KR20200067605A - The transparent electrode device - Google Patents

Abstract

The present invention relates to a transparent electrode device. According to the present invention, the configuration of the device is improved by a transparent support substrate, a nanosilver wire transparent electrode disposed on the transparent support substrate, a nano-condenser layer (nano-unit dielectrics for a condenser) disposed on the nanosilver wire transparent electrode, and the like. Accordingly, disadvantages (for example, a disadvantage that a surface of the nanosilver wire transparent electrode becomes an oxide thin film) of the nanosilver wire transparent electrode is flexibly solved by execution of functions (for example, functions of preventing surface oxidation of a nanosilver wire, preventing a burn-out phenomenon of the same, blocking harmful effects of an external environment, increasing responsibility of the nanosilver wire, etc.) of the nano-condenser layer without a particular problem, thereby enabling a device operation subject to effectively use various kinds of advantages (for example, advantages of forming a transparent electrode at low cost, increasing responsibility of the transparent electrode, lowering power consumption of the transparent electrode, finely and correcting covering a surface of the nanosilver wire, extending lifespan of the transparent electrode, reducing the entire cost of the overcoat, increasing homogeneity of a product, increasing electric characteristics of the transparent electrode, etc.) caused by overcoating of a nano-scaled dielectric condenser layer.

Description

The transparent electrode device

The present invention relates to a transparent electrode device, more specifically, the configuration of the device, <transparent support substrate>, <silver nanowire transparent electrode disposed on the transparent support substrate>, <nano capacitor disposed on the silver nanowire transparent electrode Layer (nano-unit capacitor dielectric)>, and through this, the silver nano-wire transparent electrode has the disadvantages (e.g., the disadvantage of the surface of the silver nano-wire transparent electrode changes to an oxide film), without any problems, nano capacitor layer Functional performance of (e.g., functional performance that blocks surface oxidation of silver nanowires, functional performance that blocks burn-out of silver nanowires, functional performance that blocks adverse effects of the external environment, functional performance that improves the responsiveness of silver nanowires By inducing it to be flexibly solved by, for example, various advantages (for example, being able to form a transparent electrode at an inexpensive price) due to over-coating of a dielectric capacitor layer having a nano scale at the device operator side. The advantage of improving the response performance of the transparent electrode, the advantage of lowering the power consumption of the transparent electrode, the advantage of being able to cover the surface of the silver nanowire more finely and accurately, and extending the life of the transparent electrode Can be guided to effectively enjoy the benefits of being able to reduce the overall cost of the overcoat, the benefits of improving the homogeneity of the product, the benefits of improving the electrical properties of the transparent electrode, etc.) It relates to a transparent electrode device.

With the recent rapid development of electronic device/display related technologies, technologies related to transparent electrodes are also rapidly developing.

For example, Republic of Korea Patent Publication No. 10-2014-135918 (name: method of manufacturing a transparent electrode film) (published on November 27, 2014), Republic of Korea Patent Publication No. 10-2015-39373 (name: transparent electrode and this Included electronic device) (published on April 10, 2015), Korean Patent Publication No. 10-2018-61800 (name: method for manufacturing transparent electrode) (published on August 8, 2018), Korean Patent Publication No. 10-2018- No. 109510 (Name: Manufacturing method of transparent electrode) (published on January 1, 2018), Korean Patent Publication No. 10-2018-124405 (Name: Flexible transparent electrode and manufacturing method thereof) (published on November 21, 2018) An example of such a transparent electrode according to the prior art is disclosed in more detail in et al.

On the other hand, under this conventional system, typically, the main material of the transparent electrode is, for example, ITO (Indium Tin Oxide), ATO (Antimony Tin Oxide), AZO (Antimony Zinc Oxide), silver nano, conductive polymers (for example, polyethylene (Polyethylene) ), polypyrrole, polythiophene, etc., carbon nanotubes (CNT), graphene, and the like are widely adopted.

However, since each of the above-mentioned transparent electrode materials has serious disadvantages as follows, it is inevitable that a large number of people are forced to employ them in the next-generation display products (for example, flexible display products, wearable display products, etc.).

First of all, metal oxides such as ITO (Indium Tin Oxide), ATO (Antimony Tin Oxide), and AZO (Antimony Zinc Oxide) can show very good conductivity, but due to the inherent characteristics of the metal, flexibility is considerably reduced. As a result, the next-generation flexible substrate has a serious disadvantage that is difficult to use.

In addition, in the case of the coating using silver nano or silver nano wire, the coating procedure is very difficult, and since it has unnecessary surface oxidation due to rapid bonding with oxygen after coating, it has good permeability and flexible characteristics. Nevertheless, it has serious disadvantages that are difficult to use in next-generation display products.

