KR101621282B1 - Photosensitive coating solution and coated conductive film for transparent electrode using the same - Google Patents

Abstract

The present invention relates to a photosensitive coating composition and a coated conductive film for a transparent electrode using the same, wherein a difference in electric conductivity is formed in a local region of the conductive film by using a simple exposure and cleaning method without direct etching of the conductive film containing the conductive nanomaterial, So that electricity can flow in the form of a pattern while ensuring insulation stability of the insulation portion. The present invention relates to a conductive nanomaterial comprising 0.01 to 5% by weight of a conductive nanomaterial, 0.01 to 0.5% by weight of a nanoparticle, 0.01 to 3% by weight of a photosensitive material and 1% by weight or less of a binder, wherein the nanoparticle comprises oxide nanowires, Particles or carbon nanoparticles, and a coated conductive film for a transparent electrode using the same.

Description

[0001] The present invention relates to a photosensitive coating composition and a coated conductive film for a transparent electrode using the same,

The present invention relates to a coated conductive film, and more particularly, to a method of forming a coating film by a wet coating process on a composition including a conductive nanomaterial such as a metal nanowire or nano carbon, A wiring pattern, and a coated conductive film for a transparent electrode using the same.

The conductive thin film including metal nanowires or nanocarbon can be formed by coating on a substrate as a conductive film formed by successive contact of conductive nanomaterials in the form of wires, tubes, and nanoparticles. The conductive film including metal nanowires or nanocarbon can be formed as a conductive film having electrical conductivity by forming a dispersion by coating with various substrates by a simple solution process and thus can be used as a transparent electrode and a circuit electrode in a touch panel, have.

 In order to use a conductive film composed of a metal nanowire or nano carbon 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.

 Photolithography and a laser etching process are mainly applied as a conventional method of forming a wiring pattern on a substrate having a conductive film formed thereon. 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 wiring pattern is formed by etching the conductive film in a specific pattern by a wet or dry method. The laser etching method is a method of forming a wiring pattern by etching a conductive film in a specific pattern using a laser.

This method can form a fine pattern of the conductive film using existing known processes. However, due to the difference in the distribution of metal nanowires or nano-carbons in the etched region and the non-etched region in the conductive film having the wiring pattern, light reflectance, light transmittance and haze difference are formed. Thereby causing a problem that the wiring pattern of the conductive film is visually recognized.

In addition, in the case of the photolithography process, a separate process is required to form a wiring pattern of the conductive film, which requires a further additional processing cost and low productivity.

U.S. Patent No. 8,018,568 (September 23, 2011)

It is therefore 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 electric conductivity in a local region of a conductive film by using a simple exposure method without direct etching of a conductive film including a conductive nanomaterial A photosensitive coating composition and a coated conductive film for a transparent electrode using the same.

Another object of the present invention is to provide a conductive film having a conductive layer having a different electric conductivity in a localized region but a conductive nanomaterial corresponding to a conductive filler of the conductive film has a similar distribution density to regions having different electric conductivity, And a coated conductive film for a transparent electrode using the same.

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

It is still another object of the present invention to provide a photosensitive coating composition capable of ensuring insulation stability in an insulating region of a transparent conductive film, and a coated conductive film for a transparent electrode using the same.

In order to achieve the above object, the present invention provides a nanocomposite comprising 0.01 to 5% by weight of a conductive nanomaterial, 0.01 to 0.5% by weight of a nanoparticle, 0.01 to 3% by weight of a photosensitive material and 1% There is provided a photosensitive coating composition for the production of a coated conductive film for a transparent electrode comprising a wire, oxide nanoparticles, metal nanoparticles or carbon nanoparticles.

In the photosensitive coating composition according to the present invention, the oxide nanowire has a diameter of 10 nm to 1 탆 and a length of 1 탆 to 100 탆. The oxide nanoparticles, metal nanoparticles and carbon nanoparticles are spherical, cubic or amorphous nanoparticles having a particle size of 5 nm to 30 μm. The oxide nanowires are metal oxide nanowires or non-metal oxide nanowires. The oxide nanoparticles are metal oxide nanoparticles or non-metal oxide nanoparticles.

In the photosensitive coating composition according to the present invention, the conductive nanomaterial is a metal nanowire or a carbon nanotube. The photosensitive material is a polyvinyl alcohol having a photosensitive functional group. The binder is a water-dispersible polyurethane or a cationic polymer electrolyte.

The present invention also provides a coated conductive film for a transparent electrode formed on a substrate, comprising a nanoparticle containing oxide nanowires, oxide nanoparticles, metal nanoparticles, or carbon nanoparticles, a conductive nanomaterial, a photosensitive material and a binder, The exposed and unexposed regions are formed by exposure and cleaning, and the unexposed region has an electrical conductivity two times or more as compared with the exposed region.

