KR20220085645A - Flexible transparent conductive film, transparent electrode and transparent infrared radiation-cutting film comprising the same - Google Patents

Abstract

The present invention relates to a flexible transparent conductive film and a display and a heating sheet including the same, wherein the flexible transparent conductive film includes a polymer substrate; a first nano-thin film layer disposed on one surface of the polymer substrate and containing a first metal compound having a refractive index of 1.7 or more; disposed on the first nano-thin film layer, (i) a first metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) the first metal a second nano-thin film layer containing an oxide of or a nitride of the first metal; and a third nano-thin film layer disposed on the second nano-thin film layer and containing silver (Ag)-containing metal.

Description

Flexible transparent conductive film and transparent electrode and transparent heat shielding film including same

The present invention relates to a flexible transparent conductive film, a transparent electrode and a transparent heat shield film comprising the same, and a display including the transparent electrode and/or a transparent heat shield film, and specifically, high thermal barrier properties, high transmittance, surface ultra-low reflectivity, It relates to a flexible transparent conductive film having flexibility and low resistance properties, a transparent electrode and a transparent heat shield film including the same, and a display including the transparent electrode and/or a transparent heat shield film.

Recently, as the thickness of the display becomes thinner due to the high performance and miniaturization of the display, heat generation due to the increase in the capacity and the high integration of the elements embedded in electronic products is becoming a problem. In addition, since the thickness of the bezel of the display is also reduced, it is difficult to secure a path for dissipating the heat generated by the device to the outside, and a heat dissipation sheet is applied to solve this problem. However, as the performance of the display increases, the number of functional layers such as a heat shield sheet increases, and accordingly, the thickness of the display increases and the flexibility decreases, making it difficult to develop a flexible display.

On the other hand, the flexible transparent conductive film commonly used in displays such as touch screens is ITO, which has excellent optical/electrical properties, but cannot block heat, and because rare earth elements are used, raw material supply and demand is unstable and price competitiveness is low. In addition, since a high-temperature process is required to realize the high-permeability and low-resistance performance of the ITO film, when a PET substrate with low thermal stability is used, high performance cannot be achieved by ITO alone.

In order to replace the current ITO film, research is being conducted to secure low resistance, high transmission, weather resistance, and mass productivity with various materials such as metal mesh, CNT, graphene, and silver nanowire (AgNW). In particular, a lot of research has been done on metal mesh and silver nanowires. However, since the metal mesh and silver nanowires do not have a large heat shielding effect at a thickness of several tens of nm or a problem of interference caused in their structure, they are not suitable for use in high-performance displays requiring heat shielding properties.

In addition, the conventionally known heat shielding film discolors an object or increases the blocking rate in the ultraviolet (150 to 380 nm) and near infrared (780 to 2500 nm) region, which is 53% of solar energy, and high in the visible (380 to 780 nm) region. It is designed to have transmittance. However, the conventional heat shielding film could not block the heat of the entire infrared region including far infrared rays (6-15 μm) generated in high-performance displays.

Therefore, it is necessary to develop a flexible transparent conductive film having high transmittance in the visible ray region and high thermal barrier properties in the infrared region (particularly, far-infrared region).

An object of the present invention is to provide a flexible transparent conductive film having high thermal barrier properties, high transmittance, surface ultra-low reflectivity, flexibility, and low resistance properties.

Another object of the present invention is to provide a transparent electrode having optical properties, electrical properties, thermal stability and long life characteristics, including the above-described flexible transparent conductive film, and a display including the same.

Another object of the present invention is to provide a transparent heat shielding film having excellent thermal barrier properties and optical properties, including the above-described flexible transparent conductive film, and a display including the same.

Another object of the present invention is to provide a heating sheet capable of uniformly heating, including the above-described flexible transparent conductive film.

In order to achieve the above object, the present invention is a polymer substrate; a first nano-thin film layer disposed on one surface of the polymer substrate and containing a first metal compound having a refractive index of 1.7 or more; disposed on the first nano-thin film layer, (i) a first metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) the first metal a second nano-thin film layer containing an oxide of or a nitride of the first metal; and a third nano-thin film layer disposed on the second nano-thin film layer and containing silver (Ag)-containing metal.

In addition, the present invention is disposed on the third nano-thin film layer, (i) a second metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) ) may further include a fourth nano-thin film layer containing the oxide of the second metal or the nitride of the second metal.

In addition, the present invention is disposed on the fourth nano-thin film layer, the fifth nano-thin film layer containing a second metal compound having a refractive index of 1.7 or more; and a sixth nano-thin film layer disposed on the fifth nano-thin film layer and having a refractive index of 1.6 or less, wherein the fifth nano-thin film layer and the sixth nano-thin film layer are alternately stacked once or a plurality of times, the outermost layer is It may be a sixth nano-thin film layer.

In addition, in the present invention, when the sixth nano-thin film layer contains a silicon oxide-based material, it is disposed on the sixth nano-thin film layer, and may further include an anti-fingerprint layer formed of a fluorine-based resin.

In addition, the present invention may further include a seventh nano-thin film layer disposed on the other surface of the polymer substrate and having a refractive index of 1.5 or less.

In addition, the present invention may further include an anti-glare layer interposed between the polymer substrate and the first nano-thin film layer.

In addition, the present invention provides a transparent electrode comprising the above-described flexible transparent conductive film.

In addition, the present invention provides a transparent heat shielding film comprising the above-described flexible transparent conductive film.

In addition, the present invention provides a display including at least one of the above-described transparent electrode and the transparent heat shielding film.

In addition, the present invention provides a heating sheet comprising the above-described flexible transparent conductive film.

The flexible transparent conductive film according to the present invention sequentially includes a nano-thin film layer containing a metal compound and a nano-thin film layer containing a metal and an oxide or nitride thereof between the polymer substrate and the silver-containing nano-thin film layer, thereby providing high thermal barrier properties and high thermal barrier properties. It can exhibit permeability, surface ultra-low reflectivity, flexibility, and low resistance characteristics. Accordingly, the flexible transparent conductive film of the present invention may be used as a transparent electrode of a display or a transparent heat shielding film, and may also be used as a heating sheet.

1 is a cross-sectional view schematically showing a flexible transparent conductive film according to a first embodiment of the present invention.
2 is a cross-sectional view schematically illustrating a flexible transparent conductive film according to a second embodiment of the present invention.
3 is a cross-sectional view schematically illustrating a flexible transparent conductive film according to a third embodiment of the present invention.
4 is a cross-sectional view schematically illustrating a flexible transparent conductive film according to a fourth embodiment of the present invention.
5 is a cross-sectional view schematically illustrating a flexible transparent conductive film according to a fifth embodiment of the present invention.
6 is a cross-sectional view schematically illustrating a flexible transparent conductive film according to a sixth embodiment of the present invention.
7 is a photograph showing scratch resistance, chemical resistance, and adhesion to the flexible transparent conductive film of Example 1. FIG.
8 is a photograph showing the contact angle of the thin film according to the change in partial pressure of O ₂ of the Cu and CuO-containing thin film layers.
9 (a) and (b) are graphs respectively showing the transmittance and surface reflectance of the film according to the change in the Ag thickness of the Ag thin film layer.
10 is a photograph showing topography of the flexible transparent conductive films of Examples 2-3 and Comparative Examples 2-3.
11 is a photograph showing the NCM phase for the flexible transparent conductive films of Examples 2-3 and Comparative Examples 2-3.
12 (a) to (d) are graphs showing light transmittance, reflectance, surface reflectance and light transmittance after reliability evaluation in the visible ray region for the flexible transparent conductive film of Example 4, respectively.
13 is a graph showing the reflectance in the infrared region of the flexible transparent conductive film of Example 4;
14 is a graph showing an increase rate of sheet resistance compared to an initial stage after a bending test for the flexible transparent conductive film of Example 4;
15 (a) to (d) are photographs showing the heat shielding properties of the films of Controls 1 to 3 and Example 4, respectively.
16 is an XPS graph in which the components of each thin film are analyzed according to an inflow of oxygen or nitrogen when a second nano-thin film layer is formed according to Example 1. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Examples of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, and the scope of the present invention is not limited to the following examples Examples are not limited thereto. In this case, the same reference numerals refer to the same structures throughout this specification.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

In addition, since the size and thickness of each component shown in the drawings are arbitrarily indicated for convenience of description, the present invention is not necessarily limited to the illustrated bar. In order to clearly express various layers and regions in the drawings, the thicknesses are enlarged. And in the drawings, for convenience of description, the thickness of some layers and regions are exaggerated.

In addition, throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In addition, throughout the specification, "on" or "on" means not only a case located above or below the target part, but also includes a case where there is another part in the middle, and must be in the direction of gravity It does not mean that it is positioned above with respect to .

And, in the present specification, terms such as “first” and “second” do not indicate any order or importance, but are used to distinguish components from each other.

1 to 6 are cross-sectional views schematically showing flexible transparent conductive films according to first to sixth embodiments of the present invention, respectively.