For reference, in the related art, in order to prevent surface oxidation of silver nano or silver nano wire coatings, measures to further arrange an over coating layer made of acrylic or a similar resin on the surface of silver nano or silver nano wire coatings were also devised. However, the overcoating layer made of acrylic or a similar resin, for example, raises the electrical resistance value, which is an intrinsic characteristic of silver nanowires, thereby inhibiting the function of the silver nanowires, problems in coating stability for large area coatings, and transparency Since it causes problems such as the inhibition of the homogeneity of the electrode, it is inevitable to follow a large crowd to commercialize the conventional overcoat layer for preventing surface oxidation.

On the other hand, like each of the above materials, in the case of the conductive polymer according to the prior art, the flexible characteristics are excellent, but have a high resistance value, and in particular, due to the unique color of the conductive polymer, the next-generation display product There are serious disadvantages that are difficult to use.

Furthermore, graphite-based materials such as carbon nanotubes (CNT), graphene, etc., inevitably limit the limitations of the dispersion technology to make the coating solution, and the limitations of the binder technology to bond with the substrate, due to the properties of the materials. It has serious disadvantages that are difficult to use in next-generation display products.

No. 10-2014-135918 (Name: Manufacturing method of transparent electrode film) (published on Nov. 27, 2014) Korean Patent Publication No. 10-2015-39373 (name: transparent electrode and electronic device including the same) (published on April 10, 2015) Republic of Korea Patent Publication No. 10-2018-61800 (name: method of manufacturing a transparent electrode) (published on August 8, 2018) Republic of Korea Patent Publication No. 10-2018-109510 (name: manufacturing method of transparent electrode) (published on January 1, 2018) Republic of Korea Patent Publication No. 10-2018-124405 (name: flexible transparent electrode and its manufacturing method) (published on November 21, 2018)

Therefore, the object of the present invention is to configure the device, <transparent support base>, <silver nanowire transparent electrode disposed on the transparent support base>, <nano capacitor layer disposed on the silver nanowire transparent electrode (for nano unit capacitors) Dielectric)>, and through this, the disadvantages of the silver nanowire transparent electrode (e.g., the disadvantage of the surface of the silver nanowire transparent electrode turning into an oxide thin film) without any problems (e.g., electrical resistance, which is a unique characteristic of the silver nanowire) Raise the value, without inhibiting the function of the silver nanowire, the problem of deterioration of coating stability for large area coating, and the occurrence of the problem of inhibiting the homogeneity of the transparent electrode), and performing the function of the nano capacitor layer (e.g., surface oxidation of the silver nanowire) By inducing to be able to be flexibly solved by the function of blocking, the function of blocking the burn-out phenomenon of the silver nano wire, the function of blocking the adverse effects of the external environment, the function of improving the responsiveness of the silver nano wire, etc.) , On the device operator side, various advantages (eg, the advantage of being able to form a transparent electrode at an inexpensive price) due to the over-coating of the dielectric capacitor layer having a nano-scale, the advantage of improving the response performance of the transparent electrode , The advantage of being able to lower the power consumption of the transparent electrode, the advantage of being able to cover the surface of the silver nanowire more finely and accurately, the advantage of being able to extend the life of the transparent electrode, and reducing the overall cost of the overcoat. The aim is to guide you so that you can effectively enjoy the benefits, the benefits of improving the homogeneity of the product, the benefits of improving the electrical properties of the transparent electrode, etc.).

Other objects of the present invention will become more apparent from the following detailed description and accompanying drawings.

In order to achieve the above object, in the present invention, a transparent support substrate; A silver nanowire transparent electrode disposed on the transparent support substrate; Disclosed is a transparent electrode device comprising a nano capacitor layer disposed on the silver nano wire transparent electrode.

In the present invention, the configuration of the device, <transparent support substrate>, <silver nanowire transparent electrode disposed on the transparent support substrate>, <nano capacitor layer disposed on the silver nanowire transparent electrode (nano-condenser dielectric)> In order to improve the system, under the implementation environment of the present invention, the device operating entity side has no problems (eg, the disadvantage of the surface of the silver nanowire transparent electrode being changed to an oxidized thin film) of the silver nanowire transparent electrode (for example, the silver nanowire). Raise the value of electrical resistance, which is an inherent characteristic of silver, to inhibit the function of silver nanowires, to reduce coating stability for large-area coating, and to prevent the problem of inhibiting homogeneity of transparent electrodes), and to perform the function of the nano capacitor layer (for example, It is flexible by performing functions that block the surface oxidation of silver nanowires, functions that block the burn-out phenomenon of silver nanowires, functions that block the adverse effects of the external environment, and functions that improve the responsiveness of silver nanowires). In the end, various advantages (eg, the advantage of being able to form a transparent electrode at a low price, and the ability to improve the response performance of the transparent electrode) due to the over-coating of the dielectric capacitor layer having nanoscale , The advantage of being able to lower the power consumption of the transparent electrode, the advantage of being able to cover the surface of the silver nanowire more finely and accurately, the advantage of being able to extend the life of the transparent electrode, and reducing the overall cost of the overcoat. Can effectively enjoy the benefits of being able to improve the homogeneity of the product, the advantages of being able to improve the electrical properties of the transparent electrode, etc.).