In the coated conductive film according to the present invention, the non-exposed region may have a lower residual amount of the photosensitive material than the exposed region in the cleaning process.

In the coated conductive film according to the present invention, the exposed region is more impregnated with the photosensitive nanomaterial and the nanoparticles than the non-exposed region.

According to the present invention, after forming a photosensitive thin film including a photosensitive material and a binder together with a conductive nanomaterial on a substrate, the photosensitive thin film is exposed and washed according to the shape of a wiring pattern to be formed, A wiring pattern having a conductivity difference can be formed.

That is, the photosensitive coating composition forming the photosensitive thin film contains photosensitive materials, binders and other compositions in addition to the conductive nanomaterials. When the photosensitive thin film is exposed to ultraviolet rays, physical or chemical bonds between the photosensitive material and the photosensitive material and other compositions are 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 a photosensitive film results in a relatively large amount of photosensitive material and other compositions being removed from the unexposed portion as compared to the exposed portion, so that the exposed and unexposed portions form a pattern of electrical current flow The difference in the electrical conductivity is enough to be able to do.

As described above, the present invention forms a wiring pattern capable of flowing electricity in a specific pattern form by forming a difference in electrical conductivity in a local region of a coated conductive film by using a simple exposure method without direct etching on a coated conductive film including a conductive nanomaterial can do.

The coated conductive film according to the present invention forms a wiring pattern by a post-exposure cleaning process to form a difference in electric conductivity in the local region. However, the conductive nanomaterial corresponding to the conductive filler of the coated conductive film is distributed in different regions having different electric conductivity And has a similar distribution structure and distribution density.

The present invention also relates to a coated conductive film comprising a conductive nanomaterial that is not chemically and physically etched in a specific region for pattern formation of a coated conductive film, is not oxidized or sulfide formed by a chemical method and is not physically damaged by the conductive nanomaterial Film. This makes it possible to control the electrical flow characteristics of the conductive nanomaterials without directly etching the coated conductive film and solve the problem of pattern visibility due to the difference in the distribution of the conductive nano-density, Can be simplified.

In addition, since the coated conductive film according to the present invention includes nanoparticles, it provides structural stability compared to the exposed areas not containing nanoparticles. Thus, the transparent conductive film can provide reliability for insulation stability, external impact, environmental change, etc., and provide improved pattern accuracy based on structural stability in an insulating region.

1 is a perspective view showing a conductive substrate on which a coated conductive film including nanoparticles according to the present invention is formed.
2 is an enlarged view of a portion "A" in Fig.
3 is a flow chart according to the method of manufacturing the coated conductive film of FIG.
FIGS. 4 to 7 are views showing respective steps according to the manufacturing method of FIG.
8 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 the first embodiment of the present invention.
9 to 11 are photographs showing a coated conductive film manufactured according to the first embodiment of the present invention.
12 and 13 are photographs showing a coated conductive film manufactured according to the third embodiment of the present invention.

In the following description, only parts necessary for understanding the embodiments of the present invention will be described, and the description of other parts will be omitted so as not to obscure the gist of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor is not limited to the meaning of the terms in order to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely 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 variations are possible.

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

1 is a perspective view showing a conductive substrate on which a coated conductive film including nanoparticles according to the present invention is formed. 2 is an enlarged view of a portion "A" in Fig.

Referring to FIGS. 1 and 2, a conductive substrate 100 according to the present invention includes a substrate 10, a conductive material layer 21 formed on the substrate 10, and conductive nanomaterials 21, nanoparticles 22, And a coating conductive film 20 for a transparent electrode on which wiring patterns 29 are formed by exposure and cleaning.

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 10,000 mu m.

The photosensitive coating composition forming the coating conductive film 20 may include nanoparticles 22, conductive nanomaterials 21, photosensitive materials and binders, and other compositions such as dispersants, additives, and the like . For example, the photosensitive coating composition comprises 0.01 to 5% by weight of the conductive nanomaterial 21, 0.01 to 0.5% by weight of the nanoparticles 22, 0.01 to 3% by weight of the photosensitive material and 1% by weight or less of the binder, do. And the photosensitive coating composition may further comprise up to 5% by weight of the additive.

The conductive nanomaterial 21 is a material that forms a conductive network of the coated conductive film 20 and can be electrically connected to each other to be coated on the substrate 10 to form the coated conductive film 20. As the conductive nanomaterial 21, metal nanowires or carbon nanotubes can be used. For example, silver nanowires, copper nanowires, gold nanowires, and the like may be used as the metal nanowires, but the present invention is not limited thereto. 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. Metal nanowires include metal nanotubes.

