KR102004025B1 - Transparent conductor and display apparatus comprising the same - Google Patents

Transparent conductor and display apparatus comprising the same Download PDF

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Publication number
KR102004025B1
KR102004025B1 KR1020160031194A KR20160031194A KR102004025B1 KR 102004025 B1 KR102004025 B1 KR 102004025B1 KR 1020160031194 A KR1020160031194 A KR 1020160031194A KR 20160031194 A KR20160031194 A KR 20160031194A KR 102004025 B1 KR102004025 B1 KR 102004025B1
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South Korea
Prior art keywords
nanowire
group
transparent conductor
transparent
meth
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KR1020160031194A
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Korean (ko)
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KR20170107332A (en
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김영훈
심대섭
강경구
김도영
신동명
임지현
한지영
황오현
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삼성에스디아이 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/08—Several wires or the like stranded in the form of a rope
    • H01B5/10—Several wires or the like stranded in the form of a rope stranded around a space, insulating material, or dissimilar conducting material
    • H01B5/102—Several wires or the like stranded in the form of a rope stranded around a space, insulating material, or dissimilar conducting material stranded around a high tensile strength core
    • H01B5/104—Several wires or the like stranded in the form of a rope stranded around a space, insulating material, or dissimilar conducting material stranded around a high tensile strength core composed of metallic wires, e.g. steel wires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

And a transparent conductive layer formed on the base layer, wherein the transparent conductive layer has a first nanowire group containing at least one nanowire having a length of 1 mu m or more and less than 20 mu m and a second nanowire group having a length of 20 mu m or more and 40 mu m Wherein the ratio of the average length of the nanowires of the first nanowire group to the nanowire group of the second nanowire group is from 1: 2 to 1: 4, And a display device including the same are provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent conductor and a display device including the transparent conductor.

The present invention relates to a transparent conductor and a display device including the transparent conductor.

The metal nanowire-containing transparent conductor may be included in a touch screen panel or the like of a display device. The metal nanowire-containing transparent conductor has a structure in which a conductive network formed of metal nanowires is impregnated in the matrix.

The metal nanowire-containing transparent conductor can be made by coating a metal nanowire dispersion on a substrate layer. Since the metal nanowires are mainly oriented in the coating direction of the dispersion due to the nanowire shape, the transparent conductor or the patterned transparent conductor thereof is not uniform in line resistance in the vertical and horizontal directions, When used in a device, the yield may drop.

The background art of the present invention is described in Korean Patent Publication No. 2012-0053724.

A problem to be solved by the present invention is to provide a transparent conductor having a high channel resistance uniformity, an excellent channel forming yield, and a low haze, thereby having excellent optical characteristics.

Another problem to be solved by the present invention is to provide a transparent conductor having a low surface resistance and a good appearance.

The transparent conductor of the present invention comprises a base layer and a transparent conductive layer formed on the base layer, wherein the transparent conductive layer includes a first nanowire group containing at least one nanowire having a length of 1 m or more and less than 20 m Wherein the ratio of the average length of the nanowires of the first nanowire group to the nanowire group of the second nanowire group is 1: 2 To 1: 4.

The display device of the present invention may include the transparent conductor of the present invention.

The present invention provides a transparent conductor having high channel resistance uniformity, excellent channel formation yield, and low haze, and having excellent optical characteristics.

The present invention provides a transparent conductor having a low surface resistance and good appearance.

1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.
2 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.
3 is a cross-sectional view of a display device according to an embodiment of the present invention.
4 is a cross-sectional view of a display device according to another embodiment of the present invention.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

The terms "upper" and "lower" in this specification are defined with reference to the drawings, wherein "upper" may be changed to "lower", "lower" What is referred to as "on" may include not only superposition, but also intervening other structures in the middle. On the other hand, what is referred to as "directly on," " directly above, "or" directly formed, "

As used herein, "(meth) acrylic" means acrylic and / or methacrylic.

As used herein, the term "aspect ratio" means the ratio (L / d) of the longest length (L) of the metal nanowires to the shortest diameter (d) of the cross section of the metal nanowires, Mean length of nanowire "means the sum of the lengths of the nanowires of the group of nanowires divided by the total number of nanowires. The average length of the nanowires can be measured with a scanning electron microscope (SEM).