1 is an exemplary view conceptually showing a detailed configuration of a transparent electrode device according to the present invention.
Figure 2 is an exemplary view conceptually showing a preparation step for manufacturing a transparent electrode device according to the present invention.
3 to 5 are process flow charts sequentially showing the manufacturing procedure of the transparent electrode device according to the present invention.
6 is an exemplary view conceptually showing a transparent electrode device according to another embodiment of the present invention.

Hereinafter, a transparent electrode device according to the present invention will be described in more detail with reference to the accompanying drawings.

As shown in FIG. 1, the transparent electrode device 1 according to the present invention is a transparent support substrate 2 having flexible characteristics (eg, PET film, acrylic film, urethane film, PO film, PI film, PP film) Etc.), and the silver nanowire transparent electrode 4 disposed on the transparent support substrate 2 and the nanocapacitor layer 5 disposed on the silver nanowire transparent electrode 4 are systematically combined. Is done.

At this time, in the present invention, the silver nanowires are dispersed in various dispersions, or the silver nanowires are coated alone to form the silver nanowire transparent electrode 4 and, on the surface thereof, inorganic oxides having dielectric properties are made of a coating solution. , To form the nano capacitor layer 5.

Here, the nanocapacitor layer 5 is neodyne oxide (Nd2O3), magnesium titanate (MgTiO3), calcium titanate (CaTiO3), barium titanate (BaTiO3), bismuth oxide (Bi2O3), titanium oxide (TiO2), or zirtanate It has a material of any one of lead cosan (Pb(Ti, Zr)O3).

In addition, the nano-condenser layer 5, in a liquid state, has a feature coated on the silver nanowire transparent electrode 4 by a roll-to-roll process.

Here, the nanocapacitor layer 5 of the present invention preferably has a nano-unit thickness (ie, a nanoscale thickness) of 10 nm to 1000 nm. At this time, when the nano capacitor layer 5 has a thickness of less than 10 nm, the problem of losing the inherent function of overcoating (for example, a problem that the surface oxidation of the silver nanowire transparent electrode 4 cannot be blocked, etc.) This may occur, and when the nano condenser layer 5 has a thickness exceeding 1000 nm, the thickness becomes too thick (for example, the meaning of maintaining the thickness in nano units is lost), for example, a silver nanowire transparent electrode A problem in that the surface resistance of (4) falls, a problem that the nano capacitor layer 5 cannot perform a role as a nano capacitor may occur.

As described above, in the present invention, neodium oxide (Nd2O3), magnesium titanate (MgTiO3), calcium titanate (CaTiO3), barium titanate (BaTiO3), bismuth oxide (Bi2O3), titanium oxide (TiO2), or lead zirconate titanate (Pb(Pb)) Inorganic oxides such as Ti and Zr)O3) are liquefied and coated on the silver nanowire transparent electrode 4 with roll to roll. In this case, all materials containing titanium oxide can be used, and various manufacturing methods are used depending on the characteristics. With it, you can make an overcoat thin film that can protect silver nanowires.

In the present invention, when making a dielectric layer material, that is, a nano-capacitor coating solution as a raw material for the nano-condenser layer 5, hydrothermal synthesis, sol-gel synthesis, supercritical synthesis, heating, nano-dispersion, solid-phase reaction, oxalate, organic acid method Various synthetic methods, such as, can be used, or by various dispersion methods, nano-units can be made to make nano-dielectric materials to be used in the present invention.

At this time, in the case of the sol-gel synthesis, the starting material may be made using titanium tetrachloride, or another material containing titanium in a tetra structure may be used. In the case of the hydrothermal synthesis method, the same procedure can be performed, and in the case of the nano-dispersion, titanium oxide (Nd2O3), magnesium titanate (MgTiO3), and calcium titanate (CaTiO3) are produced by titanium and heat synthesis for each material. Barium titanate (BaTiO3), bismuth oxide (Bi2O3), titanium oxide (TiO2), or lead zirconate titanate (Pb(Ti, Zr)O3) may be used after being nano-sized using a ball mill.