1 to 7, the flexible transparent conductive film (100A to 100F) according to the present invention is a polymer substrate (1); and a multi-layered nano-thin film layer on one surface of the polymer substrate 1, wherein the multi-layered nano-thin film layer includes a first nano-thin film layer 10 containing a first metal compound having a refractive index of 1.7 or more; (i) a first metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) an oxide of the first metal or a nitride of the first metal A second nano-thin film layer 20 containing; and a third nano-thin film layer 30 containing silver (Ag)-containing metal. In addition, the flexible transparent conductive film of the present invention is disposed on the third nano-thin film layer 30, (i) from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al). A fourth nano-thin film layer 40 containing the selected second metal, and (ii) an oxide of the second metal or a nitride of the second metal may be further included. In addition, the flexible transparent conductive film of the present invention is disposed on the fourth nano-thin film layer 40, the fifth nano-thin film layer 50 containing a second metal compound having a refractive index of 1.7 or more; and a sixth nano-thin film layer 60 disposed on the fifth nano-thin film layer 50 and having a refractive index of 1.6 or less. In this case, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 may be alternately stacked once or a plurality of times, and the outermost layer may be the sixth nano-thin film layer 60 . In addition, in the flexible transparent conductive film of the present invention, when the sixth nano-thin film layer 60 contains a silicon oxide-based material, it is disposed on the sixth nano-thin film layer 60, and an anti-fingerprint layer 70 formed of a fluorine-based resin. may further include. In addition, the flexible transparent conductive film of the present invention may further include a seventh nano-thin film layer 80 disposed on the other surface of the polymer substrate 1 and having a refractive index of 1.5 or less. In addition, the flexible transparent conductive film of the present invention may further include an anti-glare layer interposed between the polymer substrate 1 and the first nano-thin film layer.

Hereinafter, a flexible transparent conductive film 100A according to a first embodiment of the present invention will be described with reference to FIG. 1 .

As shown in FIG. 1, the flexible transparent conductive film 100A according to the first embodiment of the present invention includes a polymer substrate 1; and a first nano-thin film layer 10 , a second nano-thin film layer 20 , and a third nano-thin film layer 30 sequentially stacked on the polymer substrate 1 .

(1) polymer substrate

In the flexible transparent conductive film 100A of the present invention, the polymer substrate 1 supports and protects other components disposed on one side or both sides, and is a substrate excellent in flexibility and light transparency. The polymer substrate 1 may have a single layer or a plurality of layers.

The polymer substrate 1 usable in the present invention is not particularly limited as long as it is a light-transmitting polymer film commonly known in the art, specifically, a light-transmitting polymer film having insulation and heat resistance.

Specifically, examples of the polymer substrate 1 include polyethylene terephthalate (PET), polyimide (PI) (eg, Kapton film), polyethersulfone (PES), polyacrylate (Polyacrylate) , PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyarylate (Polyarylate), polycarbonate (PC), and polymer films such as cellulose triacetate (CTA), cellulose acetate propionate (CAP), and cyclo olefin polymer (COP), but are not limited thereto. Among them, polyethylene terephthalate (PET) film has high light transmittance and can be manufactured at low temperature at low cost, and is suitable as the polymer substrate 1 in terms of light transmittance, durability, processability, manufacturing cost, and the like.

The light transmittance of the polymer substrate 1 is not particularly limited, and may be, for example, about 80% or more in a visible light wavelength band. In this case, the optical properties of the flexible transparent conductive film itself of the present invention may be further improved.

In addition, the surface of the polymer substrate 1 may be subjected to O ₂ plasma treatment using an inductively coupled plasma treatment apparatus. In this case, the resistivity of the multi-layered nano-thin film layer disposed on one surface of the polymer substrate 1, particularly the third nano-thin film layer containing silver (Ag)-containing metal, can be lowered to less than 1×10 ^-2 Ω·cm have.

In addition, the thickness of the polymer substrate is not particularly limited, and may be, for example, in the range of about 20 to 700 μm, specifically, in the range of about 25 to 300 μm.

(2) first nano-thin film layer

In the flexible transparent conductive film 100A of the present invention, the first nano-thin film layer 10 is a seed layer disposed on one surface of the polymer substrate 1, and includes a metal compound (hereinafter, 'first metal compound'). ) is a thin film layer formed of The first nano-thin film layer 20 may be uniformly formed on the polymer substrate 1 without a change in surface roughness. In addition, the first nano-thin film layer 20 can increase the thin film density when the second nano-thin film layer formed in the island growth mode is formed, which is the thermal, Chemical stability can be improved.

In addition, since the first nano-thin film layer 10 has a high refractive index in the range of about 1.7 or more, specifically about 2 to 2.4, the optical properties of the flexible transparent conductive film 100A can be improved.

The first metal compound usable in the present invention is not particularly limited as long as it is a metal compound having a refractive index of 1.7 or more in the art, for example, a silicon nitride-based material [eg, Si ₃ N ₄ , SiNx (0<x<2)], metal nitrides such as titanium nitride-based materials (eg, TiN, TiN _x (0<y<1)], aluminum nitride-based materials (eg, AlN, AlNx (0<x<1)); Niobium oxide-based material [eg, NbO, Nb ₂ O ₃ , NbO ₂ , Nb ₂ O _5, NbOx(0<x<3)], aluminum oxide-based material [eg, Al ₂ O ₃ , AlOx(0<x<) 2)], and the like may be a metal oxide. In this case, the first nano-thin film layer 10 may be a single layer or a plurality of layers.

According to an example, the first nano-thin film layer 10 is, as shown in FIG. 1 , a silicon nitride-based material (eg, at least one of Si ₃ N ₄ and SiNx (0<x<2)), a titanium nitride-based material [Example: at least one of TiN and TiN _x (0<y<1)], aluminum nitride-based material [eg, at least one of AlN and AlNx (0<x<1)], niobium oxide-based material [eg: At least one selected from the group consisting of NbO, Nb ₂ O ₃ , NbO ₂ , Nb ₂ O ₅ , and NbOx (0<x<3)], and an aluminum oxide-based material (eg, Al ₂ O ₃ and AlOx (0) At least one of <x<2)] may be a single-layered nano-thin film layer containing at least one selected from the group consisting of.

Specifically, the first nano-thin film layer 10 may be a nano-thin film layer containing a silicon nitride-based material (eg, at least one of Si ₃ N ₄ and SiNx (0<x<2)).

According to another example, although not shown, the first nano-thin film layer 10 is disposed on the polymer substrate 1, the first nano-thin film layer 1A containing a metal oxide having a refractive index of 1.7 or more; and a 1B nano-thin film layer disposed on the 1A nano-thin film layer and containing a metal nitride having a refractive index of 1.7 or more.

Specifically, the first nano-thin film layer 10 is disposed on the polymer substrate 1, and a niobium oxide-based material having a refractive index of 1.7 or more [eg, NbO, Nb ₂ O ₃ , NbO ₂ , Nb ₂ O ₅ and NbOx 1A nano-thin film layer containing (at least one selected from the group consisting of 0<x<3)]; and a 1B nano-thin film layer disposed on the 1A nano-thin film layer and containing a silicon nitride-based material having a refractive index of 1.7 or higher (eg, at least one of Si ₃ N ₄ and SiNx (0<x<2)) can do.

The ratio (D _1B /D _1A ) of the thickness (D _1B ) of the first nano-thin film layer 1B to the thickness (D _1A ) of the nano-thin film layer 1A may be 1 to 1:4. As such, when the first nano-thin film layer 10 is a plurality of layers, the transmittance and reflectance of a specific wavelength region (eg, visible light region, infrared region) can be easily adjusted compared to the case of a single layer.

The thickness of the first nano-thin film layer 10 is not particularly limited, and may be, for example, about 10 to 60 nm, specifically about 10 to 40 nm, and more specifically about 30 to 40 nm. If the thickness of the first nano-thin film layer 10 is within the above-described range, optical properties, electrical properties and weather resistance of the flexible transparent conductive film may be improved.

The method of forming the above-described first nano-thin film layer 10 may be formed according to a thin film formation method known in the art. physical vapor deposition methods such as, for example, sputtering deposition, thermal evaporation vacuum deposition, and the like; chemical vapor deposition methods such as atmospheric pressure chemical vapor deposition, low pressure chemical vapor deposition, plasma chemical vapor deposition, and the like; There is a plating method, etc., but is not limited thereto.

According to an example, the first nano-thin film layer 10 may be formed by a pulsed DC sputtering method.

The pulse DC sputtering deposition conditions are not particularly limited, but a Si plate may be used as a substrate, and an argon (Ar) gas (injection amount: about 300 to 500 sccm), etc. is used as a process gas, and the applied power is about 1,000 to 7,000 W, and the amount of nitrogen gas or oxygen gas may be about 150 to 250 sccm. In addition, the metal target to be used is selected according to the type of metal of the first metal compound, and there are, for example, Si target, Ti target, Nb target, Al target, and the like.

