KR102005262B1 - Manufacturing method of patterned flexible transparent electrode - Google Patents

Abstract

The present invention relates to a method of forming a flexible transparent electrode in which a pattern is formed without introducing a lithographic apparatus by introducing a surface treatment process in the process of manufacturing a flexible transparent electrode, and is remarkably superior to a flexible transparent electrode manufacturing process in which patterning is performed through a lithography process We propose a method to fabricate flexible transparent electrodes with embedded metal nano wires patterned with low process water and process cost.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a flexible transparent electrode,

The present invention relates to a method of forming a flexible transparent electrode in which a pattern is formed without introducing a lithographic apparatus by introducing a surface treatment process in the process of manufacturing a flexible transparent electrode, and is remarkably superior to a flexible transparent electrode manufacturing process in which patterning is performed through a lithography process We propose a method to fabricate flexible transparent electrodes with embedded metal nano wires patterned with low process water and process cost.

Generally, a transparent transparent electrode can be prepared by coating a metal nanowire on a flexible substrate or by coating a metal nanowire on a substrate having a sacrificial layer and separating it with a polymer. The metal nano wire embedded flexible electrode, which is formed by coating the metal nanowire on the sacrificial layer and removing it, has a low possibility of occurrence of short circuit when the electronic device is applied due to low surface roughness,

In order to apply a flexible transparent electrode based on a metal nanowire to an electronic device, a patterning process is indispensable and is mainly performed by using a photolithography method. That is, a photoresist is coated on a flexible transparent electrode based on a metal nanowire, and light is irradiated using an exposure apparatus, and then a pattern can be formed through development and etching processes. However, in the case of the photolithography process, additional materials such as photoresist are required, and the process equipment is expensive, raising a problem of raising the process cost.

In order to solve the problem of process unit cost of photolithography, several studies have been made to pattern metal nanowire-based flexible transparent electrodes by methods other than photolithography. In other words, a method of forming a pattern by selectively etching metal nanowires using laser equipment has been proposed. A method of selectively transferring metal nanowires on a flexible substrate using microcontact printing, a method of forming a metal nanowire seed on a substrate And a method of fabricating a flexible transparent electrode based on a metal nanowire in which a pattern is formed by selectively forming the metal nanowire. In addition, a method of patterning metal nanowires on a substrate using inkjet printing or gravure offset printing equipment has been proposed. When a curable polymer is coated thereon and cured, a flexible transparent electrode having embedded patterns of metal nanowires can be manufactured have.

However, since all of the above methods require expensive patterning equipment and complicated processes, it is impossible to completely eliminate the problems of photolithography, and a new patterning technology capable of securing cost competitiveness, in particular, a metal nanowire embedded flexible It is necessary to develop a new patterning technique suitable for a transparent electrode.

That is, since the flexible transparent electrode having the embedded metal nano wire has a smooth surface, it exhibits superior performance to the transparent electrode coated with the metal nanowire on the flexible substrate when the electronic device is applied. However, there is little research to improve the fabrication process of metal nanowire embedding type transparent electrode, and it is a simple modification step of metal nanowire electrode patterning technique coated on flexible substrate. In other words, as shown in the following patents, metal nanowires are patterned by using expensive equipment, and polymer is coated and cured thereon to form a patterned metal nanowire embedding type flexible transparent electrode.

Accordingly, the present applicant has provided a method for manufacturing a flexible transparent electrode in which a pattern is formed without a separate lithography process in Korean Registered No. 10-1685069 and Korean Registered No. 10-1705583. The above patents provide a novel manufacturing method of a flexible transparent electrode patterned by a relatively simple method by forming a pattern so that the adhesion of the substrate is improved through surface treatment on the substrate having low adhesion to the metal nanowire so that the metal nanowire does not fall off the substrate Could.

Korean Registration No. 10-1685069 (December 5, 2016) Korean Registration No. 10-1705583 (Feb.