Here, barium titanate (BaTiO3), which is frequently used as a ferroelectric, is a polycrystalline sintered body, is a ferroelectric, and is the first material widely used, and is generally used to make a magnetic capacitor (high dielectric constant meter). Although it is also used as a piezoelectric component, it is generally used that barium (Ba) or titanium (Ti) is replaced with one or two other elements to improve performance.

The barium titanate is usually known as two salts of ortho and meta, and barium titanate (Ba2TiO4=386.62) is made by heating a mixture of 2:1 of barium carbonate and titanium (IV) oxide to 1270°C. Barium autorate is a dark red powder with small isotropic crystals with a large refractive index. With cold dilute hydrochloric acid, it becomes a sol of barium chloride and titanium oxide, which is completely dissolved, and the dissolved solution can be mixed with distilled water to make a nano coating solution.

In addition, the barium metatitanate (BaTiO3=233.26) is the most famous dielectric, and five salts of different crystal types are known, of which four are perovskite structures, and the other is a hexagonal crystal system.

In the case of the perovskite type, barium chloride, barium carbonate, and titanium oxide (IV) are mixed at a molar ratio of 3.3:1.4:1, heated to 1250°C, treated with hot water and nitric acid, and made in hexagonal crystal system. It is made by dissolving an equal amount of barium carbonate and titanium (IV) oxide in alkali carbonate. Then, the general barium oxide and titanium (IV) oxide are heated to a high temperature. It may be made into a tetragonal crystal system or a hexagonal crystal system.

In the perovskite type, the equiaxed crystal system becomes stable at high temperature, and the tetragonal crystal system becomes stable at room temperature. In the middle, there are crystalline regions of three pseudo equiaxed crystal systems, exhibiting strong dielectric properties, and distinct applicability as dielectric materials. Hexagonal crystals do not exhibit strong dielectric properties. It does not decompose by alkali melting, and also does not interfere with hot and dilute nitric acid. It is reduced at a high temperature in the air stream of the reducing gas. When melted with platinum, platinum is exchanged for some titanium. It is also used as a dielectric by making continuous hybrid crystals with strontium metatitanate (SrTiO3).

In conclusion, in the present invention, as shown in FIG. 1, after the primary coating of the silver nanowire transparent electrode 4 on the transparent support substrate 2, a second overcoating with a dielectric having a binder performance is performed, and through this, the silver nano By polarizing the wire transparent electrode 4 in nano-scales finely, a transparent electrode having strong dielectric performance is produced.

The nano capacitor layer 5 according to the present invention has a capacitance defined by the following equation.

<Mathematics>

(여기서, C는 나노 콘덴서층(5)이 가지는 커패시턴스, ε은 나노 콘덴서층(5)이 가지는 고유 유전율, A는 나노 콘덴서층(5)이 가지는 면적, 나노 콘덴서층(5)의 두께)

(Where C is the capacitance of the nano capacitor layer 5, ε is the dielectric constant of the nano capacitor layer 5, A is the area of the nano capacitor layer 5, the thickness of the nano capacitor layer 5)

Of course, as the capacitance value increases, the nanocapacitor layer 5 side of the present invention can exhibit more excellent and various characteristics flexibly.

]에서, 분모의 L 값은 극단적으로 작아지는데 반해, 분자의 A 값은 넓이 단위 스케일(예컨대, ㎠, ㎡ 등)로 커질 수밖에 없게 되며(참고로, ε값은 거의 상수 상태를 유지하게 됨), 결국, 본 발명의 구현환경 하에서, 나노 콘덴서층(5) 측에서는 매우 큰 커패시턴스 값을 자연스럽게 가질 수 있게 되고, 그 결과, 별다른 어려움 없이, 예를 들어, 은나노 와이어의 표면산화를 차단하는 기능, 은나노 와이어의 번-아웃 현상을 차단하는 기능, 외부환경의 악영향을 차단하는 기능, 은나노 와이어의 응답성을 향상시키는 기능 등을 폭 넓게 발휘할 수 있게 된다.At this time, since the nanocapacitor layer 5 side of the present invention has a nanoscale thickness of 10 nm to 1000 nm as described above, the above equation [

], while the L value of the denominator is extremely small, the A value of the molecule is forced to increase on a unit scale (e.g., cm2, m2, etc.) (for reference, the ε value remains almost constant) , In the end, under the implementation environment of the present invention, it is possible to naturally have a very large capacitance value on the nanocapacitor layer 5 side. As a result, without much difficulty, for example, a function of blocking surface oxidation of silver nanowires, silver nano The function of blocking the burn-out phenomenon of the wire, the function of blocking the adverse effects of the external environment, and the function of improving the responsiveness of the silver nanowire can be widely exhibited.