(3) second nano-thin film layer

In the flexible transparent conductive film 100A of the present invention, the second nano-thin film layer 20 is a portion disposed on the first nano-thin film layer 10, and includes a metal (hereinafter, 'first metal') and the first metal. oxides or nitrides. The second nano-thin film layer 20 is a thin film layer formed by growing in an island shape while injecting oxygen (O ₂ ) or nitrogen (N ₂ ) during formation. Since the particle phase is mixed, the third nano-thin film layer 30, which is the main thin-film layer, can minimize defects such as pin-holes, and thus the morphology of the third nano-thin film layer 30 can be improved. have. In addition, since the first metal (eg, Cu) in the second nano-thin film layer 20 is more reactive than silver (Ag), it may be oxidized before silver (Ag) to form an oxide film, thereby forming the second nano-thin film layer ( 20) not only slows the oxidation rate of silver (Ag) in the third nano-thin film layer 30 , but the formed oxide film may protect the third nano-thin film layer.

The second nano-thin film layer 20 of the present invention includes (i) a first metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) the first It contains the oxide of a metal or the nitride of the said 1st metal.

Specifically, the second nano-thin film layer 20 is a first metal particle; and the oxide particles of the first metal or the nitride particles of the first metal are mixed, or the first metal oxide particles (or the first metal nitride particles) are dispersed in a matrix of the first metal particles. According to an example, the second nano-thin film layer 20 is a copper (Cu) particle phase; and copper oxide (CuO and/or CuOx) particles are mixed.

Here, the first metal oxide is not only a metal oxide having a stoichiometric composition (eg, CuO, Cu ₂ O; TiO ₂ ; ZrO ₂ ; Al ₂ O ₃ ), as well as a non-(non-) due to excess or loss of oxygen when forming a thin film. -Stoichiometric* composition of the first metal oxide (eg, CuxOy, TixOy, ZrxOy, AlxOy) is also mixed at the same time. In addition, the first metal nitride includes not only the first metal nitride having a stoichiometric composition (eg, Cu ₃ N, TiN, ZrN, AlN), but also non-chemical stoichiometry* due to excess or loss of nitrogen during thin film formation. A first metal nitride having a composition (eg, CuxNy, TixNy, ZrxNOy, AlxNy) is also mixed at the same time.

According to an example, the second nano-thin film layer 20 may be formed by introducing oxygen gas (O ₂ ) or nitrogen gas (N ₂ ) at an inflow amount of about 40 to 50 sccm during sputtering. At this time, the second nano-thin film layer 20 includes the first metal and the first metal oxide or the first metal nitride in a weight ratio of 70:30 to 52:48, specifically 60:40 to 55:45 by weight, more specifically as 60:40 to 57:43 weight ratio. According to another example, the second nano-thin film layer 20 may have a Cu2p3/2 peak with a binding energy of 952 to 954 eV and a Cu2p1/2 peak with a binding energy of 932 to 944 eV according to the XPS analysis method. The second nano-thin film layer 20 may improve the thin film density of the third nano-thin film layer 30 .

In addition, the thickness of the second nano-thin film layer 20 is not particularly limited, and may be, for example, in the range of 5 to 20 nm. If the thickness of the second nano-thin film layer is within the above-described range, both optical and electrical properties of the flexible transparent conductive film may be improved.

Since the method of forming the above-described second nano-thin film layer 20 is the same as described in the method for forming the above-described first nano-thin film layer, it is omitted. According to one example, the second nano-thin film layer 20 may be formed by a pulsed DC sputtering method or a DC sputtering method.

The sputtering deposition conditions are not particularly limited, but a Si plate may be used as a substrate, and a target made of the metal (M ¹ ) (eg, Cu) is used, and an argon (Ar) gas (injection amount: about 400 to 500 sccm) and the like, and the applied power is in the range of about 10 to 2,000 W, and the amount of oxygen gas (O ₂ ) or nitrogen gas (N ₂ ) may be about 40 to 50 sccm.

(4) third nano thin film layer

In the flexible transparent conductive film 100A of the present invention, the third nano-thin film layer 30 is a main thin-film layer disposed on the second nano-thin film layer 20, and contains silver (Ag)-containing metal. The third nano-thin film layer 30 may improve the optical and electrical properties of the flexible transparent conductive film as well as thermal conductivity.

The silver (Ag)-containing metal usable in the present invention may be a silver-alloy containing silver (Ag) alone or at least one metal other than silver (Ag). For example, the silver-containing metal is silver (Ag); or at least one metal selected from the group consisting of gold (Au), chromium (Cr), titanium (Ti), copper (Cu), indium (In), niobium (Nb), nickel (Ni), and tin (Sn) It may be an alloy between (M) and silver (Ag). In this case, it is appropriate that the metal (M) has lower chemical reactivity than silver (Ag), such as gold (Au), in addition to the above-mentioned types. In one example, the silver (Ag)-containing metal is Ag; two-component alloys such as Ag-Au, Ag-Cr, Ag-Ti, Ag-Cu, Ag-In, and Ag-Nb; three-component alloys such as Ag-Cu-Ni, Ag-In-Sn, and Ag-Cu-In; It may be one selected from the group consisting of quaternary alloys such as Ag-Ti-In-Sn and Ag-Cu-Ni-Ng.

Here, in the alloy, the content ratio (Ag:M) of silver (Ag) and the metal (M) alloyed with silver may be in a weight ratio of 78:22 to 99:1, specifically 92:8 to 96:4 by weight. can be

According to an example, the third nano-thin film layer 30 may be a nano-thin film layer formed of silver (Ag). According to another example, the third nano-thin film layer 30 may be an Ag-Au-based alloy.

The surface roughness (Rq) of the third nano-thin film layer 30 may be in the range of about 0.2 to 2.0. As such, the third nano-thin film layer 30 has excellent surface morphological properties.

The thickness of the third nano-thin film layer 30 is not particularly limited, and may be, for example, in the range of 5 to 20 nm, specifically, in the range of 10 to 15 nm. If the thickness of the third nano-thin film layer 30 is in the above-described range, the sheet resistance of the third nano-thin film layer is about 15 Ω/sq or less, specifically, about 13 to 8 Ω/sq, and the thermal conductivity is about 400 to In the range of 450 W/m·k, electrical properties and thermal conductivity properties can be improved without deterioration in light transmittance of the flexible transparent conductive film.

Since the method of forming the above-described third nano-thin film layer 30 is the same as described in the method of forming the above-described first nano-thin film layer, it is omitted. According to an example, the third nano-thin film layer 30 may be formed by a DC sputtering method.

The DC sputtering deposition conditions are not particularly limited, but a Si plate may be used as a substrate, a silver (Ag) target is used, argon (Ar) etc. are used as a process gas, and the applied power is about 600 to 1,000 W range, and the amount of argon gas may be about 400 to 500 seem. If the third nano-thin film layer includes silver-alloy, in addition to the silver (Ag) target, a target made of a metal (M) alloyed with silver (Ag) is also used.

Hereinafter, a second embodiment of the present invention will be described with reference to FIG. 2 . In order to avoid duplication, descriptions of the already described components will be omitted.

2 is a cross-sectional view of a flexible transparent conductive film 100B according to a second embodiment of the present invention, comprising: a polymer substrate 1; and a first nano-thin film layer 10 , a second nano-thin film layer 20 , a third nano-thin film layer 30 , and a fourth nano-thin film layer 40 sequentially stacked on one surface of the polymer substrate 1 .

As shown in FIG. 2 , the fourth nano-thin film layer 40 is a portion disposed on the third nano-thin film layer 30 , and includes a metal (hereinafter, 'second metal') and an oxide or nitride of the second metal. include The fourth nano-thin film layer 40 is a thin film layer formed by growing in an island shape while injecting oxygen (O ₂ ) or nitrogen (N ₂ ) during formation, similarly to the second nano-thin film layer 20 , and the first metal Since the particle phase and the oxide or nitride particle phase of the first metal are mixed, oxidation of the third nano-thin film layer 30 can be prevented, and the interlayer adhesion is improved to prevent thermal and mechanical deformation, thereby improving weather resistance. have.

The fourth nano-thin film layer 40 of the present invention includes (i) a second metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) the second It contains the oxide of a metal or the nitride of the said 2nd metal.

Specifically, the fourth nano-thin film layer 40 is a second metal particle; and the oxide particles of the second metal or the nitride particles of the second metal are mixed, or the oxide particles of the second metal (or nitride particles of the second metal) are dispersed in a matrix of the second metal particles. have. In this case, the fourth nano-thin film layer 40 may have the same or different components and contents from the second nano-thin film layer 20 . That is, when the fourth nano-thin film layer 40 is different from the second nano-thin film layer 20 , the second metal is different from the first metal, or a second metal oxide or second metal different from the second nano-thin film layer 20 . It may contain a nitride, or a content ratio between the second metal and the second metal oxide (or the second metal nitride) may be different.

According to an example, the fourth nano-thin film layer 40 is a copper (Cu) particle phase; and copper oxide (at least one selected from the group consisting of CuO, Cu ₂ O and CuOx) particle phases are mixed. At this time, the second nano-thin film layer 20 is also in the form of copper (Cu) particles; and copper oxide (at least one selected from the group consisting of CuO, Cu ₂ O and CuOx) particle phases are mixed. However, in the fourth nano-thin film layer 40, the copper content in the thin film is higher than the copper oxide content, whereas in the second nano-thin film layer 20, the copper content in the thin film is smaller than the copper oxide content.