It is an object of the present invention to provide a novel method of manufacturing a patterned flexible transparent electrode. More specifically, the present invention aims to provide a new method for manufacturing a patterned flexible transparent electrode in which the manufacturing steps are further simplified by applying metal nanowires to the substrate itself without having to form a separate release layer on the substrate. Another object of the present invention is to provide a novel method for manufacturing a flexible transparent electrode that does not require a separate hydrophilic treatment on the release layer.

The inventors of the present invention have confirmed that when a substrate having a specific surface energy is used, the adhesion between the substrate and the metal nanowire is excellent even without forming a separate release layer, thereby completing the present invention.

That is, according to the present invention, since adhesion between a conventional substrate and a metal nanowire is low, plasma or ultraviolet-ozone treatment is performed on the substrate to control the adhesion force between the metal nanowire and the substrate, The adhesion of the metal nanowires to the metal nanowires is high without any special treatment, and the metal nanowires can be present on the substrate even after the curable polymer resin is applied and cured. Accordingly, the present invention provides a novel manufacturing method for improving adhesion between a curable polymer resin and a metal nanowire by surface-treating the metal nanowire, thereby separating the metal nanowire impregnated in the curable polymer resin from the substrate I want to.

According to an aspect of the present invention, there is provided a method of manufacturing a metal nanowire including: a) forming a metal nanowire coating layer by coating a metal nanowire solution on a substrate having a surface energy of 35 to 60 mJ / m 2;

b) hydrophilizing a part of the metal nanowire coating layer;

c) applying and curing a curable polymer resin on the metal nanowire coating layer to produce a polymer film having the metal nanowire coating layer embedded therein; And

d) separating the polymer film embedded with the metal nanowire coating layer from the substrate to obtain a flexible transparent electrode having a patterned metal nanowire layer;

The present invention relates to a method of manufacturing a flexible transparent electrode in which a pattern is formed.

In one embodiment of the method of the present invention, the adhesion between the substrate of step a) and the nanowire coating layer may be 110 to 160 mN / m.

In one embodiment of the production method of the present invention, in the step b), the hydrophilizing treatment may be plasma, ultraviolet-ozone, electron beam or ion beam treatment.

In one embodiment of the production method of the present invention, the plasma or ion beam treatment may be one using one or more gases selected from the group consisting of O ₂ , H ₂ , N ₂ and Ar.

In one embodiment of the production method of the present invention, in the hydrophilization treatment in the step b), the substrate A and the nanowire coating layer B in the step a) and the hydrophilicized nanowire coating layer C ) And the curable polymer resin (D) satisfy the following formulas (1) and (2).

Adhesion between A and B> Adhesion between B and D (Equation 1)

Adhesion between A and C <Adhesion between C and D (Equation 2)

In one embodiment of the production method of the present invention, in the step b), the mask may be placed in the hydrophilization treatment and the hydrophilization treatment may be performed to hydrophilize the maskless portion.

In one embodiment of the manufacturing method of the present invention, the metal nanowire is formed of a metal such as Ag, Cu, Al, Au, Pt, Ni, Ti, May be selected from alloys thereof, have a diameter of 10 to 50 nm, a length of 10 to 50 nm, and an aspect ratio of 500 to 800.

In an embodiment of the manufacturing method of the present invention, the metal nanowire solution may include a metal nanowire, a hydrophilic polymer binder, and a polar quantum solvent.

In one embodiment of the production process of the present invention, the application may be selected from spin coating, bar coating, roll to roll coating.

In one embodiment of the method of the present invention, the metal nanowire coating layer in the step a) may have a surface energy of 110 to 200 mJ / m 2.

The present invention can provide a new manufacturing method in which the process is shortened because it is not necessary to form a separate release layer.

In addition, the present invention can produce a flexible transparent electrode having a pattern formed by a simple process as compared with a conventional method using photolithography.