In the present specification, "channel resistance deviation value" means a value obtained by subtracting a value obtained in each of the x-axis direction and the y-axis direction, when one direction of the transparent conductor or the patterned transparent conductor is x- Means the value calculated by the following Equation 1 using line resistances R x and R y . The lower the channel resistance deviation value, the higher the channel resistance uniformity. For example, the x-axis direction may be the direction in which the metal nanowire dispersion is coated in the formation of the transparent conductive layer, and in this case R y ≥ R x :

<Formula 1>

Channel resistance deviation value = (R y - R x ) / R x x 100

Hereinafter, a transparent conductor according to an embodiment of the present invention will be described with reference to FIG. 1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.

Referring to FIG. 1, a transparent conductor 100 according to an exemplary embodiment of the present invention may include a base layer 110 and a transparent conductive layer 120.

The base layer 110 may support the transparent conductive layer 120 and protect the transparent conductive layer 120. The base layer 110 may include a resin film having a light transmittance of 85% to 100%, more specifically 90% to 99% at a wavelength of 550 nm. Within this range, the optical characteristics of the transparent conductor can be improved. Specifically, the resin may be selected from the group consisting of polyester, polyolefin, polysulfone, polyimide, silicone, polystyrene, polyacrylic, polyvinyl chloride resin including polycarbonate, cyclic olefin polymer, polyethylene terephthalate and polyethylene naphthalate But is not limited thereto. The base layer 110 may have a thickness of 10 占 퐉 to 200 占 퐉, specifically 30 占 퐉 to 150 占 퐉, more specifically, 30 占 퐉 to 100 占 퐉. Within this range, the substrate layer may be used for the transparent conductor. 1, the base layer 110 is a single layer, but the base layer may be a multi-layer, and a functional layer may be formed on the base layer 110 although not shown in FIG. The functional layer may be formed as a separate layer independently of the substrate layer or may be formed such that one side of the substrate layer is a functional layer, providing hard coating, corrosion prevention, antireflection, adhesion enhancement, oligomer elution preventing function and the like .

The transparent conductive layer 120 is formed on the substrate layer 110 and can provide conductivity and flexibility to the transparent conductive material 100. [ The transparent conductive layer 120 may be formed directly on the base layer 110.

The transparent conductive layer 120 includes a first group of nanowires 121, a second group of nanowires 122 and a matrix 123. The first group of nanowires 121 includes a second group of nanowires 122, The ratio of the average length of the nanowires of the first nanowire group 121 and the second nanowire group 122 may be 1: 2 to 1: 4. The transparent conductor 100 of the present embodiment includes two types of nanowires having different lengths in the transparent conductive layer 120, thereby lowering the channel resistance deviation value, resulting in high channel resistance uniformity, excellent channel formation yield, The optical characteristics can be excellent and the surface resistance can be low. Specifically, the transparent conductor 100 may have a channel resistance deviation value of 100% or less, specifically 30% to 90%, and a haze of 1.0% or less, specifically 0.01% to 1.0% at a wavelength of 550 nm. In the above range, when the transparent conductor is patterned and used for a display device, the deviation of the channel resistance is reduced according to the angle of the channel, so that it is more advantageous for driving the device and can be more easily used for the optical display device.

The first nanowire group 121 is included in the transparent conductive layer 120 and has a smaller length than the second nanowire group 122 to be described later. When the transparent conductive layer 120 is formed, the second nanowire group 122 It is possible to lower the channel resistance deviation value of the transparent conductor 100 by suppressing the orientation in only one direction. FIG. 1 illustrates a case where the first nanowire group 121 is completely impregnated into the transparent conductive layer 120, but the present invention is not limited thereto. The first nanowire group 121 may be formed on the outside of the transparent conductive layer 120 Some may be exposed. As shown in FIG. 1, when the first nanowire group 121 is completely impregnated into the transparent conductive layer 120, the oxidation of the nanowire can be reduced and the sheet resistance of the transparent conductive material 100 can be further lowered.