Here, the second metal oxide is not only a metal oxide having a stoichiometric composition (eg, CuO, Cu ₂ O; TiO ₂ ; ZrO ₂ ; Al ₂ O ₃ ), as well as a non-(non) due to excess or loss of oxygen when forming a thin film. - A second metal oxide having a stoichiometric composition (eg, CuxOy, TixOy, ZrxOy, AlxOy) is also mixed at the same time. In addition, the second metal nitride is not only a second metal nitride having a stoichiometric composition (eg, Cu ₃ N, TiN, ZrN, AlN), but also non-stoichiometric due to excess or loss of nitrogen during thin film formation. A second metal nitride having a composition (eg, CuxNy, TixNy, ZrxNOy, AlxNy) is also mixed at the same time.

According to an example, the fourth nano-thin film layer 40 may be formed by introducing oxygen gas (O ₂ ) or nitrogen gas (N ₂ ) at an inflow amount of about 40 to 50 sccm during sputtering. In this case, the fourth nano-thin film layer 40 includes a second metal and a second metal oxide or a second metal nitride in a weight ratio of 70:30 to 52:48, specifically 60:40 to 55:45 by weight, more specifically as 60:40 to 57:43 weight ratio. According to another example, the fourth nano-thin film layer 40 may have a Cu2p3/2 peak with a binding energy of 952 to 954 eV and a Cu2p1/2 peak with a binding energy of 932 to 944 eV according to the XPS analysis method. The fourth nano-thin film layer 40 can prevent oxidation of the third nano-thin film layer 30 , and improve interlayer adhesion to prevent thermal and mechanical deformation, thereby improving weather resistance.

In addition, the thickness of the fourth nano-thin film layer 20 is not particularly limited, but it is appropriate to be thinner than the thickness of the second nano-thin film layer in terms of optical properties, chemical, thermal, and mechanical stability of the film. According to an example, the thickness (D ₂ ) of the second nano-thin film layer may be in the range of about 5 to 20 nm, specifically, in the range of about 5 to 10 nm, and the thickness (D ₄ ) of the fourth nano-thin film layer is in the range of about 1 to 20 nm range, specifically about 2.5 to 10 nm. In this case, the ratio (D ₄ /D ₂ ) of the thickness (D ₄ ) of the fourth nano-thin film layer to the thickness (D ₂ ) of the second nano-thin film layer may be about 0.2 to 1.

Since the method of forming the above-described fourth nano-thin film layer 40 is the same as described in the method for forming the above-described first nano-thin film layer, it is omitted. According to an example, the fourth nano-thin film layer 40 may be formed by a pulsed DC sputtering method or a DC sputtering method, similarly to the second nano-thin film layer 20 .

The sputtering deposition conditions are not particularly limited, but a Si plate may be used as a substrate, and a target made of the metal (M ¹ ) (eg, Cu) is used, and an argon (Ar) gas (injection amount: about 400 to 500 sccm) and the like, and the applied power is in the range of about 10 to 700 W, and the amount of oxygen gas (O ₂ ) or nitrogen gas (N ₂ ) may be about 40 to 50 sccm.

Hereinafter, a third embodiment of the present invention will be described with reference to FIG. 3 . In order to avoid duplication, descriptions of the already described components will be omitted.

3 is a cross-sectional view of a flexible transparent conductive film 100C according to a third embodiment of the present invention, comprising: a polymer substrate 1; and a multi-layered nano-thin film layer laminated on one surface of the polymer substrate 1, wherein the multi-layered nano-thin film layer is a first nano-thin film layer 10, a second nano-thin film layer 20, and a third nano-thin film layer 30 , a fourth nano-thin film layer 40 , a fifth nano-thin film layer 50 , and a sixth nano-thin film layer 60 .

In the flexible transparent conductive film 100C of the present invention, the fifth nano thin film layer 50 is a high refractive index thin film layer having a refractive index of about 1.7 or more, and can increase the transmittance of the film, and the sixth nano thin film layer 60 is about 1.6 or less With a low refractive index thin film layer having a refractive index of , it is possible to lower the reflectivity of the film. In addition, they can prevent air or moisture from penetrating into the film. Therefore, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 are sequentially disposed on the fourth nano-thin film layer 40, thereby matching the refractive index of the film to improve optical properties while blocking oxygen and moisture. It is possible to improve the chemical stability of the film.

In the present invention, the fifth nano-thin film layer 50 is not particularly limited as long as the refractive index is a metal compound having a refractive index of about 1.7 or more, specifically about 2 to 2.4, for example, a silicon nitride-based material [eg, Si ₃ N ₄ , SiNx (0 <x<2)], titanium nitride-based materials [eg TiN, TiN _x (0<y<1)], aluminum nitride-based materials [eg AlN, AlNx(0<x<1)], etc. Niobium oxide-based material [eg, NbO, Nb ₂ O ₃ , NbO ₂ , Nb ₂ O _5, NbOx(0<x<3)], aluminum oxide-based material [eg, Al ₂ O ₃ , AlOx(0<x<) 2)], and the like may be a metal oxide.

According to an example, the fifth nano-thin film layer 50 may be a thin film layer made of a silicon nitride-based material (eg, at least one of Si ₃ N ₄ and SiNx (0<x<2)).

In addition, the sixth nano-thin film layer 60 is not particularly limited as long as the refractive index is about 1.6 or less, specifically about 1.5 or less, if it is a metal oxide or a light-transmitting polymer, for example, a silicon oxide-based material [eg, SiO ₂ and SiOx (0 < x < 2)], poly(methyl methacrylate) [poly(methyl methacrylate), PMMA], poly(methyl acrylate) [poly(methyl acrylate)], and the like. Among them, silicon oxide-based materials [eg, at least one of SiO ₂ and SiOx (0<x<2)] minimize the formation of pinholes and thus have excellent moisture permeation prevention effects, as well as separate surfaces when forming an anti-fingerprint layer. There is no need to perform processing.

Although not shown, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 may be alternately stacked a plurality of times, and the outermost layer may be the sixth nano-thin film layer 60 . In this case, the number of stacking may be 2 to 6 times. However, in terms of productivity, uniformity, and weather resistance of the film, it is appropriate to alternately stack the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 no. 2 to 4.

The total thickness of the fifth nano-thin film layer(s) 50 and the sixth nano-thin film layer(s) 60 is not particularly limited, and may be, for example, in the range of 40 to 100 nm.

At this time, the ratio between the thickness (total thickness) of the fifth nano-thin film layer(s) 50 and the thickness (total thickness) of the sixth nano-thin film layer(s) 60 is not particularly limited, and may be 1:1 to 5. have. In this case, the thickness (total thickness) of the fifth nano-thin film layer(s) 50 is not particularly limited, and may be, for example, about 10 to 100 nm, specifically about 30 to 60 nm, more specifically about 50 to 60 nm. and the thickness (total thickness) of the sixth nano-thin film layer(s) 60 is not particularly limited, and may be, for example, about 10 to 100 nm, specifically about 30 to 60 nm, more specifically about 50 to 60 nm .

In addition, it is appropriate to adjust the total thickness of the fourth nano-thin film layer 40, the fifth nano-thin film layer(s) 50 and the total thickness of the sixth nano-thin film layer(s) 60 in the range of about 100 to 500 nm. do. In this case, the thermal conductivity between the fourth nano-thin film layer 40 , the fifth nano-thin film layer 50 , and the sixth nano-thin film layer 60 and the third nano-thin film layer 30 is improved, so that the heat shielding property of the film can be further improved. have.

Since the method of forming the above-described fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 is the same as described in the above-described method for forming the first nano-thin film layer, it is omitted. According to an example, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 may be formed by a pulsed DC sputtering method.

When forming the fifth nano-thin film layer 50, pulse DC sputtering deposition conditions are not particularly limited, but a Si plate may be used as a substrate, and a target of a metal selected from Si, Ti, Al and Nb is used, and a process gas is used. Argon (Ar) gas (injection amount: about 300 to 500 sccm), etc. is used, and the applied power is in the range of about 1,000 to 7,000 W, and the amount of oxygen gas (O ₂ ) or nitrogen gas (N ₂ ) is about 150 to 250 may be sccm.

Hereinafter, a fourth embodiment of the present invention will be described with reference to FIG. 4 . In order to avoid duplication, descriptions of the already described components will be omitted.

4 is a cross-sectional view of a flexible transparent conductive film 100D according to a fourth embodiment of the present invention, comprising: a polymer substrate 1; and a multi-layered nano-thin film layer laminated on one surface of the polymer substrate 1, wherein the multi-layered nano-thin film layer is a first nano-thin film layer 10, a second nano-thin film layer 20, and a third nano-thin film layer 30 , a fourth nano-thin film layer 40 , a fifth nano-thin film layer 50 , a sixth nano-thin film layer 60 , and an anti-fingerprint layer 70 . At this time, although not shown, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 are alternately stacked a plurality of times, and the outermost layer may be the sixth nano-thin film layer 60 .

