the resistance of FG is 3 ~ 10kΩ.

Example  2

(0.5% by weight), a polyurethane binder (0.04% by weight) and triethylene glycol (0.5% by weight), which are water-soluble photosensitive materials, in addition to the carbon nanotubes (0.03% by weight) To prepare a coating solution.

The carbon nanotubes are single wall carbon nanotubes, and the silver nanowires are 20 to 40 nm in diameter and 10 to 30 μm in length. The coating solution was coated on the PET film by a bar coating method, and the coated substrate was dried at a temperature of 130 DEG C for 1 minute. The sheet resistance of the dried photoconductive film had a resistance which was not measurable by a sheet resistance meter (10 M? / Sq or more). The photosensitive composite conductive film was irradiated with ultraviolet rays for 3 seconds in a specific pattern form using a chromium photomask and post baking at 130 ° C for 5 minutes. And washed with water as a solvent and dried. As shown in Fig. 9, the ultraviolet ray exposure area was a straight line having various line widths, and the insulation property according to the exposure line width was examined.

 As a result, a transparent conductive film was formed in which the ultraviolet exposure line was visually recognized with a slight opaque line, and the opaque line of the exposure line was not visually recognized when another polymer material was over-coated thereon or another film was bonded. As shown in FIG. 9, the exposure line has a straight line shape having different line widths, and the resistance is measured with each exposure line as a boundary. AB resistance, BC resistance, CD resistance, and DE resistance are all 10MΩ / sq or more, so that the resistance of the exposure line is high enough that resistance measurement by the resistance measuring device is not possible. EF resistance is 40 to 60 kΩ and FG resistance is 10 kΩ Respectively. The areas A, B, C, D, E, F, and G are areas with high electrical conductivity to the areas where the photosensitive material, anti-shrinkage agent, In this region, the sheet resistance value was 110 ~ 130? / Sq, the light transmittance was 89.5%, and the haze was 1.5.

 B, C, D, E, F, and C were exposed to the ultraviolet rays of the same condition under the same condition, in order to confirm that there was no damage to the silver nanoair due to ultraviolet exposure. The sheet resistance of each region was measured. The sheet resistances of the A, B, C, D, E, F and G regions before UV exposure were measured at 110-140? / Sq and the light transmittance was 89% and the haze was 1.5. , The sheet resistance of the E, F, and G regions was 110 to 130? / Sq, and the light transmittance was 89.4% and the haze was 1.5 at 5 seconds or less.

To confirm the insulation stability of the ultraviolet exposure area, the patterned film was stored in an oven at 130 ° C for 1 hour and AB resistance, BC resistance, CD resistance, DE resistance, EF resistance and FG resistance value were measured. As a result, AB resistance, BC resistance, CD and DF resistance were more than 10MΩ / sq, and resistance of 40kΩ for DE, 40kΩ for EF and 4kΩ for FG resistance were decreased.

Comparative Example  One

A silver nano wire coating solution similar to that of Example 1 was coated on a substrate except that diethylene glycol was not included, and a pattern composed of a region having a high conductivity and a region having a low conductivity was formed by an exposure and a washing method.

The AB resistance, the BC resistance, the CD resistance, and the DE resistance value in FIG. 9 are all 10 M OMEGA / sq or more, so that the resistance of the exposure line is high enough that the resistance measurement by the resistance measuring device is not possible. The EF resistance is 20 to 40 kΩ and the FG resistance is 3 to 10 kΩ Level resistance was measured. The areas A, B, C, D, E, F, and G are areas with high electrical conductivity to areas where photosensitive materials and other compositions have been removed by washing into respective unexposed areas. In this region, the sheet resistance value was 120 ~ 150? / Sq, the light transmittance was 90%, and the haze was 1.5.

In order to confirm the insulation stability of the ultraviolet exposure area, the films were stored in an oven at 130 ° C for 1 hour and AB resistance, BC resistance, CD resistance, DE resistance, EF resistance and FG resistance value were measured. As a result, AB resistance, BC resistance and CD resistance were more than 10MΩ / sq, but resistance of DE resistance 4 ~ 10 kΩ, EF resistance and FG resistance were all lower than 10kΩ. That is, as the thin film shrinks in the heat treatment process at 130 ° C., the photosensitive material and the conductive particles in the exposed portion are rearranged to form an electrical connection, thereby making the insulating property weak.