The nanoparticles 22 are oxide nanowires, oxide nanoparticles, metal nanoparticles, and carbon nanoparticles. The nanoparticles 22 have low electrical conductivity than metal nanowires or carbon nanotubes, or have a small aspect ratio of the particles, ) Is a material with low electrical connectivity. This kind of nanoparticles 22 does not significantly affect the electrical conductivity of the coated conductive film 20, but can improve the insulation stability in the exposed region 25. [

 Such nanoparticles 22 may have a linear, spherical, cubic, amorphous particle shape having a size of 5 nm or more. When the photosensitive material is crosslinked by ultraviolet rays, the nanoparticles 22 are impregnated with the photosensitive material and remain in the exposed area 25 without being removed in the washing process. In addition, these nanoparticles 22 have a specific size, and generally have a temperature change, a size and a volume stability against an external impact, and when the composite material is combined with a photosensitive material, the combined photosensitive material may have a volume , And minimizes the shape change. Thus, the exposed regions 25 containing these nanoparticles 22 have structural stability compared to the exposed regions that do not include the nanoparticles 22.

The oxide nanowire may have a diameter of 10 nm to 1 탆 and a length of 1 탆 to 100 탆. The oxide nanowires are metal oxide nanowires or non-metal oxide nanowires. The oxide nanoparticles, metal nanoparticles and carbon nanoparticles may be spherical, cubic or amorphous nanoparticles having a particle size of 5 nm to 30 μm. The oxide nanoparticles are metal oxide nanoparticles or non-metal oxide nanoparticles.

At this time, the higher the composition ratio of the conductive nanomaterial 21 included in the photosensitive coating solution, 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 it exceeds 5 wt%, there is a disadvantage that dispersion of the conductive nanomaterial 21 in solution is difficult. Therefore, the conductive nanomaterial 21 is preferably used in an amount of 0.1 to 0.5% by weight.

The higher the composition ratio of the nanoparticles (22) contained in the photosensitive coating liquid, the higher the insulation stability of the coating conductive film (20). However, when the concentration is too high, that is, when the concentration is more than 0.5% by weight, the coating conductive film 20 may not be removed much in the cleaning process in the unexposed region 27, ) Can be increased. On the contrary, when the content of the nanoparticles 22 is 0.01% by weight or less, the insulation stability of the coated conductive film 20 may hardly be affected. Therefore, the nanoparticles 22 are preferably used in an amount of 0.01 to 0.5% by weight.

The photosensitive material is a material which undergoes cross-linking by ultraviolet exposure, and has a low solubility in a solvent in a post-exposure cleaning process, thereby forming a relatively low electric conductivity region. Such a photosensitive material is preferably a material that is exposed to one or more energy irradiation such as light (infrared light, visible light, ultraviolet light), heat, laser, etc., and the energy source is not limited thereto.

For example, as the photosensitive material, an aqueous photosensitive material having photosensitivity to ultraviolet rays may be used. As the water-soluble photosensitive material, a polyvinyl alcohol material having a photosensitive functional group and polyvinyl alcohol having N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal functional group may be used, but the present invention is not limited thereto.

The photosensitive 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 1% by weight is suitable for forming the pattern of the transparent electrode. However, if the photosensitive material is added too much, the photosensitive material in the unexposed area 27 may be removed during the post-exposure cleaning process, and the conductive nanomaterial 21 may be removed as well, thereby causing the transparent electrode to be damaged or the resistance to be increased.

As the binder, a water-dispersible polyurethane or a cationic polyelectrolyte may be used. Examples of cationic electrolytes include poly (diallydimethylammonium chloride), poly (allyamine hydrochloride), poly (3,4-ethylenedioxythiophene) (PEDOT), poly (2-vinylpyridine), poly (ethylenenimine), 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 of 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 conductive nanomaterial 21 corresponding to the conductive filler so that the conductive nanomaterial 21 does not fall off the coated conductive film 20 from which the conductive nanomaterial 21 corresponding to the conductive filler is manufactured during the solvent cleaning process for manufacturing the coated conductive film 20. That is, if the binder is not included in the photosensitive coating solution, the conductive nanomaterial 21 is removed as a photosensitive material or the coating conductive film is not formed or the uniformity of the resistance is greatly reduced during the solvent washing process of the coated conductive film.