In the present invention, the anti-fingerprint layer 70 is a portion disposed on the sixth nano-thin film layer, and may impart anti-contamination and water repellency to the film.

The anti-fingerprint layer 70 is not particularly limited as long as it is a material capable of imparting anti-fingerprint properties conventionally in the art, and may be, for example, a composition for forming an anti-fingerprint layer including a fluorine-based resin and a solvent.

Examples of the fluorine-based resin include perfluoropolyether, and specifically, perfluoropoly(methylene oxide), perfluoropoly(ethyleneoxide), and perfluoropolydioxolane. (dioxolane)), perfluoropolytrioxocane (Perfluoropoly(trioxocane)), etc., which may be used alone or in combination of two or more.

The solvent is not particularly limited as long as it can easily form a coating film and dry while dissolving the fluorine-based resin, for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane. a perfluoroaliphatic hydrocarbon having an alkyl group or cycloalkyl group having 5 to 20 carbon atoms; perfluoroaromatic hydrocarbons having an aryl group having 6 to 18 carbon atoms, such as bis(trifluoromethyl)benzene; There are polyfluorinated aliphatic hydrocarbons having an alkyl group having 1 to 20 carbon atoms, such as perfluorobutyl methyl ether and ethylnonafluoro isobutyl ether, and these may be used alone or in combination of two or more.

The thickness of the anti-fingerprint layer 70 is not particularly limited, and may be, for example, in the range of about 5 to 25 nm.

The method of forming the above-described anti-fingerprint layer 70 is not particularly limited as long as it is a coating film forming method commonly known in the art, for example, a casting method, a dip coating, a die coating, a roll) Various methods such as coating, slot die, comma coating, inkjet printing, doctor blade coating, gravure printing, gravure offset printing, screen printing, or a mixture thereof may be used.

Hereinafter, a fifth embodiment of the present invention will be described with reference to FIG. 5 . In order to avoid duplication, descriptions of the already described components will be omitted.

5 is a cross-sectional view of a flexible transparent conductive film 100E according to a fifth embodiment of the present invention, comprising: a polymer substrate 1; and an anti-glare layer (80) sequentially stacked on one surface of the polymer substrate (1); It includes a first nano-thin film layer 10 , a second nano-thin film layer 20 , and a third nano-thin film layer 30 . Although not shown, a fourth nano-thin film layer 40 may be further disposed on the third nano-thin film layer 30 . In addition, a fifth nano-thin film layer 50 and a sixth nano-thin film layer 60 may be further disposed on the fourth nano-thin film layer 40 . In this case, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 may be alternately stacked once or a plurality of times, and the outermost layer may be the sixth nano-thin film layer 60 . In addition, an anti-fingerprint layer 70 may be further disposed on the sixth nano-thin film layer 60 .

In the present invention, the anti-glare layer 80 is a portion interposed between the polymer substrate 1 and the first nano-thin film layer 10, and includes a material capable of scattering light in the art and is incident on the film from the outside. Visibility can be improved while preventing glare by scattering the light.

According to an example, the anti-glare layer 80 may include a binder resin; And it may be formed of a composition for anti-glazing comprising at least one of inorganic particles and organic particles.

The binder resin usable in the present invention is not particularly limited as long as it can bind particles in the art, and for example, an acrylic resin or the like.

Non-limiting examples of the inorganic particles include silica, titania, zirconia, alumina, and the like, and the organic particles are polymer beads, non-limiting examples of which include polymethyl methacrylate, polystyrene, polymethyl methacrylate and styrene. copolymers and the like.

The average particle diameter (D50) of these particles is not particularly limited, and may be, for example, about 20 μm or less, specifically, about 2 to 15 μm. When the average particle diameter of the inorganic particles or organic particles is within the above-mentioned range, an excellent anti-glare effect can be exhibited.

The content of the particles is not particularly limited, and may be, for example, 30 to 100 parts by weight based on 100 parts by weight of the binder resin.

The thickness of the anti-glare layer 80 is not particularly limited, and may be, for example, in the range of 5 to 17 μm.

The method of forming the above-described anti-glare layer 80 is not particularly limited as long as it is a method of forming a coating film commonly known in the art, for example, a casting method, a dip coating, a die coating, a roll (roll). ) coating, slot die, comma coating, inkjet printing, doctor blade coating, gravure printing, gravure offset printing, screen printing, or a mixture thereof can be used in various ways.

Hereinafter, a sixth embodiment of the present invention will be described with reference to FIG. 6 . In order to avoid duplication, descriptions of the already described components will be omitted.

6 is a cross-sectional view of a flexible transparent conductive film 100F according to a sixth embodiment of the present invention, comprising: a polymer substrate 1; a first nano-thin film layer 10, a second nano-thin film layer 20, and a third nano-thin film layer 30 sequentially stacked on one surface of the polymer substrate 1; and a seventh nano-thin film layer 90 disposed on the other surface of the polymer substrate. Although not shown, a fourth nano-thin film layer 40 may be further disposed on the third nano-thin film layer 30 . In addition, a fifth nano-thin film layer 50 and a sixth nano-thin film layer 60 may be further disposed on the fourth nano-thin film layer 40 . In this case, the fifth nano-thin film layer 50 and the sixth nano-thin film layer 60 may be alternately stacked once or a plurality of times, and the outermost layer may be the sixth nano-thin film layer 60 . In addition, an anti-fingerprint layer 70 may be further disposed on the sixth nano-thin film layer 60 .

In the present invention, the seventh nano-thin film layer 90 is a portion disposed on the other surface (eg, the lower surface) of the polymer substrate 1, and has a refractive index of 1.5 or less. The seventh nano-thin film layer 90 may increase the transmittance of light incident to the multilayer thin film by lowering the reflectance of light incident to the other surface (eg, the lower surface) of the substrate.

The seventh nano-thin film layer 90 is not particularly limited as long as it is an organic or inorganic material capable of forming a thin film having a refractive index of 1.5 or less, for example, a metal oxide or a light-transmitting polymer having a refractive index of 1.5 or less, and specifically a silicon oxide-based material [eg: SiO ₂ and SiOx (at least one of 0<x<2)], poly(methyl methacrylate) [poly(methyl methacrylate), PMMA], poly(methyl acrylate) [poly(methyl acrylate)], etc. .

In this case, the seventh nano-thin film layer 90 may be a single layer or a plurality of layers. According to one example, the seventh nano-thin film layer 90 may be a single-layer nano-thin film layer made of SiO ₂ . According to another example, although not shown, the seventh nano-thin film layer 90 is disposed on the other surface of the polymer substrate 1, and a metal oxide having a refractive index of 1.5 or less [eg, SiO ₂ and SiOx (0 <x < 2) 7A nano-thin film layer containing at least any one; and a 7B nano-thin film layer disposed on the 7A nano-thin film layer and containing a light-transmitting polymer (eg, PMMA) having a refractive index of 1.5 or less. In this case, the ratio (D _7B /D _7A ) of the thickness (D _7B ) of the 7B nano-thin film layer to the thickness (D _7A ) of the 7A nano-thin film layer may be 1: 0.5-5.

The thickness of the seventh nano-thin film layer(s) 90 is not particularly limited, and may be, for example, about 10 to 60 nm. If the thickness of the seventh nano-thin film layer 90 is within the above-described range, the reflectance may be decreased while increasing the transmittance of the film.

The method of forming the above-described seventh nano-thin film layer 90 may be formed according to a thin film forming method known in the art. physical vapor deposition methods such as, for example, sputtering deposition, thermal evaporation vacuum deposition, and the like; chemical vapor deposition methods such as atmospheric pressure chemical vapor deposition, low pressure chemical vapor deposition, plasma chemical vapor deposition, and the like; plating method; There is a roll-to-roll wet method such as micro gravure, and the like, but is not limited thereto.

According to an example, the seventh nano-thin film layer 90 may be formed by a pulsed DC sputtering method, a DC sputtering method, or a roll-to-roll wet method (eg, micro gravure).

The pulse DC sputtering deposition conditions are not particularly limited, but a Si plate or the like may be used as a substrate, argon (Ar) gas (injection amount: about 300 to 500 sccm), etc. is used as a process gas, and the applied power is about 1,000~ 7,000 W, and the amount of oxygen gas may be 10-150 sccm. Moreover, there exist a Si target etc. as a metal target used.

The above-described flexible transparent conductive films 100A, 100B, 100C, 100D, 100E, and 100F of the present invention have excellent flexibility, optical properties and electrical properties, as well as excellent thermal barrier properties. In addition, when a current is applied to the flexible transparent conductive film 100A, heat generation characteristics may be exhibited.

According to an example, the flexible transparent conductive films 100A, 100B, 100C, 100D, 100E, and 100F of the present invention may satisfy at least one of the following physical properties (i) to (vii).

(i) light transmittance of 85% or more at a wavelength of 380~780 nm, (ii) a reflectance of 5% or less at a wavelength of 380~780 nm, (iii) the rate of change in transmittance over time after standing at 80 °C and 80% for 168 hours 3% or less, (iv) a sheet resistance of 8 to 12 Ω/sq, (v) a far-infrared reflectance of 80% or more at a thermal wavelength of 6 to 15 μm, (vi) a heating element at about 80 ° C with attached to a glass substrate ( Example: After standing on a heat transfer plate) for 10 minutes, the surface temperature of the glass substrate may be about 25 to 33 ° C., and (vii) the surface reflectance may be 0.3% or less.