The first group of nanowires 121 may contain at least one metal nanowire having a length of 1 탆 or more and less than 20 탆. Within this range, it is possible to lower the value of the channel resistance deviation of the transparent conductor and lower the haze and the sheet resistance. The average length of the nanowires of the first nanowire group 121 may be 5 탆 to 18 탆, specifically, 5 탆 to 15 탆. The first nanowire group 121 may include less than 50 wt%, specifically 10 wt% to 30 wt% of the total of the first nanowire group 121 and the second nanowire group 122. The channel resistance variation value of the transparent conductor can be lowered and the haze can be lowered in the above average length and content range to improve the optical characteristics. The metal nanowire may have an aspect ratio of 10 to 5000, specifically 500 to 1000, more specifically 500 to 700. The metal nanowire may have a cross-sectional diameter of more than 0 nm but not more than 100 nm, specifically, 10 nm to 100 nm, more specifically, 10 nm to 30 nm. In the aspect ratio and the diameter range, a high aspect ratio can be achieved to increase the conductivity of the transparent conductor and reduce the surface resistance. The metal nanowire may be formed of a metal including at least one of silver, copper, aluminum, nickel, and gold, and may specifically include silver nanowires.

The second group of nanowires 122 are included in the transparent conductive layer 120 and may form a conductive network to provide conductivity to the transparent conductive layer 120 and lower the sheet resistance. 1 illustrates a case where the second nanowire group 122 is completely impregnated into the transparent conductive layer 120, but the present invention is not limited thereto and may be partially exposed to the outside of the transparent conductive layer 120. As shown in FIG. 1, when the second nanowire group 122 is completely impregnated into the transparent conductive layer 120, oxidation of the nanowire is prevented and the sheet resistance can be further lowered.

The second group of nanowires 122 may include at least one metal nanowire having a length of 20 mu m or more and 40 mu m or less. Within this range, it is possible to lower the value of the channel resistance deviation of the transparent conductor and lower the haze and the sheet resistance. The average length of the nanowires of the second group of nanowires 122 may be 20 [mu] m to 35 [mu] m. The second group of nanowires 122 may include at least 50 wt%, specifically at least 70 wt% to 90 wt% of the first group of nanowires 121 and the second group of nanowires 122. The sheet resistance of the transparent conductor can be lowered and the conductivity can be improved in the above average length and content range. The metal nanowires of the second nanowire group 122 may be formed of the same or different aspect ratios, cross-sectional diameters, and metal materials as the metal nanowires of the first nanowire group 121 described above.

The entire first nanowire group 121 and the second nanowire group 122 may be included in the transparent conductive layer 120 in an amount of 40% by weight to 80% by weight, specifically 50% by weight to 70% by weight. Within the above range, the conductivity of the transparent conductor can be increased.

The matrix 123 is formed on the base layer 110 to strengthen the bond between the base layer 110 and the transparent conductive layer 120 and to form the first nanowire group 121 and the second nanowire group 122, The oxidation resistance of the metal nanowires is prevented so that the sheet resistance of the transparent conductor 100 is prevented from rising and the optical characteristics, chemical resistance, solvent resistance, durability (reliability), etchability, etc. of the transparent conductor 100 can be increased have.

The matrix 123 may be formed of a composition for a matrix containing a pentafunctional or higher (meth) acrylic compound, a bifunctional or trifunctional (meth) acrylic compound, and an initiator.

The (meth) acrylic compound having five or more functional groups may include at least one of a (meth) acrylic monomer and a (meth) acrylic oligomer in a pentafunctionality to a tenth functionality, specifically a pentafunctionality or a hexafunctionality. The (meth) acrylate monomer having five or more functional groups is preferably a monomer containing at least a (meth) acrylic monomer having five or more functionalities of a polyhydric alcohol of C3 to C20 and having at least one of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Caprolactone-modified dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. The (meth) acrylic oligomer having five or more functional groups may be at least one of a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a silicon containing (meth) acrylate oligomer .