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 weight% or less to prevent the conductive nanomaterial 21 from falling off the substrate 10 during the post-exposure cleaning. At this time, if the content of the binder is high, the adhesion of the conductive nanomaterial 21 to the substrate 10 is improved, but the resistance of the coated conductive film 20 may increase. If the binder is absent or is too small, the conductive nanomaterial 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 0.1% by weight or less, the adhesion of the conductive nanomaterial 21 to the substrate 10 is maintained without the binder, and thus the production of the coated conductive film 20 according to the present invention is performed You may.

The dispersing agent may be classified into a dispersing agent for metal nanowires and a dispersant for nanocarbon according to the conductive nanomaterial (21) to be used. For example, hydroxypropyl methyl cellulose (HPMC), carboxymethyl cellulose (CMC), and 2-hydroxy ethyl cellulose (HC) may be used as the dispersing agent of the silver nano wire. Examples of dispersants for carbon nanotubes include sodium dodecyl sulfate (SDS), lithium dodecyl sulfate (LDS), sodium dodecylbenzenesulfonate (SDBS), sodium dodecylsulfonate (DTBS), dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) , Triton X-series, and poly (vinylpyrrolidone).

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.

Conductive polymer, graphene, and the like may also be included in the photosensitive coating liquid for further improving the conductivity and improving the adhesion of the coated conductive film 20.

The coated conductive film 20 according to the present invention includes a conductive nanomaterial 21 uniformly formed on a 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 electrical conductivity of the exposed region 25 and the non-exposed region 27 may have a difference of two times or more.

The coated conductive film 20 may be formed of one layer including the conductive nanomaterial 21, the photosensitive material and the binder, or may have a structure in which a layer of the photosensitive material 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 conductive nanomaterial 21, the photosensitive material and the binder before being formed into the coating conductive film 20, that is, before the ultraviolet light exposure and cleaning, has a very low electric 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 conductive nanomaterial 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 non-exposed region 29 form a difference in solubility 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.

In addition, there is a binder that can be included in the coating liquid, and the binder serves to fix the metal nanowires or the carbon nanotubes not to be removed during the cleaning process. And additives for improving coating properties, improving environmental durability, improving adhesion, and improving corrosion resistance.

On the other hand, when the coated conductive film is formed by using only the metal nanowire or the carbon nanotube as the conductive nanomaterial, the exposed region 25 having a low electrical conductivity may slightly lose its insulation stability. The reason for this is that since the metal nanowires having high electrical conductivity or the carbon nanotubes are present in the exposed region 25, when the external impact is applied or the volume of the conductive nanomaterial 21 changes due to temperature change, If it is connected, the insulation may drop a little.

In order to compensate for this, when the insulating region includes the nanoparticles 22 having a relatively low electrical conductivity or a small aspect ratio, the change in shape and volume of the exposed region 25 with respect to an external impact or a temperature change is reduced, The nanoparticles 22 are sandwiched between particles such as nanowires, carbon nanotubes, and the like, which interfere with electrical connectivity and maintain the insulating property.

The oxide nanowires, oxide nanoparticles, metal nanoparticles, and carbon nanoparticles in the unexposed region 27 may be partially or wholly cleaned or removed during the cleaning process, or may be electrically connected to the metal nanowires or carbon nanotubes Since the conductivity is ensured, the electric conductivity is not greatly affected.

In the present invention, the non-exposed region 27 has a higher solubility than the exposed region 25, but may exhibit opposite characteristics depending on the type of the photosensitive substance. That is, when the exposed region 25 has a higher solubility than the unexposed region 27, the exposed region 25 can be formed as a wiring pattern.

The widths of the exposed region 25 and the non-exposed region 27 forming the coated conductive film 20 are 1 탆 or more and the shape of the wiring pattern 29 is determined by exposure. The shape of the wiring pattern 29 is usually determined according to the shape of the mask used for exposure.

The method of manufacturing the coated conductive film 20 according to the present invention will now be described with reference to FIGS. 1 to 7. FIG. Here, FIG. 3 is a flow chart according to the method of manufacturing the coating conductive film 20 of FIG. And FIGS. 4 to 7 are views showing respective steps according to the manufacturing method of FIG.

First, as shown in FIG. 4, a substrate 10 on which a coated conductive film is to be formed is prepared.

Next, as shown in FIG. 5, a photosensitive thin film 23 including a conductive nanomaterial, nanoparticles, a photosensitive material, and a binder is formed on the substrate 10 in step S51. That is, the photosensitive coating composition according to the present invention is applied to form a photosensitive thin film 23. Wherein the photosensitive coating composition comprises conductive nanomaterials, nanoparticles, photosensitive materials, binders and water, and may further comprise other compositions. 0.01 to 5% by weight of a conductive nanomaterial, 0.01 to 0.5% by weight of a nanoparticle, 0.01 to 3% by weight of a photosensitive material, 1% by weight or less of a binder and 5% by weight or less of other composition.