The flexible transparent conductive film (100A, 100B, 100C, 100D, 100E, 100F) of the present invention can be applied to various fields requiring excellent flexibility, optical, electrical, mechanical properties, heat shielding properties, heat dissipation properties, and the like. For example, the flexible transparent conductive film 100A, 100B, 100C, 100D, 100E, 100F of the present invention may be used as a transparent electrode of a display or a transparent heat shielding film.

According to one example, a display according to the present invention includes a transparent electrode containing a flexible transparent conductive film 100A, 100B, 100C, 100D, 100E, 100F. The transparent electrode may be an electrode in fields such as a plasma display (PDP), a liquid crystal display (TFT-LCD), an organic light emitting diode (OLED), a flexible display, and an organic thin film transistor (OTFT).

According to another example, the display according to the present invention includes a light source; and a transparent heat shielding film containing flexible transparent conductive films 100A, 100B, 100C, 100D, 100E, and 100F attached to the light source. At this time, the flexible transparent conductive film (100A, 100B, 100C, 100D, 100E, 100F) of the present invention transfers the heat in the vertical direction among the heat emitted from the light source in the horizontal direction to spread the internal heat over the entire surface. You can (release). In particular, the third nano-thin film layer 30, which is the main thin film layer in the flexible transparent conductive film, slowly transfers heat in the vertical direction conducted from the light source in the horizontal direction to release it to the outside, and consequently blocks the heat conducted in the vertical direction. . Therefore, the flexible transparent conductive film (100A, 100B, 100C, 100D, 100E, 100F) of the present invention can quickly dissipate the internal heat conducted in the horizontal direction to the outside, as well as block the heat conducted in the vertical direction. Therefore, it is possible not only to prevent a decrease in function or lifespan due to deterioration of the display, but also to reduce an image or discomfort when a user of the display comes into contact with the display.

On the other hand, the present invention provides a heating sheet including the above-described flexible transparent conductive film (100A, 100B, 100C, 100D, 100E, 100F).

The flexible transparent conductive film (100A, 100B, 100C, 100D, 100E, 100F) may act as a transparent planar heating element that generates heat when a current is applied.

Hereinafter, the present invention will be specifically described by way of Examples, but the following Examples and Experimental Examples are merely illustrative of one aspect of the present invention, and the scope of the present invention is not limited to the Examples and Experimental Examples below.

<Example 1>

A first nano thin film layer [SiNx thin film layer (thickness: 30 nm, refractive index: 2.02)] on the upper surface of the PET film (thickness: 125 μm, light transmittance: 92%); Second nano-thin film layer [Cu and CuO-containing thin film layer (thickness: 7 nm); Third nano-thin film layer [Ag thin film layer (thickness: 10 nm)]; Fourth nano-thin film layer [Cu and CuO-containing thin film layer (thickness: 5 nm) ]; 5th nano thin film layer [SiNx thin film layer (thickness: 30 nm, refractive index: 2.02)]; 6th nano thin film layer [SiOx thin film layer (thickness: 35 nm, refractive index: 1.46)] were sequentially deposited through a pulse DC sputtering device, respectively to prepare a flexible transparent conductive film, wherein the deposition conditions of each layer are described in Table 1 below.

Deposition conditions first nano-thin film layer SiNx thin film layer Applied power (kW) 7 Ar/N ₂ inflow (sccm) 500/250 Deposition rate (m/min) 0.5 second nano-thin film layer Cu and CuO-containing thin film layer Applied power (kW) 0.2 Ar/O ₂ inflow (sccm) 440/50 Deposition rate (m/min) 6 3rd nano thin film layer Ag thin layer Applied power (kW) 0.7 Ar/N ₂ inflow (sccm) 440 Deposition rate (m/min) 3 4th nano thin film layer Cu and CuO-containing thin film layer Applied power (kW) 0.1 Ar/O ₂ inflow (sccm) 440/50 Deposition rate (m/min) 6 5th nano-thin film layer SiNx thin film layer Applied power (kW) 7 Ar/N ₂ inflow (sccm) 500/250 Deposition rate (m/min) 0.8 6th nano thin film layer SiOx thin film layer Applied power (kW) 7 Ar/O ₂ inflow (sccm) 500/70 Deposition rate (m/min) 0.8

<Comparative Example 1>

In Example 1, when the second and fourth nano-thin film layers were formed, the Ar/O ₂ inflow was changed to 440/0 sccm instead of 440/50 sccm during deposition conditions to form Cu thin-film layers instead of Cu and CuO-containing thin-film layers, respectively. Except that Then, in the same manner as in Example 1, a flexible transparent conductive film was prepared.

<Experimental Example 1> - Evaluation of physical properties of flexible transparent conductive film

The physical properties of each of the flexible transparent conductive films prepared in Example 1 and Comparative Example 1 were evaluated as follows, and the results are shown in Table 2 and FIG. 7 .

(1) scratch resistance

Under the conditions of a load of 500 gf, a speed of 30 cycles/mim, and a moving distance of 50 mm, steel wool #0000 was reciprocated for 10 cycles on the surface of the flexible transparent conductive film to evaluate scratch resistance. At this time, when a scratch (scratch) was observed on the surface of the flexible transparent conductive film with the naked eye under LED 50 W lighting, it was indicated as "Fail", and when no scratch was observed, it was indicated as "No Scratch".

(2) chemical resistance

Scratch resistance was evaluated by rubbing the surface of the flexible transparent conductive film with a cotton cloth moistened with ethanol for 100 cycles under the conditions of a load of 500 gf, a speed of 30 cycles/mim, and a moving distance of 50 mm. At this time, when a scratch (scratch) was observed on the surface of the flexible transparent conductive film with the naked eye under LED 50 W lighting, it was indicated as "Fail", and when no scratch was observed, it was indicated as "No Scratch".

(3) Adhesiveness

According to ASTM D 3359 test method, adhesion was tested as follows.

100 cells were formed by vertically cutting at intervals of 1 mm in width and 1 mm in length on the surface of the flexible transparent conductive film, and then attaching a test tape on the grid pattern of the cut flexible transparent conductive film and peeling it at 90 degrees to make a film was evaluated for adhesion. At this time, according to the ratio of the area to be peeled compared to the total area of the film, it was classified and displayed as follows.

** Criteria for classification of crosscuts (ASTM D 3359) **

i) 5B: 0%, ii) 4B: less than 5%, iii) 3B: more than 5%, less than 15%, iv) 2B: more than 15%, less than 35%, v) 1B: more than 35%, less than 65% , vi) 0B: 65% or more

(4) transmittance, reflection color

Transmittance, reflectance, and reflected color (a ^* R and b ^* R) in the visible light region of the flexible transparent conductive film of Example 1 were measured using a spectrophotometer, respectively.

(5) surface reflectance

After attaching a test black tape (TOMOEGAWA's Black PET film soft look B) to the lower surface of the PET film of the flexible transparent conductive film, the reflectance of the film was measured.

Transmittance (%) Surface Reflectance (%) a ^* R b ^* R Example 1 85.4 0.51 -0.03 -0.85

As can be seen from FIG. 7 , the flexible transparent conductive film of Example 1 did not cause scratches even when reciprocating steel wool #0000 10 times. On the other hand, the flexible transparent conductive film of Comparative Example 1 was scratched when steel wool #0000 was reciprocated 10 times.

In addition, unlike the film of Comparative Example 1, the film of Example 1 did not generate scratches when the cotton cloth soaked in ethanol was rubbed 100 times.

In addition, in the Cross Cut test, in the film of Example 1, damaged cells were not observed. On the other hand, in the film of Comparative Example 1, most of the cells were damaged.

As described above, it was confirmed that the flexible transparent conductive film according to the present invention was excellent in scratch resistance, chemical resistance, and adhesion properties.

<Experimental Example 2>

In the preparation of the flexible transparent conductive film according to Example 1, the contact angle of the thin film according to the change in O ₂ partial pressure when the Cu and CuO-containing thin film layer was formed was measured using a contact angle analyzer (SEO, Inc.), and the result is shown in Table 3 and FIG. 8 . In FIG. 8, (a) shows an O ₂ partial pressure of 0 sccm, (b) shows an O ₂ partial pressure of 20 sccm, and (c) shows an O ₂ partial pressure of 50 sccm.

** test requirements **

i) Tension of Test liquid: 72.8

ii) Drop amount: 15-20 μl

iii) Drop material: Deionized water

O ₂ partial pressure (sccm) 0 20 50 Contact angle (°) 77 74 70

As can be seen from Table 3 and FIG. 8 , the contact angle decreased as the O ₂ partial pressure increased when the Cu and CuO-containing thin film layers were formed. That is, as the O ₂ partial pressure increased, the surface energy of the Cu and CuO-containing thin film layers increased.