The bifunctional or trifunctional (meth) acrylic compound is a non-urethane-based bifunctional or trifunctional (meth) acrylic compound. The (meth) acrylic monomer may be a (meth) acrylic monomer or an alkoxy group of a non-modified C2 to C20 polyhydric alcohol (Meth) acrylic monomer of a C 2 to C 20 polyhydric alcohol modified with an alkyl (meth) acrylate or methacrylate (meth) acrylate. The (meth) acrylic monomers of the non-modified C2 to C20 polyhydric alcohols include trimethylol propane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (Meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. The (meth) acrylic monomer of the C2 to C20 polyhydric alcohol modified with an alkoxy group may include one or more of ethoxylated trimethylol propane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate . The (meth) acrylic compound having 5 or more functional groups is contained in an amount of 5 to 40% by weight, specifically 5 to 30% by weight, based on the weight of the solid matrix composition, and the bifunctional or trifunctional (meth) 25% by weight to 85% by weight, specifically 25% by weight to 60% by weight. Within the above range, the transparency of the transparent conductor can be high and reliability. As used herein, "solids" means the entirety of the composition for a matrix except for the solvent.

The initiator may be a photopolymerization initiator having an absorption wavelength of 150 nm to 500 nm, and may be one or more of an alpha-hydroxy ketone type or alpha-amino ketone type, for example, 1-hydroxycyclohexyl phenyl ketone or a mixture . The initiator may be included in the composition for solid matrix-based matrices in an amount of 1 wt% to 15 wt%, specifically 1 wt% to 11 wt%. Within the above range, the solid content of the matrix composition can be completely cured, and the remaining amount of the initiator remains, thereby preventing the optical characteristics of the transparent conductive layer from deteriorating.

The composition for a matrix may further include at least one of an adhesion promoter, an antioxidant, and an inorganic hollow particle.

The adhesion promoter improves the adhesion of the metal nanowire to the base layer and can improve the reliability of the transparent conductor. The adhesion promoter may include at least one of a silane coupling agent, a monofunctional (meth) acrylic monomer, and a bifunctional (meth) acrylic monomer. These may be included singly or in combination of two or more. The silane coupling agent is a commonly known silane coupling agent, and includes silane coupling agents having an epoxy group such as 3-glycidoxypropyltrimethoxysilane; A silane coupling agent containing a polymerizable unsaturated group such as vinyltrimethoxysilane; Amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; And 3-chloropropyltrimethoxysilane can be used. The monofunctional or bifunctional (meth) acrylic monomer is a monofunctional or bifunctional (meth) acrylic monomer of C3 to C20 polyalcohol, such as isobornyl (meth) acrylate, cyclopentyl (meth) (Meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di Di (meth) acrylate, and the like. The adhesion promoting agent may be included in the composition for solid matrix-based matrices in an amount of 1 wt% to 20 wt%, specifically 5 wt% to 15 wt%. Within the above range, the reliability and conductivity of the transparent conductor can be improved, and the adhesion of the transparent conductive layer can be improved.

Antioxidants can prevent oxidation of the network of metal nanowires. The antioxidant may include one or more of triazole-based, triazine-based, phosphite-based phosphorus, Hindered amine light stabilizer (HALS) based, phenol based, and metal acetylacetonate based antioxidant. These may be included singly or in combination of two or more. Specifically, the phosphorus antioxidant is tris (2,4-di-tert-butylphenyl) phosphite and the phenol antioxidant is pentaerythritol tetrakis (3- (3,5- Roxy phenyl) propionate). The antioxidant for HALS is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4- piperidinyl) sebacate, bis (2,2,6,6-tetramethyl-5-piperidinyl) sebacate, dimethyl succinate having 4-hydroxy-2,2,6,6-tetramethyl-1-piperidin- N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- Ethylamine) -1,3,5-triazine, and the like. The metal acetylacetonate antioxidant may include, but is not limited to, tris (acetylacetonato) iron (III), tris (acetylacetonato) chromium (III), and the like. The antioxidant may be contained in the composition for solid matrix-based matrices in an amount of 0.01 wt% to 10 wt%, specifically 0.5 wt% to 7 wt%. In this range, oxidation of the metal nanowires is prevented, pattern uniformity of the patterned transparent conductor is high, and it is advantageous for realizing a fine pattern.