Meanwhile, the photosensitive thin film 23 may be formed of one layer including a conductive nanomaterial, a nanoparticle, a photosensitive material and a binder, or may have a structure in which a photosensitive material layer is formed on a conductive nanomaterial layer containing nanoparticles. When the photosensitive thin film 23 is formed as a single layer such as an electron, other compositions such as a dispersing agent, an additive, etc. may be included together. In the case of the latter photosensitive film 23, other compositions such as binders, dispersants, additives and the like are included in the conductive nanomaterial layer containing the nanoparticles.

Subsequently, as shown in FIG. 6, in step S53, 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 conductive nanomaterials and nanoparticles during the exposure process.

7, the conductive thin film, which has been exposed in step S55, 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 direct etching of the coating conductive film 20 and can be formed in 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 material.

The photosensitive thin film according to the present invention includes conductive nanomaterials, nanoparticles, photosensitive materials and binders, and may include other composition materials such as dispersants and additives.

As described above, the conductive substrate 100 according to the present invention is formed by forming a photosensitive thin film containing a photosensitive material together with conductive nanomaterials and nanoparticles on a substrate 10, exposing the photosensitive thin film to the shape of a wiring pattern 29 to be formed The coated conductive film 20 having the wiring pattern 29 having the electrical conductivity difference between the exposed region 25 and the unexposed region 27 can be formed.

That is, the photosensitive thin film includes conductive nanomaterials, nanoparticles, and other compositions such as dispersants and additives. When the photosensitive thin film is exposed to light, physical or chemical bonds between the photosensitive materials or between the photosensitive material and the other composition are 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.

In addition, the conductive substrate 100 according to the present invention forms a coating conductive film 20 having a different electrical conductivity in the local region by forming the wiring pattern 29 in the post-exposure cleaning process, The conductive nanomaterials corresponding to the conductive filler of the conductive film 20 may be uniformly distributed over the entire coated conductive film 20 even in regions having different electric conductivities.

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).

In addition, the coated conductive film 20 according to the present invention has a problem that a pattern visibility problem occurs due to the presence of the conductive nanomaterials in the exposed region 25 and the unexposed region 27 similarly even when the exposure and cleaning are performed .

Also, because the coated conductive film 20 according to the present invention comprises nanoparticles, it provides structural stability compared to the exposed areas 25 without nanoparticles. Therefore, the transparent conductive film 20 can provide reliability for insulation stability, external impact, environmental change, and the like, and can provide improved pattern accuracy based on the structural stability in the insulating region.

The characteristics of the coated conductive film will be described below with reference to the conductive substrate according to the present invention. In the first to fourth embodiments, the photosensitive polyvinyl alcohol as a water-soluble photosensitive material is a polyvinyl alcohol having photosensitive functional groups of N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal.

First Embodiment

The conductive substrate according to the first embodiment of the present invention uses 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 30 탆 in length. At this time, the silver nano wire coating liquid contains silver nano wire (0.15 wt%), photosensitive polyvinyl alcohol (0.6 wt%) as a water-soluble photosensitive material, dispersant HPMC (0.2 wt%) and water dispersible polyurethane binder The remainder is water so that the amount is 100 wt%.

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 ° C for 1 minute. The sheet resistance value of the dried photosensitive thin film was high (not less than 10 MΩ / sq) so as not to be measured by the sheet resistance meter. The photosensitive thin film was irradiated with ultraviolet rays for 3 seconds in a specific pattern form using a chromium photomask, and post baking was performed at 130 캜 for 5 minutes. Then, the coated conductive film according to the first embodiment formed on the substrate can be obtained by washing with water as a solvent and drying.

The exposed areas of the coated conductive film according to the first embodiment were formed by straight lines having various line widths as shown in Fig. 8, and the insulating properties according to the exposure line width were examined. 8 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 the first embodiment of the present invention.

Referring to FIG. 9, the ultraviolet exposure line is formed of a transparent conductive film that is visible with a slight translucent line, but the translucent line of the exposure line is not visible when another polymer material is overcoated or adhered thereto.

The exposure line has a linear shape with different line widths, and the resistance is measured with each exposure line as a boundary. The first exposure line 41 formed between the A region and the B region has a line width of 150 mu m. And the second exposure line 42 formed between the B region and the C region has a line width of 100 mu m. The third exposure line 43 formed between the C region and the D region has a line width of 60 mu m. The fourth exposure line 44 formed between the D region and the E region has a line width of 40 mu m. The fifth exposure line 45 formed between the E region and the F region has a line width of 30 mu m. And the sixth exposure line 46 formed between the F region and the G region has a line width of 20 mu m. The first to sixth exposure lines were formed to have a length of 80 mm.