Comparative Example  2

An aqueous dispersion containing carbon nanotubes / silver nano wires similar to those of Example 2 was coated on a PET film by a bar coating method except that triethylene glycol was not included, thereby forming the same pattern.

The AB resistance, the BC resistance, the CD resistance, and the DE resistance value in FIG. 9 were all 10 M OMEGA / sq or more, and the resistance of the exposure line was high enough that the resistance measurement by the resistance measuring instrument was impossible. The EF resistance was 55 kΩ and the FG resistance was 4 kΩ Was measured. The areas A, B, C, D, E, F, and G are areas with high electrical conductivity to areas where photosensitive materials and other compositions have been removed by washing into respective unexposed areas. In this region, the sheet resistance value was 120 ~ 150? / Sq, the light transmittance was 90%, and the haze was 1.5.

 B-C resistance, C-D resistance, D-E resistance, E-F resistance, and F-G resistance values were measured in order to confirm insulation stability at a high temperature. As a result, the resistance of A-B, B-C and C-D resistors was more than 10MΩ / sq, which is better than the resistance of the resistance meter. However, resistance was decreased to 18k for D-F resistance and 10kΩ for E-F resistance.

That is, the thin film was shrunk in the heat treatment process at 130 ° C, and the photosensitive material and the conductive particles in the exposed portion were rearranged and electrically connected to each other, resulting in poor insulation.

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 thereof 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
100: conductive substrate

Claims (16)

Metal nanowires or metal nanoribbons, ultraviolet sensitive materials, anti-shrinkage agents, binders and solvents,
After being coated on the substrate, exposure and cleaning processes are performed to form an exposed area and a non-exposed area,
Wherein the non-exposed region has a higher electrical conductivity than the exposed region.
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, 1 wt% or less of a binder, and 0.001 to 30 wt% of a bulk shrinkage inhibitor.
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. Coating liquid composition.
The method according to claim 1,
Further comprising 0.001 to 5 wt% of other additives selected from the group consisting of carbon nanotubes, graphene, oxide graphene, carbon nanoplates, carbon black, and conductive polymers.
The method according to claim 1,
Wherein the metal nanowire is silver nano wire, gold nanowire, or copper nanowire.
The method according to claim 6,
Wherein the metal nanowire is a silver nanowire. ≪ RTI ID = 0.0 > 21. < / RTI >
The method according to claim 1,
Wherein the ultraviolet light sensitive material is a polyvinyl alcohol having a photosensitive functional group.
The method according to claim 1,
Wherein the binder is a water-dispersible polyurethane or a cationic polymer electrolyte.
The method according to claim 1,
Wherein the solvent is water or an alcohol.
The method according to claim 1,
The volumetric shrinkage inhibitor may be selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyethylene glycol derivatives, polyethylene oxide, polyvinyl alcohol, poly (hydroxyethyl methacrylate), poly (hydroxymethyl methacrylate) , N-methyl-2-pyrrolidone, dimethylformamide, and a water-soluble or alcohol-soluble hydrogel.
A coated conductive film for a transparent electrode formed on a substrate,
An exposed region and an unexposed region in which exposure and cleaning treatments have been performed are formed, which includes a metal nanowire, an ultraviolet sensitive material, a binder, an anti-shrinkage agent and a solvent,
Wherein the non-exposed region has a higher electrical conductivity than the exposed region.
delete 13. The method of claim 12,
Wherein the metal nanowire is a silver nanowire, the ultraviolet sensitive material is a polyvinyl alcohol having a photosensitive functional group, the binder is a water-dispersible polyurethane or a cationic polymer electrolyte, and the solvent is water or an alcohol. Coated conducting film.
12. A method for forming a conductive film, comprising: coating a substrate with a photosensitive coating liquid composition for producing a coating conductive film according to any one of claims 1 to 11 to form a conductive film;
Exposing the substrate on which the conductive film is formed to ultraviolet light according to a predetermined specific pattern to form an exposed region and an unexposed region; And
Cleaning the substrate on which the exposed area and the unexposed area are formed
Wherein the transparent conductive film is a transparent conductive film.
16. The method of claim 15,
Wherein the cleaning liquid used in the cleaning step is water.

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