The inorganic hollow particles may have a refractive index of 1.4 or less, specifically 1.33 to 1.38. The average particle size (D50) of the inorganic hollow particles may be 30 nm to 100 nm, specifically 40 nm to 70 nm. May be included in the matrix within the above range, and may be advantageously applied as a transparent conductive layer. The inorganic hollow particles may be selected from the group consisting of silica, mullite, alumina, silicon carbide (SiC), MgO-Al 2 O 3 -SiO 2 , Al 2 O 3 -SiO 2 , MgO-Al 2 O 3 -SiO 2 -LiO 2 , Or a mixture thereof, and they may be surface-treated. The inorganic hollow particles may be contained in the particles themselves, but may be contained in the solution containing the inorganic hollow particles. The inorganic hollow particles may be present in the matrix composition in an amount of from 10% 50% by weight, and 15% by weight to 50% by weight. In the above range, the transmission b * value of the transparent conductor can be lowered and the transmittance can be increased.

The composition for a matrix may further comprise a solvent. The solvent may include at least one of ketone solvents such as methyl isobutyl ketone, and alcohol solvents such as isopropyl alcohol and ethanol. The composition for a matrix may further comprise an additive. The additives may include antistatic agents, ultraviolet absorbers, viscosity modifiers, heat stabilizers, dispersants, thickeners, and the like.

The composition for a matrix may have a viscosity of 0.1 cP to 20 cP at 25 캜. Within the above range, the coating property of the matrix composition is improved and uniformly coated with a thin film, so that the transparent conductive layer can have uniform physical and chemical properties.

The transparent conductive layer 120 may have a thickness of 10 nm to 1 탆, specifically 10 nm to 200 nm. In this range, it can be used in an optical display device.

The transparent conductor 100 may have transparency in a visible light region, for example, a wavelength of 400 nm to 700 nm. Specifically, the transparent conductor 100 may have a total light transmittance of 90% or more, specifically 90% to 99%. Within this range, transparency is good and can be used as a transparent conductor. The transparent conductor 100 has a surface resistance measured by a 4-probe or a non-contact type surface resistance meter of 100? / ?, specifically 30? /? To 100? / ?, more specifically 30? /? . In the above-mentioned range, the surface resistance is low and can be used as an electrode film for a touch panel, and can be applied to a large-area touch panel. The thickness of the transparent conductor 100 may be 10 占 퐉 to 250 占 퐉, specifically, 50 占 퐉 to 200 占 퐉. In the above range, it can be used as a transparent electrode film including a film for a touch panel, and can be used as a transparent electrode film for a flexible touch panel. The transparent conductor 100 is in the form of a film and is patterned by etching or the like, and can be used as a transparent electrode film of a touch panel, an E-paper, or a solar cell.

Hereinafter, a transparent conductor according to another embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.

2, the transparent conductor 100 'of the present embodiment is formed by patterning a transparent conductive layer 120' into a transparent nonconductive layer 120b including a transparent conductive layer 120a and a matrix 123 only The transparent conductor 100 is substantially the same as the transparent conductor 100 of the embodiment of the present invention. The transparent conductive layer 120 'may be formed by patterning the transparent conductive layer 120 according to an embodiment of the present invention in a conventional manner. Specifically, the patterning may include forming a photoresist layer on the transparent conductive layer 120, placing the patterned mask on the photoresist layer, UV exposure, developing, baking, and etching .

Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIG. 3 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

3, an optical display 200 according to an exemplary embodiment of the present invention includes a display unit 210, a polarizer 220, a transparent electrode member 230, a window film 240, an adhesive layer 250, And the transparent electrode member 230 may be formed of a transparent conductor according to embodiments of the present invention. 3 illustrates a structure in which a display unit 210, a polarizer 220, a transparent electrode member 230, and a window film 240 are stacked in this order. The display unit 210, the transparent electrode member 230, The polarizer 220, and the window film 240 may be stacked in this order.