Accordingly, in forming the Cu and CuO-containing thin film layer of the flexible transparent conductive film according to the present invention, the wettability of the Cu and CuO-containing thin film is improved as the O ₂ partial pressure increases, so that the thin film density of the film can be increased. could be estimated

<Experimental Example 3> - Transmittance and surface reflectance of the film according to the thickness change of the Ag thin film layer

For the flexible transparent conductive film of Example 1, the transmittance and surface reflectance of the film according to the thickness change of the Ag thin film were measured as follows, and the results are shown in FIG. 9 .

1) Preparation of Samples 1 to 5: A film was prepared according to Example 1, except for increasing the applied power from 700 W to 780 W when forming the Ag thin film layer, in the same manner as in Example 1 to prepare Samples 1 to 5 was prepared.

2) Transmittance: The transmittance of Samples 1 to 5 was measured using a spectrophotometer.

3) Surface reflectance: A black tape for testing was attached to the lower surface of the PET film of the flexible transparent conductive film, and then the reflectance of the film was measured.

As a result of the measurement, the transmittance of Samples 1 to 5 was constant even when the thickness of the Ag thin film layer increased. On the other hand, the surface reflectance of Samples 1 to 5 was low depending on the thickness of the Ag thin film layer, and in particular, when the applied power was about 740 to 780 W during Ag deposition, the surface reflectance was about 0.27% or less.

<Example 2>

1A nano thin film layer [Nb ₂ O _x thin film layer (thickness: 30 nm, refractive index: 2.3]; 1B nano thin film layer [SiNx thin film layer (thickness: 30)) on the upper surface of the PET film (thickness: 125 μm, light transmittance: 92%) nm, refractive index: 2.02)]; second nano-thin film layer [Cu and CuO-containing thin-film layer (thickness: 7 nm)]; and third nano-thin film layer [Ag thin-film layer (thickness: 10 nm)] sequentially through a pulsed DC sputtering apparatus, respectively. was deposited to prepare a flexible transparent conductive film, wherein the deposition conditions of each layer are shown in Table 4 below.

Deposition conditions 1A nano thin film layer Nb ₂ O _x thin film layer Applied power (kW) 7 Ar/O ₂ inflow (sccm) 500/250 Deposition rate (m/min) 3 1B nano thin film layer SiNx thin film layer Applied power (kW) 7 Ar/N ₂ inflow (sccm) 500/250 Deposition rate (m/min) 3 second nano-thin film layer Cu and CuO-containing thin film layer Applied power (kW) 0.2 Ar/O ₂ inflow (sccm) 440/50 Deposition rate (m/min) 6 3rd nano thin film layer Ag thin layer Applied power (kW) 0.7 Ar/N ₂ inflow (sccm) 440 Deposition rate (m/min) 3

<Example 3>

In Example 2, the same as in Example 2, except that the deposition rate was changed to 1.5 m/min instead of 3 m/min, respectively, to form the first A and 1B nano-thin film layers when the first A and 1B nano-thin film layers were formed to prepare a flexible transparent conductive film.

<Comparative Example 2>

In Example 2, when forming the second nano-thin film layer, the Ar/O ₂ inflow was changed to 440/0 sccm instead of 440/50 sccm during deposition conditions to form a Cu thin film layer instead of Cu and CuO-containing thin film layer. In the same manner as in Example 2, a flexible transparent conductive film was prepared.

<Comparative Example 3>

In Example 2, 1A and 1B nano-thin film layers were formed by changing the deposition rate to 1.5 m/min instead of 3 m/min, respectively, when forming the first A and 1B nano-thin film layers, and deposition conditions when forming the second nano-thin film layer A flexible transparent conductive film was prepared in the same manner as in Example 2, except that the Ar/O ₂ input amount was changed to 440/0 sccm instead of 440/50 sccm to form a Cu thin film layer instead of Cu and CuO-containing thin film layer did

<Experimental Example 4> - Analysis of surface properties of flexible transparent conductive film

The surface properties of the flexible transparent conductive films of Examples 2-3 and Comparative Examples 2-3 were analyzed using an atomic force microscope (AFM) to analyze the topography and NCM phase of each film, and the results are shown in Table 5, 10 and 11 are shown.

Example 2 Example 3 Comparative Example 2 Comparative Example 3 Surface roughness (Rq) 1.051 1.035 1.192 2.222

As a result of the analysis, the surface roughness (Rq) value of the flexible transparent conductive films of Examples 2-3 was decreased compared to the flexible transparent conductive films of Comparative Examples 2-3. It can be seen that the films of Examples 2-3 in FIGS. 10 and 11 also have a flatter Ag thin film layer than the films of Comparative Examples 2-3.

<Example 4>

A first nano thin film layer [SiNx thin film layer (thickness: 30 nm, refractive index: 2.02)] on the upper surface of the PET film (thickness: 125 μm, light transmittance: 92%); a second nano-thin film layer [Cu and CuO-containing thin film layer (thickness: 7 nm)]; a third nano thin film layer [Ag thin film layer (thickness: 10 nm)]; a fourth nano-thin film layer [Cu and CuO-containing thin film layer (thickness: 7 nm)]; 5th nano thin film layer [SiNx thin film layer (thickness: 30 nm, refractive index: 2.02)]; A sixth nano thin film layer [SiOx thin film layer (thickness: 35 nm, refractive index: 1.46)] was sequentially deposited through a pulsed DC sputtering apparatus, respectively. Then, on the lower surface of the PET film, 7A nano thin film layer [SiOx thin film layer (thickness: 100 nm, refractive index: 1.46)] and 7B nano thin film layer [organic thin film layer (Yulchon low refractive index-2, thickness: 100 nm) , refractive index: 1.35)] were sequentially deposited through a pulsed DC sputtering device to prepare a flexible transparent conductive film. In this case, the deposition conditions of each layer are as described in Table 6 below.

Deposition conditions first nano-thin film layer SiNx thin film layer Applied power (kW) 7 Ar/N ₂ inflow (sccm) 500/250 Deposition rate (m/min) 0.5 second nano-thin film layer Cu and CuO-containing thin film layer Applied power (kW) 0.2 Ar/O ₂ inflow (sccm) 440/50 Deposition rate (m/min) 6 Third nano-thin film layer Ag thin layer Applied power (kW) 0.7 Ar/N ₂ inflow (sccm) 440 Deposition rate (m/min) 3 4th nano thin film layer Cu and CuO-containing thin film layer Applied power (kW) 0.1 Ar/O ₂ inflow (sccm) 440/50 Deposition rate (m/min) 6 5th nano thin film layer SiNx thin film layer Applied power (kW) 7 Ar/N ₂ inflow (sccm) 500/250 Deposition rate (m/min) 0.8 6th nano thin film layer SiOx thin film layer Applied power (kW) 7 Ar/O ₂ inflow (sccm) 500/70 Deposition rate (m/min) 0.8 7A nano thin film layer Nb ₂ Ox thin film layer Applied power (kW) 4.5 Ar/O ₂ inflow (sccm) 500/20 Deposition rate (m/min) 2.0 7B nano thin film layer SiNx thin film layer Applied power (kW) 7 Ar/N ₂ inflow (sccm) 500/250 Deposition rate (m/min) 0.5

<Experimental Example 5> - Evaluation of physical properties of flexible transparent conductive film 1

The physical properties of the flexible transparent conductive film prepared in Example 4 were evaluated as follows, and the results are shown in Table 7 and FIGS. 12 to 14 below.

1) Light transmittance, reflectance, color difference, and haze: Using a spectrophotometer, light transmittance, reflectance, color difference, and haze were measured in the visible region, respectively. In Table 7 below, Vis T is a light transmittance at a wavelength of 550 nm, and Vis R is a reflectance at a wavelength of 550 nm.

2) Surface reflectance: A black tape for testing was attached to the lower surface of the PET film of the flexible transparent conductive film, and then the reflectance of the film was measured.

3) Sheet resistance: The sheet resistance value of the transparent electrode layer in the glass assembly was measured using a non-contact sheet resistance measuring instrument (NAGY, model name: SRM-12).

4) Reliability (85 ℃, 85 %RH, 168 hr): After leaving the flexible transparent conductive film under a temperature of 85 ℃ and a humidity of 85% for 168 hours, the light transmittance for the visible region was measured using a spectrophotometer. measured.

5) Far-infrared reflectance: The reflectance in the infrared region of the flexible transparent conductive film was measured using FT-IR equipment.

6) Bending test: The flexible transparent conductive film was bent 100,000 times with a radius of curvature of 7 mm using a planar body no-load U-fold test equipment (DLDMLS-FS, YUASA), and then the increase rate of sheet resistance compared to the initial stage was measured. In this case, an OMO film (CXM-125T-U1 manufactured by OIKE) was used as control A.

Vis T (%) Vis R (%) Surface Reflectance (%) Haze (%) Sheet resistance (Ω/sq) Example 4 91.5 2.7 0.22 0.3 10.3

As can be seen from Table 7 and FIG. 1 , the flexible transparent conductive film of Example 1 had excellent optical and electrical properties. In particular, the flexible transparent conductive film of Example 1 exhibited ultra-low reflection properties with a surface reflectance of 0.22% (see FIG. 12(c)). In addition, the film of Example 1 had a far-infrared reflectance of about 80% or more in the vicinity of 15 µm (see FIG. 13 ).