On the other hand, a hard coating layer 3 for improving adhesion of the silver nanowire transparent electrode 4 is additionally formed at the interface between the transparent support base 2 and the silver nanowire transparent electrode 4.

In this case, the composition forming the hard coating layer (3) is an acrylic functional group, a methacrylic functional group or an oligomer (Oligomer) having various functional groups, a monomer (Momomoer) or a mixture of oligomers and monomers, and various composite inorganic materials as required Uses a solvent to control viscosity and fluidity, a photoinitiator for absorbing energy from a light source to cause a polymerization reaction, and an antioxidant for inhibiting an oxidation reaction, a polymerization inhibitor, and uv to show stable properties to uv Blockers, absorbents, and small levels of leveling agents are used to stabilize the surface roughness.

At this time, the hard coating layer 3 preferably has a thickness of 2 μm to 5 μm, and a refractive index of 1.4 to 1.52. Here, the hard coating layer 3 may have aero silica as an additional component for improving the bonding strength with the silver nanowire transparent electrode 4 depending on the situation. In this case, the aero silica is 1% to 10%. A solid component having a content of is to form the constituent components of the hard coating layer (3).

In the above-described present invention, while simultaneously solving the large-area application problem and late responsiveness, rapid oxidation and deterioration problem, high-cost low-efficiency problem, production stability problem, which was always a problem in the existing silver nanowire, the silver nanowire transparent electrode ( 4) You can guide them to have even better performance.

Due to the present invention, it is possible to make the transparent silver nanowire transparent electrode 4 at low cost, and also, by overcoating the silver nanowire transparent electrode 4 as the nano capacitor layer 5 of an inorganic material, that is, a dielectric component, Durability can be improved. In particular, by strengthening the heat resistance, it is possible to solve all the phenomenon that the silver nano-wire transparent electrode 4 is easily burned out.

In addition, in the present invention, by using a dielectric (that is, the nano-condenser layer 5 of the dielectric component) as an overcoating, it is possible to make a transparent electrode showing excellent response speed even under a high resistance silver nanowire environment.

In particular, the dielectric (ie, the nano-condenser layer 5 of the dielectric component) employed in the present invention is a material that does not generate a direct current, and when an electric field is applied, both the non-polar molecule and the polar molecule within the electric moment of the electric dipole By forming the, it is possible to perform a function of canceling a certain amount of the surrounding electric field, and in the end, it is possible to have very excellent electrical properties on the transparent electrode device 1 side of the present invention.

Furthermore, in the present invention, as the nano-condenser layer 5 of the dielectric component is used, when an electric field is applied, electrically polarized molecules are entirely aligned, so that the direction of the electric field due to polarization is reversed to that of the external electric field, As a result, the strength of the electric field in the dielectric becomes smaller than that of the external electric field, so that, in the end, the transparent electrode device 1 side of the present invention can exhibit excellent performance even with a small capacitance.

In this way, in the present invention, the configuration of the transparent electrode device 1 is <transparent support substrate 2>, <silver nanowire transparent electrode 4 disposed on the transparent support substrate 2>, <silver nanowire transparent electrode (4) Since the nanocapacitor layer 5 (nanocondenser dielectric for nano-scaled capacitors) disposed on> is improved, under the implementation environment of the present invention, the disadvantages of the silver nanowire transparent electrode 4 on the device operator side (E.g., the disadvantage that the surface of the silver nanowire transparent electrode turns into an oxidized thin film) without any problems (e.g., by raising the electric resistance value, which is a unique characteristic of the silver nanowire, impairing the function of the silver nanowire, for large area coating) Without the problem of coating stability deterioration, the problem of inhibiting the homogeneity of the transparent electrode, etc., performing the function of the nano capacitor layer (e.g., performing the function of blocking the surface oxidation of the silver nano wire, performing the function of blocking the burn-out phenomenon of the silver nano wire, It can be flexibly solved by performing a function to block the adverse effects of the external environment, performing a function to improve the responsiveness of the silver nanowires, and, finally, various advantages (e.g., due to the overcoating of the nanoscale dielectric capacitor layer) , The advantage of being able to form a transparent electrode at an inexpensive price, the advantage of being able to improve the response performance of the transparent electrode, the advantage of being able to lower the power consumption of the transparent electrode, and to cover the surface of the silver nanowires more finely and accurately. The advantage of being able to extend the life of the transparent electrode, the advantage of being able to reduce the overall cost of the overcoat, the advantage of being able to improve the homogeneity of the product, and the electrical properties of the transparent electrode can be improved. You can enjoy the benefits that you have).

Hereinafter, a detailed embodiment of the transparent electrode device 1 according to the present invention will be described in detail.