In addition, the present invention is advantageous in that it does not require expensive equipment, is simple in process, and easily adjusts the line width of the pattern, compared with a method of forming patterns by gravure offset, gravure printing, inkjet prining and the like.

The flexible transparent electrode manufactured by the manufacturing method of the present invention is less likely to cause a short circuit when applied to an electronic material because the metal nanowire is embedded in the polymer resin and the surface is smooth, and it can be applied to various electronic devices such as OLED and solar cell Do.

1 is a schematic view showing a manufacturing method of the present invention.
2 is an optical microscope photograph of a transparent electrode prepared according to Example 1. Fig.
3 is an optical microscope photograph of the substrate prepared according to Example 1. Fig.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described more fully hereinafter with reference to the accompanying drawings, It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

One aspect of the present invention is

a) applying a metal nanowire solution on a substrate having a surface energy of 35 to 60 mJ / m &lt; 2 &gt; to form a metal nanowire coating layer;

b) hydrophilizing a part of the metal nanowire coating layer;

c) applying and curing a curable polymer resin on the metal nanowire coating layer to produce a polymer film having the metal nanowire coating layer embedded therein; And

d) separating the polymer film embedded with the metal nanowire coating layer from the substrate to obtain a flexible transparent electrode having a patterned metal nanowire layer;

.

1, a substrate 10 having a surface energy of 35 to 60 mJ / m 2 is prepared (S1), and the substrate 10 A metal nanowire solution is applied to the substrate to form a metal nanowire coating layer 20 (S2). Thereafter, a mask 30 having a pattern formed on the metal nanowire coating layer 20 is raised and hydrophilized (S3) to form a metal nanowire coating layer 20 having a partially hydrophilized (40) step S4 ). Thereafter, a polymer film 50 in which the metal nanowire coating layer is embedded is coated (S5) by applying and curing a curable polymer resin on the metal nanowire coating layer 20, and the hydrophilicized metal nanowire coating layer The embedded polymer film 50 is separated to obtain a flexible transparent electrode having a patterned metal nanowire layer (S6).

Specifically, each step is characterized in that the step a) is characterized in using a substrate having excellent adhesion to the metal nanowire coating layer.

The inventors of the present invention have confirmed that the adhesion between the metal nanowire and the coating layer is excellent without forming a separate release layer in the range of surface energy of the substrate of 35 to 60 mJ / m 2. When the surface energy of the substrate is less than 35 mJ / m 2, the adhesion between the substrate and the metal nanowire coating layer is weak, so that a portion not subjected to the surface treatment is also separated and no pattern is formed. When the surface energy exceeds 60 mJ / The adhesion between the metal nanowire coating layers was so strong that the metal nanowires were not separated from the substrate and thus the pattern was not formed.

The type of the substrate is not limited, but it may be made of a polymer material, or may be a polymer substrate having a separate surface treatment.

Specifically, the substrate may be a polymer substrate made of an acrylic resin, a polyester resin, or the like, and more specifically, it may be a sheet or a film made of a polyethylene terephthalate resin, but is not limited thereto. The thickness of the substrate is not limited, but may be 10 to 1000 탆, more preferably 100 to 800 탆, but is not limited thereto.

The metal nanowire solution may include a metal nanowire, a hydrophilic polymer binder, and a polar quantum solvent.

In one embodiment of the present invention, the metal nanowire is made of a metal such as silver (Ag), copper (Cu), aluminum (Al), gold (Au), platinum (Pt), nickel (Ni), titanium And may be one or a mixture of two or more, but is not limited thereto.

In one aspect of the present invention, as the density of the metal nanowires decreases, the transmittance increases, but the electrical conductivity decreases. Therefore, it is preferable to select the density, length and diameter of the metal nanowires considering the permeability and the sheet resistance depending on the purpose of use . More specifically, the metal nanowires may have a diameter of 10 to 50 nm, a length of 10 to 50 nm, and an aspect ratio of 500 to 800, but are not limited thereto.