The resistance values of the first to fourth exposure lines 41, 42, 43 and 44 were all 10 MΩ / sq or more, and the insulation of the exposure line was high enough that the resistance measurement by the resistance measuring device was impossible. The resistance value of the fifth exposure line 45 was 20 to 30 kΩ, and the resistance value of the sixth exposure line 46 was measured to be 2 kΩ.

The regions A, B, C, D, E, F, and G are regions that have a high electrical conductivity to a region where the photosensitive material is removed by washing into each unexposed region. 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 examine the surface morphologies of the portions irradiated with ultraviolet rays and those not irradiated with ultraviolet rays, an ultraviolet exposure line and a non-exposed region were observed with an electron microscope, as shown in Figs. 9 to 11 are photographs showing the coated conductive film manufactured according to the first embodiment of the present invention.

As a result of the analysis, the ultraviolet ray exposure area area 10 (a) and (b) and the ultraviolet ray unexposed area area 11 (c) and (d) It was almost impossible to find out.

However, in the enlarged electron microscope images (b) and (d), in the ultraviolet exposure line region (b), the silver nano wire is covered by the photosensitive material and the binder as compared with the ultraviolet non- The characteristics are not good and the resistance is increased. The binder, polyurethane, can bond the silver nano wire to the substrate to prevent detachment of the silver nano wire during the cleaning process.

B, C, D, E, and E after exposing again 5 seconds to ultraviolet rays of the same condition on the conductive substrate according to the first embodiment, in order to confirm the damage of the silver nano wire itself by the ultraviolet ray exposure, F, and G, respectively. The sheet resistances of the A, B, C, D, E, F, and G regions before UV exposure were 120-150? / Sq and the light transmittance was 90%. The sheet resistance of the A, B, C, D, E, F, and G areas was 120 ~ 150 Ω / sq and the light transmittance was 90% after 5 seconds of ultraviolet exposure. Able to know.

In order to confirm the insulation stability of the exposed area, the coated conductive film according to the first embodiment was stored in an oven at 130 ° C for 1 hour, and AB resistance, BC resistance, CD resistance, DE resistance, EF resistance, Respectively. As a result, it was confirmed that the A-B resistance, B-C resistance, and C-D resistance exceeded the measurement range of the resistance measuring device by more than 10 MΩ / sq. However, the D-E resistance of 4.6 kΩ, the E-F resistance, and the F-G resistance all decreased to less than 1 kΩ. That is, it is judged that the insulating property is partially deteriorated due to the electrical connection by rearranging the photosensitive material and the conductive nanomaterial in the exposed region in the 130 ° heat treatment process.

Second Embodiment

In the second embodiment, a coating liquid containing zinc oxide nanowires having a diameter of 100 nm and a length of 1 to 5 μm as nanoparticles is coated on a substrate in addition to a silver nanowire dispersion liquid, a photosensitive polyvinyl alcohol as a water-soluble photosensitive material, and a water dispersible polyurethane binder To form the same pattern. (0.1 wt%), zinc oxide nanowire (0.1 wt%), photosensitive polyvinyl alcohol (0.6 wt%) as a water-soluble photosensitive material, dispersant HPMC (0.2 wt%), water dispersible polyurethane binder % By weight), and the remainder is water so that the total amount is 100% by weight.

As shown in FIG. 8, the AB resistance, the BC resistance, the CD resistance, and the DE resistance were all 10 M OMEGA / sq or more, and the insulation resistance of the exposure line was high enough to make resistance measurement impossible with the resistance meter. The resistance was measured at the level of 3kΩ. That is, the A, B, C, D, E, F, and G regions are areas having high electrical conductivity to the 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 1.7.

In order to confirm the insulation stability at a high temperature, the coated conductive film according to the second embodiment of the form as shown in Fig. 8 was stored in a 130 degree oven for 1 hour, and AB resistance, BC resistance, CD resistance, DE resistance , EF resistance, and FG resistance were measured. As a result, it is confirmed that the A-B resistance, B-C resistance, C-D resistance and D-E resistance exceed 10 MΩ / sq and the resistance of the E-F resistance is 34 kΩ and the F-G resistance is 1 kΩ.

As described above, since the coated conductive film according to the second embodiment includes nanoparticles such as zinc oxide nanowires, it can be confirmed that the insulation stability is improved as compared with an exposed region not containing zinc oxide nanowires.

Third Embodiment

In the third embodiment, a pattern composed of a region having a high conductivity and a region having a low conductivity was formed using a carbon nanotube / silver nano wire photosensitive coating solution.