<Example 1> (See Fig. 2)

1. Preparation step of transparent support material (2) (S1)

As the transparent support substrate (2), PET (Polyethylene terephthalate) having a thickness of 100 micron called U43R, produced by Kolon in Korea, which has excellent optical performance, is basically 90% because it has high optical properties. It exhibits the above transmittance performance. In addition, the urethane primer on the surface, more specifically, consists of a 50-100 nm layer of a primer layer made of a polyester layer, providing stable adhesion performance when forming a hard coating layer on the surface of the U43R base. do.

2. Preparation step of hard coating solution (S2)

In order to implement a stable hard coating layer 3 on the prepared transparent support base 2, due to the structural characteristics of U43R, the refractive index (RI value) of the hard coating layer 3 is appropriately between 1.42 and 1.48, so it is generally used. All of the possible hard coatings can be used, but a hard coating solution containing an inorganic material was prepared. The inorganic material used accordingly does not have to be specified in the erotic silica, but OX50 (10 g) provided by Evonik was used.

First, the prepared distilled water (80 mL) and methanol (20 mL) were previously stirred for 10 minutes at 1000 rpm in a high-speed stirrer.

Subsequently, EVONIC's OX50 (1KG) was added to the stirred solution, and sodium polyacrylate (1G) was placed in an autoclave, and reacted at 750°C for 12 hours at 750 atm to make ultra-fine nano-sized silica sol. At this time, the silica sol has a size of 10-20 nm, and may serve to induce adhesion of a material such as silver nano in hard coating.

Next, 100G of urethane acrylate oligomer (EB-1200) and a reactive monomer, trimethyrolpropane triacrylate (TMPTA) 20G, tri(2-hydroxy ethyl) isocyanate diacrylate (THEICDA) 20G in a beaker. And, photoinitiator hydroxy cyclohexyl phenyl ketone (IGCURE 184) 1G, and benzophenone (BP) 1G was added to the above-described silica sol 3ML, the solvent methyl ethyl ketone (MEK) 150G and toluene (Toluene) 150g After the addition, 0.3 g of the antioxidant dibutyl hydroxytoluene (BHT) was added again, and for the safety of the resin, 0.3 g of the polymerization inhibitor hydroquinone and 1 g of the sunscreen HALS were added, followed by high speed. The mixture was stirred for 30 minutes at 500 RPM in a stirrer to make a hard coating solution for easy attachment of silver nanowires.

3. Step of preparing the silver nanowire (S3)

In order to manufacture silver nanowires having an ultra-fine structure, silver nanowires are introduced into a hydrothermal synthesizer with an ionic liquid, which is a general method, and an aqueous solution in which silver salts are dissolved, and the temperature and pressure are changed while the silver nanowires are used. It was manufactured (of course, it is also possible to use silver nanowires commonly available on the market).

4. Preparing a nanocondenser coating solution composed of a dielectric (S4)

First, barium titanate (BaTiO3) is prepared by a hydroxide method. The oxalate method is a method of synthesizing BT through pyrolysis of raw material barium titanyl oxalate, and it is important to obtain particulate BTO as a starting material for BT synthesis below 100 nm. The hydrothermal synthesis method can generally produce barium titanate (BaTiO3) having a narrow particle size distribution.

At this time, 150G of barium titanate (BaTiO3), 150G of distilled water, and 150G of methanol are placed in an autoclave to make a supercritical state under 1200atm at a temperature of 300°C for 12 hours to make barium titanate (BaTiO3) into a nanoparticle size. At this time, the primary particle size of the barium titanate (BaTiO3) made was 10-20 nm in size.

5. Manufacturing the transparent electrode device 1 (see FIGS. 3 to 5)

On the prepared U43 PET film, a hard coating solution having a refractive index of 1.46 was uniformly coated with micro gravure coating. Heated at 80°C for 1 minute, all the solvent in the hard coating solution was blown away, and cured to 200MJ through a UV curing machine while leaving an acrylic solid content to make a hard coating layer 3 having a strength of 500G 2H (FIG. 3).

On the surface of the prepared hard coating layer 3, the prepared silver nanowire (refer to item 3 above) was coated using a slot die to thereby form a silver nanowire transparent electrode 4 (see FIG. 4). The coated silver nanowire transparent electrode 4 was cured at 150 degrees for 2 minutes. At this time, as the silver nanowire transparent electrode 4 and some radicals and silicas on the surfaces of the hard coating layer 3 undergo a plastic change, the hard coating layer 3 and the silver nano wire are combined, and thus on the hard coating layer 3. A silver nanowire transparent electrode 4 was made.