In one embodiment of the present invention, the content of the metal nanowires in the metal nanowire solution may be 0.1 to 1.0 wt%, more preferably 0.2 to 0.5 wt%, but is not limited thereto.

In one embodiment of the present invention, the hydrophilic polymeric binder is easy to disperse metal nanowires using a polymeric binder containing a hydroxy group, and is easily applied to a substrate to form a thin film. After the hydrophilic polymeric binder is cured, So that it is easy to produce a polymer film in which the metal nanowire coating layer is embedded. As the non-limiting examples of the polymer binder including the hydroxy group, a polymer polyol or a polysaccharide polymer may be used. More specifically, the polymer polyol may have a weight average molecular weight of 1000 to 500,000. The polysaccharide polymer may include a cellulose-based polymer or a chitosan-based polymer.

The content of the hydrophilic polymer binder in the metal nanowire solution may be 0.05 to 5% by weight, more preferably 0.1 to 4% by weight. The thickness of the metal nanowire coating layer is preferably in the range of no.

In one embodiment of the invention, the polar protic solvent is selected from, for example, water, ethanol, methanol, isopropyl alcohol, butyl alcohol, ethylene glycol, propylene glycol, diacetone alcohol, methoxyethanol, methoxypropanol, And may be any one or a mixture of two or more, but is not limited thereto.

In one embodiment of the present invention, the application of the metal nanowire solution may be performed by a method such as spin coating, bar coating, roll to roll coating, doctor blade, slot die coating, and the like, but is not limited thereto.

In one embodiment of the present invention, the thickness of the metal nanowire coating layer is not limited, but may be 25 to 90 nm, more preferably 70 to 40 nm.

More specifically, the metal nanowire solution is spin-coated by spin coating at 500 to 3000 rpm for 30 seconds to 10 minutes, and heat-treated at 80 to 110 ° C for 30 seconds to 5 minutes to form a metal nanowire coating layer . At this time, when the metal nanowire solution is slowly applied, it may remain unevenness, so it is preferable to uniformly apply the coating solution by controlling the application time and the spin coating speed. In addition, since the density of the metal nanowires may vary depending on the application speed during spin coating, it is preferable to adjust the spin coating speed so that the density of the metal nanowires can be adjusted according to the application of the transparent electrode. The method of coating the metal nanowires is not limited to spin coating, and various techniques such as bar coating, doctor blade, and slot die coating techniques can be applied.

The metal nanowire coating layer may have a surface energy of 110 to 200 mJ / m 2. The metal nanowire coating layer has an excellent adhesion with the substrate in the above range, and the adhesion to the curable polymer resin can be improved by hydrophilizing treatment.

In the step a), the adhesion between the substrate and the nanowire coating layer may be 110 to 160 mN / m. The adhesion between the substrate and the nanowire coating layer in the above range is excellent and can be maintained without being impregnated in the curable polymer resin to be coated thereafter.

Next, in step b), hydrophilic treatment is performed on a portion of the metal nanowire layer, and a mask having a pattern is formed on the metal nanowire layer, and plasma, ultraviolet-ozone, electron beam, or ion beam treatment is performed, The hydrophilic portion is hydrophilized.

In one aspect of the present invention, the mask is used for forming a metal nanowire pattern, and the mask is formed in a pattern shape to be formed on the transparent electrode. The material of the mask may be, for example, a siloxane-based polymer, a silicone rubber, or a metal material, but not limited thereto, and any mask used for the plasma treatment or ultraviolet-ozone treatment may be used without limitation. More specifically, the siloxane-based polymer may be a polydimethylsiloxane (PDMS) from the viewpoint of preventing the plasma from penetrating through the strong contact with the release layer, but the present invention is not limited thereto. In addition, from the viewpoint of forming a fine pattern, it may be a metal, and the kind of the metal is not limited.