In addition, the film of Example 1 had an increase rate of sheet resistance of less than 3% compared to the initial stage even after bending 100,000 times, and was excellent in mechanical flexibility (see FIG. 14 ).

<Experimental Example 6> - Measurement of heat shielding properties of flexible transparent conductive film

The heat shielding properties of the flexible transparent conductive film prepared in Example 4 were measured as follows, and the results are shown in FIG. 15 .

The laminate in which the flexible transparent conductive film of Example 4 was attached to a glass substrate was left on a heat transfer plate at 80° C. for 10 minutes, and then the surface temperature of the glass substrate was measured using an infrared camera. At this time, as Control 1, a laminate having a PET film attached to an organic substrate was used, as Control 2, a laminate having an ITO film (NittoDenko) attached to a glass substrate was used, and as Control 3, an AgNW film (LG) on a glass substrate. electronic company) was used.

As can be seen from the measurement results, as can be seen in Figure 15, in the case of Control 1 to which the PET film was applied, there was no heat blocking effect (see Figure 15 (a)), In the case of Controls 2-3 to which the ITO film or AgNW film was applied, At 69.7 °C and 64.8 °C, respectively, the thermal blocking effect was insufficient (see FIGS. 15(b) to (c)). On the other hand, when the flexible transparent conductive film of Example 4 was applied, the surface temperature of the glass substrate was about 31.8° C., and the heat blocking effect was high (see FIG. 15( d )).

As described above, it was confirmed that the flexible transparent conductive film according to the present invention can exhibit a thermal barrier effect.

<Example 5>

A flexible transparent conductive film was prepared in the same manner as in Example 1, except that an Ag-Au thin film layer (Ag:Au=92:8 weight ratio) was formed instead of the Ag thin film layer formed in Example 1. When the Ag-Au thin film layer was formed, a current of 1 A/s was applied to the Ag target, and a current of 0.5 A/s was applied to the Au target.

<Experimental Example 7>

The flexible transparent conductive film of Example 5 was left for 14 days at a temperature of 85° C. and a humidity of 85%, and then light transmittance and sheet resistance at a wavelength of 550 nm were measured, respectively, and the results are shown in Table 8.

85℃ 85%RH, 0hr 85℃ 85%RH, 7 days 85℃ 85%RH, 14 days Transmittance (%) sheet resistance
(Ω/sq) Transmittance (%) sheet resistance
(Ω/sq) Transmittance (%) sheet resistance
(Ω/sq) Example 5 66.19 18 65.87 20 65.68 20

<Experimental Example 8>

In manufacturing the flexible transparent conductive film of the present invention, transmittance (T), haze and Surface resistance (RS) was measured, respectively, and the results are shown in Table 9.

As a result of the measurement, it was found that the transmittance, haze, and sheet resistance of the Ag-Au thin film layer, which is the third nano-thin film layer, were constant after reliability evaluation when the Au content was 4 to 8.5 wt%.

<Experimental Example 9>

When forming the second nano-thin film layer according to Example 1, in order to confirm the composition of the thin film according to the inflow amount of oxygen (O ₂ ) or nitrogen (N ₂ ), X-ray photoelectron analysis (X-ray) for the formed thin film layer photoelectron spectroscopy (XPS) was performed, and the results are shown in FIG. 16 . At this time, in FIG. 16 , Cu is a case where oxygen and nitrogen inflow is 0 sccm when forming a thin film, CuO ₂₀ is a case in which oxygen inflow is 20 sccm when forming a thin film, and CuO ₅₀ is a case in which oxygen inflow is 50 sccm when forming a thin film. , CuN ₂₀ means a case where the nitrogen inflow amount when forming a thin film is 20 sccm, and CuN ₅₀ means a case where the nitrogen inflow amount when forming a thin film is 50 sccm.

As a result of analyzing the second nano-thin film layer, a Cu2p3/2 peak with a binding energy of 952 to 954 eV and a Cu2p1/2 peak with a binding energy of 932 to 944 eV are respectively shown (see FIG. 16 ).

100A, 100B, 100C, 100D, 100E, 100F: flexible transparent conductive film,
1: polymer substrate, 10: first nano-thin film layer,
20: second nano-thin film layer, 30: third nano-thin film layer,
40: fourth nano-thin film layer, 50: fifth nano-thin film layer,
60: 6th nano thin film layer, 70: anti-fingerprint layer,
80: anti-glare layer, 90: 7th nano-thin film layer

Claims (21)

polymer substrate;
a first nano-thin film layer disposed on one surface of the polymer substrate and containing a first metal compound having a refractive index of 1.7 or more;
disposed on the first nano-thin film layer, (i) a first metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) the first metal a second nano-thin film layer containing an oxide of or a nitride of the first metal; and
A third nano-thin film layer disposed on the second nano-thin film layer and containing silver (Ag)-containing metal
Including, a flexible transparent conductive film. 3. The method of claim 2,
The first metal compound is at least one selected from a silicon nitride-based material, a titanium nitride-based material, an aluminum nitride-based material, a niobium oxide-based material, and an aluminum oxide-based material, a flexible transparent conductive film. According to claim 1,
The first nano-thin film layer is
1A nano-thin film layer disposed on the polymer substrate and containing a metal oxide having a refractive index of 1.7 or more; and
1B nano thin film layer disposed on the 1A thin film layer and containing a metal nitride having a refractive index of 1.7 or more
That comprising a, flexible transparent conductive film. The method of claim 1,
The thickness of the first nano-thin film layer is in the range of 10 to 60 nm, a flexible transparent conductive film. According to claim 1,
The second nano-thin film layer will have a thickness in the range of 5 to 20 nm, a flexible transparent conductive film. According to claim 1,
The third nano-thin film layer will have a thickness in the range of 1 to 10 nm, a flexible transparent conductive film. According to claim 1,
The third nano-thin film layer has a surface roughness (Rq) in the range of 0.2 to 2.00, a flexible transparent conductive film. According to claim 1,
disposed on the third nano-thin film layer, (i) a second metal selected from the group consisting of copper (Cu), titanium (Ti), zirconium (Zr), and aluminum (Al), and (ii) the second metal Of, the flexible transparent conductive film further comprising a fourth nano-thin film layer containing the oxide or the nitride of the second metal. 9. The method of claim 8,
The fourth nano-thin film layer will be thinner than the thickness of the second nano-thin film layer, a flexible transparent conductive film. 9. The method of claim 8,
a fifth nano-thin film layer disposed on the fourth nano-thin film layer and containing a second metal compound having a refractive index of 1.7 or more; and
A sixth nano-thin film layer disposed on the fifth nano-thin film layer and having a refractive index of 1.6 or less
further comprising,
The fifth nano-thin film layer and the sixth nano-thin film layer are alternately stacked once or a plurality of times, and the outermost layer is a sixth nano-thin film layer, a flexible transparent conductive film. 11. The method of claim 10,
The total thickness of the fifth nano-thin film layer(s) and the sixth nano-thin film layer(s) is in the range of 40 to 100 nm, the flexible transparent conductive film. 11. The method of claim 10,
The total thickness of the fourth nano-thin film layer, the fifth nano-thin film layer(s) and the total thickness of the sixth nano-thin film layer(s) is in the range of 100 to 500 nm, a flexible transparent conductive film. 11. The method of claim 10,
The sixth nano-thin film layer contains a silicon oxide-based material,
Is disposed on the sixth nano-thin film layer, the flexible transparent conductive film comprising an anti-fingerprint layer formed of a fluorine-based resin. According to claim 1,
The flexible transparent conductive film further comprising an anti-glare layer interposed between the polymer substrate and the first nano-thin film layer. The method of claim 1,
The flexible transparent conductive film which is disposed on the other surface of the polymer substrate and further comprises a seventh nano-thin film layer having a refractive index of 1.5 or less. The method of claim 1,
The flexible transparent conductive film satisfies at least one of the following (i) to (vii) physical properties, a flexible transparent conductive film:
(i) a light transmittance of 85% or more at a wavelength of 380 to 780 nm;
(ii) a reflectance of 5% or less at a wavelength of 380 to 780 nm;
(iii) the rate of change of transmittance over time after standing for 168 hours at 80 °C and 80% is 3% or less,
(iv) a sheet resistance of 8 to 12 Ω/sq,
(v) a far-infrared reflectance of 80% or more at a thermal wavelength of 6-15 μm;
(vi) the surface temperature of the glass substrate may be 25 ~ 33 ℃ after leaving it for 10 minutes in a heating element (eg, heat transfer plate) of about 80 ℃ in the state attached to the glass substrate,
(vii) The surface reflectance is 0.3% or less. A transparent electrode comprising the flexible transparent conductive film according to any one of claims 1 to 16. A display comprising the transparent electrode according to claim 16. A heat shield sheet comprising the flexible transparent conductive film according to any one of claims 1 to 16. A display comprising the heat shield sheet according to claim 19. A heating sheet comprising the flexible transparent conductive film according to any one of claims 1 to 16.

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