The carbon nanotube / silver nanowire photosensitive coating solution includes single wall carbon nanotubes, silver nanowires of 20 to 40 nm in diameter, 10 to 30 μm in length, and polyethylene imine binders. At this time, the carbon nanotube / silver nanowire water dispersion liquid contains 0.1 wt% of carbon nanotubes, 0.1 wt% of silver nanowire, 0.1 wt% of HPMC, 0.6 wt% of photosensitive polyvinyl alcohol as a water-soluble photosensitive material, and 0.01 wt% of a polyethyleneimine binder, The remainder is water so that the amount is 100 wt%.

The carbon nanotube / silver nanowire water dispersion was coated on a PET film by a bar coating method, and the coated substrate was dried at a temperature of 130 ° C for 1 minute. The sheet resistance value of the dried photosensitive thin film was high (not less than 10 MΩ / sq) so as not to be measured by the sheet resistance meter. The photosensitive thin film was irradiated with ultraviolet rays for 3 seconds in a specific pattern form using a chromium photomask and subjected to subsequent heat treatment at 130 캜 for 5 minutes. Then, the coated conductive film according to the first embodiment formed on the substrate can be obtained by washing with water as a solvent and drying.

The exposed regions of the coated conductive film according to the third embodiment were formed by straight lines having various line widths as shown in Fig. 8, and the insulating properties according to the exposure line width were examined.

As a result, the ultraviolet exposure line is formed of a transparent conductive film that is visible with a slight translucent line, but the translucent line of the exposure line is not visible when another polymer material is overcoated thereon or another film is laminated thereon.

The resistance values of the first to fourth exposure lines 41, 42, 43 and 44 were all 10 MΩ / sq or more, and the insulation of the exposure line was high enough that the resistance measurement by the resistance measuring device was impossible. The resistance value of the fifth exposure line 45 was 30 to 50 kΩ, and the resistance value of the sixth exposure line 46 was measured to be 3 kΩ.

The regions A, B, C, D, E, F, and G are regions that have a high electrical conductivity to a region where the photosensitive material is removed by washing into each unexposed region. In this region, the sheet resistance value was 110 ~ 140? / Sq, the light transmittance was 89%, and the haze was 1.3.

In order to examine the surface morphology of the portion irradiated with the ultraviolet ray and the portion irradiated with the ultraviolet ray, the exposed region and the non-exposed region were observed with an electron microscope, as shown in Figs. 12 and 13.

As a result of the analysis, in the ultraviolet ray exposure area area 12 (a), (b) and the ultraviolet ray unexposed area area 13, there was almost no difference in the distribution of silver nano wires, It was found that there was almost no damage.

However, in the enlarged electron microscope images (b) and (d), in the ultraviolet exposure line region (b), the silver nano wire is covered by the photosensitive material and the binder as compared with the ultraviolet non- The characteristics are not good and the resistance is increased. (B) and (d), which are not visible in the electron microscope image due to the very small particle size of the carbon nanotubes, but in the enlarged unexposed areas. (b), carbon nanotubes can be identified in some areas although they are not clearly seen due to photosensitive materials and other compositions.

B, C, D and E after exposing the conductive substrate according to the third embodiment to ultraviolet rays of the same condition for 5 seconds to confirm that there is no damage to the silver nano wire itself due to ultraviolet exposure. , F, and G, respectively. The sheet resistances of the regions A, B, C, D, E, F, and G before UV exposure were measured to be 110-140? / Sq, with a light transmittance of 89% and a haze of 1.3. The sheet resistivity of the regions A, B, C, D, E, F and G after UV 5 sec exposure was 110 ~ 135? / Sq, the light transmittance was 89% and the haze was 1.3. It can be confirmed that there is almost no deterioration.

In order to confirm the insulation stability of the exposed area, the coated conductive film according to the third embodiment of the form as shown in Fig. 8 was stored in a 130 degree oven for 1 hour, and AB resistance, BC resistance, CD resistance, DE resistance , EF resistance, and FG resistance were measured. As a result, the resistances of A-B, B-C and C-D resistors exceeded 10 MΩ / sq, but resistance of D-E resistors of 10 kΩ, E-F resistance and F-G resistance decreased to 3 kΩ or less. That is, it is judged that the insulating property is partially deteriorated due to the electrical connection by rearranging the photosensitive material and the conductive nanomaterial in the exposed region in the 130 ° heat treatment process.