The mask may be adhered to the release layer or the hydrophobic polymer substrate, or may be spaced apart from the release layer or the hydrophobic polymer substrate.

Preferably, the mask is more closely adhered to the metal nanowire coating layer so that an accurate pattern is formed. To this end, a metal mask may be used and an alignment may be used to fix the metal mask. More specifically, a magnet, a magnet, and a jig may be provided to fix the metal mask to form a fine pattern of a desired size at a desired position to improve reliability.

Hydrophilic functional groups such as a hydroxyl group (-OH) are formed on the surface of the metal nanowire coating layer by placing a mask on the metal nanowire coating layer and performing plasma or ultraviolet-ozone, electron beam, or ion beam treatment, It may chemically react with the functional group to remain on the substrate and to secure the adhesive force to the curable polymer resin and peel off from the substrate.

At this time, the portion not subjected to the hydrophilic treatment has a sufficient adhesive force with the substrate, and the adhesive force with the substrate is higher than the adhesive force with the photo-curable polymer, so that it can be maintained without being peeled off from the substrate.

In one embodiment of the present invention, the plasma treatment may be one using one or more gases selected from the group consisting of O ₂ , H ₂ , N ₂ and Ar, and may be a method of forming a hydroxy group in the metal nanowire layer Anything that can be done is not limited. More specifically, for example, the plasma treatment may be performed at a pressure of 2.0 x 10 ^-1 to 8.0 x 10 ^-1 Torr, an RF power of 20 to 50 W using an O ₂ gas of 5 to 20 sccm For 5 to 30 minutes. More specifically, the treatment may be performed at a pressure of 3.9 x 10 ^-1 to 4.2 x 10 ^-1 Torr and an RF power of 20 to 30 W for 5 to 30 minutes using a gas of 8 to 15 sccm. By enhancing the adhesion strength with the metal nanowires in the above range, it is possible to have a stronger adhesion force than the adhesion strength between the metal nanowires and the curable polymer resin.

In addition, ultraviolet-ozone treatment is a method of cutting the main chain of a polymer by ozone generated by ultraviolet ray and ultraviolet ray irradiation and forming a surface oxidation layer. It is possible to change the surface energy of a metal nanowire coating layer or form a functional group The adhesive strength to the curable polymer resin can be further improved. Specifically, for example, a mercury lamp having a main wavelength of 200 to 280 nm, which is a UV-C region, is irradiated with ultraviolet rays / ozone irradiator having an output of 100 to 200 mW / cm ² for 5 minutes or more, more specifically 5 Min to 60 min.

The ion beam treatment may be one using one or more gases selected from the group consisting of O ₂ , H ₂ , N ₂ and Ar.

In one aspect of the present invention, in the hydrophilization treatment in step b), the substrate (A) and the nanowire coating layer (B) in step a) and the hydrophilized nanowire coating layer (c) The adhesive strength of the polymeric resin (D) may be in a range satisfying the following formulas (1) and (2).

Adhesion between A and B> Adhesion between B and D (Equation 1)

Adhesion between A and C <Adhesion between C and D (Equation 2)

Next, in the step c), a curable polymer resin is coated on the metal nanowire coating layer and cured to produce a polymer film having the metal nanowires embedded therein. In the step c), a polymer film is prepared using a curable polymer resin having excellent compatibility with metal nanowires to impregnate the metal nanowires so as to lower the surface roughness of the metal nanowires. Thus, So that the wire coating layer is impregnated to form a smooth surface.

Since the metal nanowire coating layer in the portion where the mask is located in step b) is more adhesive and compatible with the substrate, it remains on the substrate in the process of applying the curable polymer resin, and is not hydrophilized Part is improved in adhesion to the curable polymer resin, and the metal nanowires are embedded.