The nano-barium titanate (BaTiO3) coating solution is coated on the surface of the silver nano-wire transparent electrode 4 by using a slot die to protect the surface of the made silver nano-wire transparent electrode 4 and increase the dielectric constant to enhance the function of the transparent electrode. , Through this, a nano capacitor layer 5 was prepared. At this time, the coating procedure was performed at 150 degrees for 5 minutes.

<Example 2>

<1. Preparation step (S1) of the transparent support substrate 2, <2. Preparation step of hard coating solution (S2)>, <3. The step of preparing the silver nanowire (S3)> was performed in the same manner as in Example 1.

4. Preparing a nanocondenser coating solution composed of a dielectric (S4)

100 g of titanium tetrachloride and 100 g of water, 100 g of methanol, were placed in a 500 ml jacketed reactor, the ambient temperature was set to 60 degrees, and reacted at 200 RPM for 24 hours. The reacted titanium tetrachloride was made into titanium dioxide sol through polycondensation with hydrosis.

5. Manufacturing the transparent electrode device 1 (see FIGS. 3 to 5)

First, a hard coating solution made of a refractive index of 1.46 was uniformly coated with a micro gravure coating on the prepared U43 PET film, and through this, a hard coating layer 3 was prepared. At this time, by heating at 80°C for 1 minute, all of the solvent in the hard coating solution was blown away and cured to 200 MJ through a UV curing machine while leaving an acrylic solid content to make a hard coating layer 3 having a strength of 500G 2H. .

Subsequently, on the surface of the prepared hard coating layer 3, the prepared silver nanowire (see item 3 above) was coated using a slot die, and through this, the silver nanowire transparent electrode 4 was formed (see FIG. 4). . The coated silver nanowire transparent electrode 4 was cured at 150 degrees for 2 minutes. At this time, as the silver nanowire transparent electrode 4 and some radicals and silicas on the surfaces of the hard coating layer 3 undergo a plastic change, the hard coating layer 3 and the silver nano wire are combined, and thus on the hard coating layer 3. A silver nanowire transparent electrode 4 was made.

Subsequently, in order to protect the surface of the produced silver nanowire transparent electrode 4 and increase the dielectric constant to enhance the function of the transparent electrode, a coating of titanium dioxide (TiO2) coating solution is applied to the surface of the silver nanowire transparent electrode 4 using a slot die. And through this, a nano-condenser layer 5 was prepared. At this time, the coating procedure was performed at 150 degrees for 5 minutes.

<Comparative Example 1>

<1. Preparation step of transparent support material>, <2. Preparation step of hard coating solution>, <3. The step of preparing the silver nanowires> was performed in the same manner as in Examples 1 and 2 above.

4. Step of preparing the overcoat

First, ditrimethylopropane tetraacrylate (DTMPTTA) 30G, 1,6-hexadiol diacrylate (HDDA) 5G, Igacure (IGACURE 184) 1.7G, methyl ethyl ketone (MEK) 150G, and toluene 150G Was added to a stirrer and stirred at 200 RPM for 20 minutes to prepare an overcoating solution.

5. Coating step for each layer

First, a hard coating solution having a refractive index of 1.46 was uniformly coated on the prepared U43 PET film by micro gravure coating. Heated at 80°C for 1 minute to blow all the solvents inside the hard coating solution, and cured to 200MJ through a UV curing machine in the state of leaving acrylic solid content to make a hard coating having a strength of 500G 2H.

Silver nanowires were coated on the prepared hard coating layer surface using a slot die. The coated silver nanowires were cured at 150 degrees for 2 minutes. At this time, a silver nanowire layer was formed on the hard coating layer as the hard coating layer and the silver nanowire were combined while plastic radical change of some radicals and silicas of the silver nanowire and the hard coating surface.

To protect the surface of the prepared silver nanowire layer, an overcoating solution was coated with a UV curing agent, thereby making a transparent silver nanowire electrode film comparable to the present invention.

<Comparative Example 2>

<1. Preparation step of transparent support material>, <2. Preparation step of hard coating solution>, <3. The step of preparing the silver nanowires> was performed in the same manner as in Examples 1 and 2 above.

4. Step of preparing the overcoat

First, pentaerythritol triacrylate (PETA) 30G, 1,6-hexadiol diacrylate (HDDA) 5G, Igacure (IGACURE 184) 1.7G, methyl ethyl ketone (MEK) 150G and toluene 150G It was put in a stirrer and stirred at 200 RPM for 20 minutes to prepare an overcoating solution.

5. Coating step for each layer

On the prepared U43 PET film, a hard coating solution having a refractive index of 1.46 was uniformly coated with micro gravure coating. Heated at 80°C for 1 minute to blow all the solvents inside the hard coating solution, and cured to 200MJ through a UV curing machine in the state of leaving acrylic solid content to make a hard coating having a strength of 500G 2H.