Fourth Embodiment

In the fourth embodiment, the substrate is coated with a coating solution containing nanoparticles of silicon dioxide nanoparticles having a particle size of 30 to 50 nm, in addition to the carbon nanotube / silver nanowire aqueous dispersion, the photosensitive polyvinyl alcohol and the polyethylene imine binder as water-soluble photosensitive materials The same pattern was formed. At this time, the coating liquid contains 0.1 wt% of carbon nanotubes, 0.1 wt% of silver nanowire, 0.1 wt% of silicon dioxide nanoparticles, 0.1 wt% of HPMC, 0.6 wt% of photosensitive polyvinyl alcohol as a water-soluble photosensitive material, and 0.01 wt% of a polyethyleneimine binder , And the remainder is water so that the total amount is 100% by weight.

8, the AB resistance, the BC resistance, the CD resistance, and the DE resistance were all higher than 10 MΩ / sq, and the insulation of the exposure line region was high enough to make resistance measurement impossible with the resistance measuring instrument. The EF resistance was 36 kΩ, The FG resistance was measured at a resistance of 3kΩ. 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 1.7.

 In order to confirm the insulation stability at a high temperature, the coated conductive film according to the fourth embodiment as shown in Fig. 8 was stored in a 130 degree oven for 1 hour, and AB resistance, BC resistance, CD resistance, DE resistance , EF resistance, and FG resistance were measured. As a result, AB resistance, BC resistance, CD resistance, and DE resistance were more than 10MΩ / sq, and the resistance was more than the measurement range of the resistance measuring device. EF resistance was 30~50 kΩ and FG resistance was 4kΩ. You can see that there is no.

As described above, since the coated conductive film according to the fourth embodiment includes the silicon dioxide nanoparticles, it can be confirmed that the insulation stability is improved as compared with the exposed region not containing the silicon dioxide nanoparticles.

It should be noted that the embodiments disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

10: substrate
20: Coated conductive film
21: Conductive nanomaterials
23: Photosensitive thin film
25: exposed area
27: unexposed area
29: wiring pattern
30: Mask
31: pattern hole
100: conductive substrate

Claims (8)

0.01 to 5% by weight of a conductive nanomaterial forming a conductive network, 0.01 to 0.5% by weight of nanoparticles having a low electrical conductivity or an aspect ratio of a low particle relative to the conductive nanomaterial, 0.01 to 3% by weight of a photosensitive material and 1% Solids, and water as the remainder,
The conductive nanomaterial is a metal nanowire or a carbon nanotube,
Wherein the nanoparticles comprise oxide nanowires, oxide nanoparticles, metal nanoparticles, or carbon nanoparticles. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
The oxide nanowire has a diameter of 10 nm to 1 占 퐉, a length of 1 占 퐉 to 100 占 퐉,
The oxide nanoparticles, metal nanoparticles and carbon nanoparticles are spherical, cubic or amorphous nanoparticles having a particle size of 5 nm to 30 μm,
The oxide nanowires are metal oxide nanowires or non-metal oxide nanowires,
Wherein the oxide nanoparticles are metal oxide nanoparticles or non-metal oxide nanoparticles. The method according to claim 1,
The photosensitive material is polyvinyl alcohol having a photosensitive functional group of N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal,
Wherein the binder is a water-dispersible polyurethane or a cationic polymer electrolyte. A coated conductive film for a transparent electrode formed on a substrate,
Wherein the conductive nanomaterial is a metal nanowire or a carbon nanotube, the conductive nanomaterial is a metal nanowire or a carbon nanotube, the conductive nanomaterial is a conductive nanomaterial, The nanoparticles include oxide nanowires, oxide nanoparticles, metal nanoparticles, or carbon nanoparticles,
Wherein the exposed and unexposed areas are formed by exposure and cleaning, and the unexposed area has an electrical conductivity two times or more that of the exposed area. 5. The method of claim 4,
The oxide nanowire has a diameter of 10 nm to 1 占 퐉, a length of 1 占 퐉 to 100 占 퐉,
The oxide nanoparticles, metal nanoparticles and carbon nanoparticles are spherical, cubic or amorphous nanoparticles having a particle size of 5 nm to 30 μm,
The oxide nanowires are metal oxide nanowires or non-metal oxide nanowires,
Wherein the oxide nanoparticles are metal oxide nanoparticles or non-metal oxide nanoparticles. 5. The method of claim 4,
The photosensitive material is polyvinyl alcohol having a photosensitive functional group of N-methyl-4 (4'-formylstyryl) pyridinium methosulfate acetal,
Wherein the binder is a water-dispersible polyurethane or a cationic polymer electrolyte. 5. The method of claim 4,
Wherein the non-exposed region is further removed in the cleaning process to have a lower residue content than the exposed region. 5. The method of claim 4,
Wherein the exposed region is impregnated with the photosensitive nanomaterial and the nanoparticles more than the non-exposed region.

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