In one embodiment of the present invention, the curable polymer resin is preferably a resin having flexibility and a resin that is incompatible with the substrate. That is, a resin that is easy to release from the substrate after curing can be used.

From the viewpoint of forming a transparent electrode, it is more preferable that the total light transmittance is 80 to 99%, but it is not limited thereto.

From the viewpoint of heat treatment stability that can be introduced in the production of an electronic device, the glass transition temperature is more preferably 100 to 150 ° C, but is not limited thereto.

In addition, in view of the application of the flexible device, the elastic modulus of the curable polymer is preferably 1 to 2,000 MPa, but is not limited thereto.

In one embodiment of the present invention, the curable polymer resin may be an ultraviolet curable polymer resin, a thermosetting polymer resin, a room temperature moisture curing polymer resin, an infrared curing polymer resin, or the like, but is not limited thereto.

In one embodiment of the present invention, the curable polymer resin is preferably a liquid in order to smoothly form a surface layer by embedding the metal nanowire coating layer. In the liquid phase, the polymer resin is dissolved in water or a solvent, Lt; / RTI &gt;

In one embodiment of the present invention, the curable polymer resin may be one that uses an ultraviolet curable polymer in order to prevent the physical properties of the metal nanowire from deteriorating and form a polymer film having excellent transmittance. The ultraviolet curable polymer is not limited as long as it is a resin which is cured to complete solid when it is exposed to ultraviolet light of 280 to 350 nm, and it is more preferably a transparent colorless liquid. In this respect, Norland Optical Adhesive series from Norland Products can be used as an example of commercialization from this viewpoint. Specifically, for example, NOA60, NOA61, NOA63, NOA65, NOA68, NOA68T, NOA71, NOA72, NOA73, NOA74, NOA75, NOA76 and NOA78 , NOA81, NOA83H, NOA84, NOA85, NOA85V, NOA86, NOA86H, NOA87, NOA88, NOA89, and the like.

In one embodiment of the present invention, the thickness of the polymer film formed by applying the curable polymer resin is not limited, but may be 50 to 2,000 m, more preferably 100 to 300 m. The metal nanowires are embedded in the surface in the above-mentioned range, and a polymer film having a smooth surface can be formed.

Next, in step (d), a flexible transparent electrode having a patterned metal nanowire layer is prepared by separating the polymer film embedded with the metal nanowires.

At this time, as described above, adhesion strength between the metal nanowire coating layer and the curable polymer is significantly improved in the portion where the mask is not placed by plasma, ultraviolet-ozone, electron beam, or ion beam treatment, The metal nanowires except for the metal nanowires are separated in a buried state, thereby forming a pattern. That is, the pattern of the metal nanowire coating layer is determined according to the pattern of the mask.

In addition, the polymer film can be easily separated by applying a physical force, that is, by using a finger or a cotton swab.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The following physical properties were measured as follows.

1. Surface energy

Surface energy was calculated using the contact angle measured with the Phoenix 300 from SEO. The solvent used for the contact angle measurement was measured using water (Tension 72.8 / Polar 50.3, Dispersive 22.5) and glycerol (Tension 63.4 / Polar 26.4, Dispersive 37). The substrate to be measured was prepared, and the surface contact angle measured after dropping 6 용액 of the solution on the substrate was recorded. Surface energy was calculated using the measured surface contact angle and the Owens-Wendt Geometric Mean equation.

θ: contact angle of liquid

γ _LV : surface tension of the liquid

γ _S ^D : surface energy of the dispersive component of the solid

γ _L ^D : surface energy of the dispersive component of the liquid

γ _S ^P : Surface energy of the polar component of a solid

γ _L ^P : surface energy of polar component of liquid

2. Adhesion

The adhesion between the substrate and the nanowire was calculated using the obtained surface energy and work of adhesion equation.