On the surface of the hard coating layer, the prepared silver nanowires were coated using a slot die. The coated silver nanowires were cured at 150 degrees for 2 minutes. At this time, a silver nanowire layer was formed on the hard coating layer as the hard coating layer and the silver nanowire were combined while plastic radical change of some radicals and silicas of the silver nanowire and the hard coating surface.

Another transparent silver nanowire electrode film that can be compared with the present invention was made by coating the overcoat with a UV curing agent to protect the surface of the produced silver nanowire layer.

Each transparent electrode device manufactured as described above exhibited the results as shown in Table 1 below.

As in the experimental data below, the transparent electrode device 1 having an overcoating using the dielectric according to the present invention has a lower resistance value compared to Comparative Examples 1 and 2, and also after overcoating It can be seen that the low-resistance-value function is maintained while hardly causing a change in the resistance value, and further, even when coated with a large area, the product has excellent homogeneity. And even during aging, it has been found that the transparent electrode device 1 according to the present invention made of an inorganic dielectric has excellent durability.

(Resistance value data for each item) Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Resistance before overcoating 29 29 29 29 Resistance after overcoating 29 29 50 60 Large area homogeneity after overcoating
(Left/Middle/Right)
(Ω) 29/29/29 28/29/29 51/×/60 62/×/59 Resistance after aging at 80 degrees for 100 hours
(Ω) 30 29 1250 1300

According to the present invention, various modifications can be made to the present invention.

For example, as shown in FIG. 6, in the present invention, it is also possible to take a changed measure to further form the hard coating layer 3 on the rear surface of the transparent support substrate 1.

Of course, even in the case of such other implementations, the device operating subject side has the disadvantages of the silver nanowire transparent electrode 4 (eg, the disadvantage of the surface of the silver nanowire transparent electrode 4 being changed to an oxidized thin film) without any problems. By performing the function of the layer 5, it can be flexibly solved, and in the end, it is possible to effectively enjoy various advantages due to the over-coating of the dielectric capacitor layer having nanoscale.

The present invention is not limited to a specific field, and in various fields that require blocking of the outflow of the electrolyte, it exhibits an overall useful effect.

In addition, although specific embodiments of the present invention have been described and illustrated above, it is obvious that the present invention may be implemented in various ways by those skilled in the art.

Such modified embodiments should not be individually understood from the technical spirit or viewpoint of the present invention, and such modified embodiments should be within the scope of the appended claims of the present invention.

1: Transparent electrode device
2: Transparent support base
3: Hard coating layer
4: Silver nano wire transparent electrode
5: nano capacitor layer

Claims (10)

A transparent support substrate;
A silver nanowire transparent electrode disposed on the transparent support substrate;
A transparent electrode device comprising a nano capacitor layer disposed on the silver nano wire transparent electrode. The nanocapacitor layer of claim 1, wherein the nano-condenser layer is neodymium oxide (Nd2O3), magnesium titanate (MgTiO3), calcium titanate (CaTiO3), barium titanate (BaTiO3), bismuth oxide (Bi2O3), titanium oxide (TiO2), or titanate. A transparent electrode device comprising any one of lead zirconate (Pb(Ti, Zr)O3). The transparent electrode device according to claim 1, wherein the nano capacitor layer is coated on the silver nanowire transparent electrode by a roll-to-roll process in a liquid state. The transparent electrode device according to claim 1, wherein the nano capacitor layer has a thickness of 10 nm to 1000 nm. The transparent electrode device according to claim 1, wherein a hard coating layer for improving adhesion of the silver nanowire transparent electrode is further formed at an interface between the transparent support base material and the silver nanowire transparent electrode. The method according to claim 5, wherein the hard coating layer is an oligomer (Oligomer) having a functional group, a monomer (Momomoer), a composite inorganic material, a solvent for controlling viscosity and fluidity, a photoinitiator for causing a polymerization group, and preventing an oxidation reaction A transparent electrode device characterized by being formed by a coating process and a curing process of a hard coating solution containing an antioxidant, polymerization inhibitor, uv blocker, absorbent, or leveling agent. The transparent electrode device according to claim 5, wherein the hard coating layer has a thickness of 2 μm to 5 μm. 6. The transparent electrode device according to claim 5, wherein the hard coating layer has a refractive index of 1.4 to 1.52. 6. The transparent electrode device according to claim 5, wherein the hard coating layer has aero silica as an additional component. 10. The transparent electrode device according to claim 9, wherein the aero silica is a solid component having a content of 1% to 10% and constitutes a component of the hard coating layer.

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