The display unit 210 is for driving the optical display device 200 and may include an optical element including an OLED, an LED, or an LCD device formed on a substrate and a substrate. In one embodiment, the display portion 210 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective layer, and an insulating layer. In other embodiments, the display portion 210 may include an upper substrate, a lower substrate, a liquid crystal layer positioned between the upper substrate and the lower substrate, and a color filter formed on at least one of the upper substrate and the lower substrate. 3 illustrates a structure in which the display unit 210 and the transparent electrode unit 230 are stacked independently of each other, but the transparent electrode unit 230 may be formed inside the display unit.

The polarizing plate 220 is formed on the display unit 210 to realize polarized light or to prevent reflection of external light to realize a display or improve a contrast ratio of the display. The polarizer 220 may be a polarizer alone. Alternatively, the polarizer 220 may include a polarizer and a protective film formed on one or both sides of the polarizer. Although not shown in FIG. 3, a polarizing plate is further formed on the lower portion of the display unit 210, so that the contrast ratio of the display can be improved. At this time, the polarizing plate may be formed on the display unit 210 by an adhesive layer.

The transparent electrode member 230 is formed on the polarizing plate 220 and can generate an electrical signal by detecting a change in capacitance generated when the transparent electrode member 230 is touched by contact or the like. The transparent electrode assembly 230 includes a base layer 110, a first electrode 231 and a second electrode 232 formed on one surface of the base layer 110, a third electrode (not shown) formed on the other surface of the base layer 110 233, and a fourth electrode 234. 3 shows a structure in which the third electrode 233 and the fourth electrode 234 / the substrate layer 110 / the first electrode 231 and the second electrode 232 are stacked in this order. However, the substrate layer 110 The third electrode 233 and the fourth electrode 234 / the base layer 110 / the first electrode 231 and the second electrode 232 may be stacked in this order.

The window film 240 may be formed at the outermost portion of the optical display device 200 to protect the optical display device 200. The window film 240 may be formed of a glass substrate or a flexible plastic substrate.

The adhesive layer 250 is formed between the display unit 210 and the polarizer 220, between the polarizer 220 and the transparent electrode unit 230, between the transparent electrode unit 230 and the window film 240, The polarizer 220, the transparent electrode 230, and the window film 240 can be strengthened. The adhesive layer 250 may be formed of a conventional optically transparent adhesive.

Hereinafter, an optical display device according to another embodiment of the present invention will be described with reference to FIG. 4 is a cross-sectional view of an optical display device according to another embodiment of the present invention.

4, an optical display device 300 according to another embodiment of the present invention includes a transparent electrode member 230 ', a transparent electrode member 230', a third electrode 233 formed on one surface of the substrate layer 110, Except that the first electrode 231 and the second electrode 232 are further formed on the window film 240 'and the fourth electrode 234 and the fourth electrode 234, 200). &Lt; / RTI &gt;

Hereinafter, a method of manufacturing a transparent conductor according to an embodiment of the present invention will be described.

A method of manufacturing a transparent conductor according to an exemplary embodiment of the present invention includes coating a metal nanowire dispersion on a base layer to form a metal nanowire dispersion layer, coating the matrix composition on the metal nanowire dispersion layer, And curing the metal nanowire dispersion layer and the composition for a matrix.

The metal nanowire dispersion can be prepared by mixing the dispersion of the first nanowire group and the dispersion of the second nanowire group. The second nanowire group dispersion can be, but is not limited to, commercially available products from Cambrios (e.g. ClearOhm Ink). The first nanowire group dispersion may be commercially available or may be prepared by treating the second nanowire group dispersion with a probe sonicator to cut the nanowires. At this time, the probe sonicator processing time and / or power can be adjusted so that the ratio of the average length of the nanowires in the dispersion of the first nanowire group dispersion and the dispersion of the second nanowire group is 1: 2 to 1: 4. The first nanowire group dispersion is less than 50 parts by weight, specifically 10 parts by weight to 30 parts by weight, and the second nanowire group dispersion is 50 parts by weight, the total amount of the first nanowire group dispersion and the second nanowire group dispersion is 100 parts by weight Or more and specifically 70 parts by weight to 90 parts by weight.