W _1,2 : Adhesion between objects 1 and ₂

γ ₁ ^D : surface energy of the dispersive component of object 1

γ ₂ ^D : surface energy of the dispersive component of the object 2

γ ₁ ^P : Surface energy of the polar component of object 1

γ ₂ ^P : surface energy of the polar component of object 2

[Example 1]

A polyethylene terephthalate film (PET film) was prepared in a size of 25 mm x 25 mm and used as a substrate. The surface contact angle of the substrate was 64.99 °, the contact angle of glycerol was 65.48 °, and the calculated surface energy was 37.37 mJ / ㎡ (polar 29.68, dispersive 7.69).

The entire surface of the prepared PET substrate was coated with a silver nanowire transparent electrode coating solution (0.3 wt% AgNW coating solution, C3Nano Korea) at a speed of 600 rpm for 1 minute using a spin coater. The coated silver nanowires were heat treated at 100 ° C for 1 minute to evaporate the solvent. The silver nanowire coating layer had a water contact angle of 34 °, a glycerol contact angle of 73.77 °, a surface energy of 136.70 mJ / m 2 (polar 128.29, dispersive 8.05) silver nanowire coating layer was formed. The adhesion between the silver nanowire coating layer and the substrate was calculated to be 112.14 mN / m.

A mask having a pattern shape is disposed on the silver nanowire-coated PET substrate. In the case of the mask, the substrate was brought into close contact with the substrate so as not to cause an error in the surface treatment (hydrophilization treatment) region, and then ozone treatment was performed for 30 minutes in an ultraviolet lamp having a wavelength of 254 nm.

1 g of a photocurable polymer (NOA 63, Norland Products Inc, USA) was coated on the silver nanowire coating layer having been subjected to the surface hydrophilization treatment and spin-coated at 500 rpm for 1 minute in the absence of bubbles. The spin-coated sample was cured for 30 minutes using a polymer hardener having a wavelength of 365 nm.

The completely cured polymer film was separated from the substrate in the above-completed sample, and the unexposed silver nanowire coating layer remained on the substrate without being peeled off (see FIG. 3). The surface treated area was impregnated with the photocurable polymer (See Fig. 2).

[Example 2]

In Example 1, the PET substrate had a water contact angle of 57.65 deg., A glycerol contact angle of 56.1 deg., And a calculated surface energy of 43.00 mJ / m2 (polar 31.69, dispersive 11.31) . The nanowire coating layer had a water contact angle of 33.68 °, a glycerol contact angle of 73.22 °, and a surface energy of 135.40 mJ / m 2 (polar 127.45, dispersive 7.95). The adhesion between the silver nanowire coating layer and the substrate was 120.19 mN / m .

As a result, it was confirmed that the silver nanowire coating layer which had not been subjected to the surface treatment remained without being peeled off from the substrate, and that the surface treated region was impregnated with the photocurable polymer.

[Example 3]

In Example 1, the same procedure as in Example 1 was carried out except that the PET substrate had a water contact angle of 59.79 °, a glycerol contact angle of 65.68 °, and a surface energy of 44.98 mJ / m 2 (polar 41.24, dispersive 3.74) . The silver nanowire coating layer had a water contact angle of 34.21 °, a glycerol contact angle of 75.55 ° and a surface energy of 143.71 mJ / m 2 (polar 133.22, dispersive 10.48). The adhesion between the silver nanowire coating layer and the substrate was found to be 136.99 mN / m .

As a result, it was confirmed that the silver nanowire coating layer which had not been subjected to the surface treatment remained without being peeled off from the substrate, and that the surface treated region was impregnated with the photocurable polymer.

[Example 4]

In Example 1, the same procedure as in Example 1 was carried out except that the PET substrate had a water contact angle of 64.06 °, a glycerol contact angle of 66.93 °, and a surface energy of 39.23 mJ / m 2 (polar 33.71, dispersive 5.52) . The silver nanowire coating layer had a water contact angle of 35.75 °, a glycerol contact angle of 73.81 ° and a surface energy of 131.26 mJ / m 2 (polar 123.78, dispersive 8.76). The adhesion between the silver nanowire coating layer and the substrate was 118.67 mN / m .