The metal nanowire dispersion may further include a solvent to further enhance the coating properties of the metal nanowire. The solvent may include, but is not limited to, water, an organic solvent such as alcohol, and the like. The metal nanowire dispersion may further contain a binder, an initiator, an additive, and the like. The additives may be dispersants, thickeners, and the like. The binder may include at least one of a (meth) acrylate-based monofunctional monomer and a (meth) acrylate-based polyfunctional monomer. The dispersing agent can increase the dispersion of the metal nanowires and the binder. Thickening agents can increase the viscosity of the metal nanowire dispersion. The binder, initiator, and additives may be included in the metal nanowire dispersion in an amount of 0.1 wt% to 50 wt%, specifically 5 wt% to 45 wt% based on solids. Within the above range, improvement of optical characteristics, prevention of increase in contact resistance, durability and chemical resistance of the transparent conductor can be improved.

The composition for a matrix may be prepared by mixing a (meth) acrylic compound having five or more functional groups, a bifunctional or trifunctional (meth) acrylic compound, and the like. An adhesion promoting agent, an antioxidant, a solution containing an inorganic hollow particle or an inorganic hollow particle, an additive, a solvent and the like may further be contained in the composition for a matrix.

The metal nanowire dispersion is then coated on the substrate layer to form a metal nanowire dispersion layer, the composition for the matrix is coated on the metal nanowire dispersion layer, and the metal nanowire dispersion layer and the matrix composition are cured A transparent conductive layer can be formed. The coating can be performed by, but not limited to, bar coating, slot die coating, gravure coating, and roll-to-roll coating. The coating thickness can be from 10 nm to 1 탆, specifically from 20 nm to 150 nm, more specifically from 50 nm to 130 nm or from 70 nm to 120 nm. The curing can form a transparent conductive layer and increase the strength of the transparent conductive layer. The curing may include one or more of thermosetting, photo-curing. The thermal curing may be carried out at 40 캜 to 180 캜 for 1 minute to 48 hours. Photocuring can be carried out with a UV dose of 50 mJ / cm 2 to 1,000 mJ / cm 2 . The coating film for a transparent conductive layer can be dried before curing the coating film for a transparent conductive layer to shorten the curing time. Drying may be carried out at 40 캜 to 180 캜 for 1 minute to 48 hours.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example  One

A second nanowire group dispersion (Clearohm ink, Cambrios) in which a plurality of silver nanowires having a length of nanowires of 20 mu m to 30 mu m (silver nanowire average length: about 24 mu m) was dispersed was prepared. The dispersion of the second nanowire group was treated with a power of 20% in a probe sonicator for 20 seconds to obtain a dispersion of the first nanowire group (length of the silver nanowire: 10 탆 to 15 탆, average length of the silver nanowire: about 12 Mu m). The average length of the silver nanowires was measured by SEM.

10 parts by weight of the dispersion of the first nanowire group and 90 parts by weight of the dispersion of the second nanowire group were mixed and a predetermined amount of solvent was added to prepare a silver nanowire dispersion (solid concentration: 0.9%).

12.7 parts by weight of dipentaerythritol hexaacrylate (DPHA, Entis), 38.2 parts by weight of polyethylene glycol diacrylate (SR344, Sartomer), 3-aminopropyltriethoxysilane (KBE-903, , 4.9 parts by weight of a mixture of phenolic antioxidant Irganox 1010, phosphorus antioxidant Irgafos 168 (BASF) and tris (acetylacetonate) iron (III) (Sigma Aldrich) as antioxidants, Irgacure 184 , 1.6 parts by weight of a mixture of 100 parts by weight of a solid component containing 1.7 parts by weight of a binder resin (CIBA) and 34 parts by weight of hollow silica (A-2505 (solution containing 10% by weight of silica solid content), Plenox) was dissolved in 98.4 weight parts of methyl isobutyl ketone To prepare a composition for a matrix having a viscosity of 0.56 cP at 25 캜.