As a result, it was confirmed that the silver nanowire coating layer which had not been subjected to the surface treatment remained without being peeled off from the substrate, and that the surface treated region was impregnated with the photocurable polymer.

[Comparative Example 1]

In Example 1, the PET substrate had a water contact angle of 75.16 °, a glycerol contact angle of 73.02 °, and a surface energy of 28.72 mJ / m 2 (polar 19.96, dispersive 8.76). The contact angle of the nanowire coating layer was 34.27 °, the contact angle of glycerol was 75.34 °, the surface energy was 142.58 mJ / m 2 (polar 132.41, dispersive 10.17), and the adhesion between the silver nanowire coating layer and the substrate was 88.19 mN / m .

As a result, it was confirmed that the silver nanowire coating layer which had not been subjected to the surface treatment was separated from the substrate and no pattern was formed.

[Comparative Example 2]

In Example 1, the glass substrate used had a water contact angle of 17.97 °, a glycerol contact angle of 28.5 °, and a surface energy of 72.84 mJ / m 2 (polar 63.46, dispersive 9.38). The nanowire coating layer had a water contact angle of 37.78 °, a glycerol contact angle of 72.73 °, and a surface energy of 120.47 mJ / m 2 (polar 115.16, dispersive 5.317). The adhesion between the silver nanowire coating layer and the substrate was 177.23 mN / m .

As a result, it was confirmed that the patterned silver nanowire coating layer was not separated from the substrate and thus no pattern was formed.

Claims (10)

a) applying a metal nanowire solution on a substrate having a surface energy of 35 to 60 mJ / m &lt; 2 &gt; to form a metal nanowire coating layer;
b) placing a mask on the metal nanowire coating layer and performing hydrophilization treatment to hydrophilize the portion without the mask;
c) applying and curing a curable polymer resin on the metal nanowire coating layer to produce a polymer film having a hydrophilicized portion of the metal nanowire coating layer embedded therein; And
d) separating the polymer film embedded with the metal nanowire coating layer from the substrate to obtain a flexible transparent electrode having a patterned metal nanowire layer;
Wherein a pattern is formed on the flexible transparent electrode. The method according to claim 1,
Wherein the adhesion between the substrate and the nanowire coating layer in the step a) is 110 to 160 mN / m. The method according to claim 1,
Wherein the hydrophilization treatment is plasma, ultraviolet-ozone, electron beam or ion beam treatment in the step b). The method of claim 3,
Wherein the plasma or ion beam treatment uses one or more gases selected from the group consisting of O ₂ , H ₂ , N ₂ and Ar. The method according to claim 1,
In the hydrophilization treatment in the step b), the adhesion between the substrate A and the nanowire coating layer B in step a) and the hydrophilicized nanowire coating layer C and the curable polymer resin D in step c) Wherein the pattern satisfies the following formulas (1) and (2): &quot; (1) &quot;
Adhesion between AB> Adhesion between BD (Equation 1)
AC Adhesion <CD adhesion (Equation 2) delete The method according to claim 1,
Wherein the metal nanowire is selected from silver (Ag), copper (Cu), aluminum (Al), gold (Au), platinum (Pt), nickel (Ni), titanium A length of 10 to 50 nm, and an aspect ratio of 500 to 800. The method of manufacturing a flexible transparent electrode according to claim 1, The method according to claim 1,
Wherein the metal nanowire solution comprises a metal nanowire, a hydrophilic polymer binder, and a polar quantum solvent. The method according to claim 1,
Wherein the application is selected from spin coating, bar coating, and roll to roll coating. The method according to claim 1,
Wherein the metal nanowire coating layer has a surface energy of 110 to 200 mJ / m &lt; 2 &gt; in the step a).

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