The prepared silver nanowire dispersion liquid was coated on a substrate layer (polycarbonate film, Teijin, thickness: 50 占 퐉) by a spin coater, dried in an oven at 140 占 폚 for 90 seconds, and then coated with a bar coater Thereafter, the substrate was dried in an oven at 80 ° C for 90 seconds, dried in an oven at 120 ° C for 90 seconds, and then UV-cured at 200 mJ / cm 2 to form a transparent conductive layer having a thickness of 90 nm.

Example  2 and Example  3, Comparative Example  One

A transparent conductor was prepared in the same manner as in Example 1, except that the silver nanowire dispersion liquid prepared in the weight parts of the following Table 1 was used.

Comparative Example  2

In Example 1, the dispersion of the second nanowire group was treated in a probe sonicator at a power of 40% for 20 seconds to obtain a dispersion of the third nanowire group (silver nanowires having a length of 3 탆 to 8 탆, silver nanowires averaged Length: about 5 탆). A transparent conductor was prepared in the same manner as in Example 1, except that the silver nanowire dispersion liquid prepared in the weight parts of the following Table 1 was used.

Comparative Example  3

In Example 1, the dispersion of the second nanowire group was treated in a probe sonicator at a power of 10% for 20 seconds to obtain a dispersion of the fourth nanowire group (silver nanowires having a length of 15 mu m to 20 mu m, Length: about 18 mu m).

A transparent conductor was prepared in the same manner as in Example 1, except that the silver nanowire dispersion liquid prepared in the weight parts of the following Table 1 was used.

The following properties of the transparent conductor of the examples and comparative examples were evaluated, and the results are shown in Table 1 below.

(1) Surface resistance: The sheet resistance was measured using a non-contact type surface resistivity meter (EC-80P, NAPSON) for the transparent conductor. The sheet resistance was measured for a transparent conductive layer that was not patterned.

(2) Haze and total light transmittance: Haze and total light transmittance were measured using a haze meter (NDH-2000, NIPPON DENSHOKU) at a wavelength of 400 nm to 700 nm with the conductive layer directed toward the light source for the transparent conductor.

(3) Channel resistance (R x , R y ) and channel resistance deviation value: A photoresist film (Dongwoo Fine-Chem, SS-03A9) was spin-coated on the transparent conductor and dried in an oven at 120 ° C for 3 minutes. after the ultraviolet light exposure at 200mJ / cm 2 using ammonium hydroxide developer for 5% aqueous solution into 10 seconds, and, and 3 minutes and baked at 120 ℃ oven, an etching solution (Al etchant, Transene Co. Aluminum etchant type a)) Followed by dipping and etching to prepare a patterned transparent conductor. And a direction perpendicular to the x-axis is a y-axis, a direction in which the nanowire is coated is defined as x-axis and a direction perpendicular to the x- (Line resistance) R x and R y were measured at a resistance measurement length of 70 mm by using a resistivity measuring device (Sanwa, CD800a) and calculated according to the above-mentioned formula 1.

division Silver nanowire dispersion Transparent electrode characteristics A B C D R Sheet resistance
(Ω / □) Hayes
(%) Total light transmittance
(%) R x
(kΩ) R y
(kΩ) Channel resistance deviation value
(%) Example 1 10 90 - - A: B
1: 2 49.7 1.0 92.0 0.71 1.32 85.9 Example 2 20 80 - - A: B
1: 2 52.1 1.0 92.1 0.77 1.27 64.9 Example 3 30 70 - - A: B
1: 2 54.7 1.0 92.1 0.72 0.95 31.9 Comparative Example 1 - 100 - - - 53.8 0.9 92.1 0.67 1.62 141.8 Comparative Example 2 - 90 10 - C: B
1: 4.8 55.27 1.3 91.8 1.24 1.52 22.6 Comparative Example 3 - 90 - 10 D: B
1: 1.33 51.22 1.0 92.0 0.70 1.55 121.4

* A: First nanowire group: average length of silver nanowire about 12 탆

* B: second nanowire group: average length of silver nanowires about 24 m

* C: third nanowire group: average length of silver nanowire about 5 탆

* D: fourth nanowire group: mean length of silver nanowires about 18 m

* R: ratio of silver nanowire average length

As shown in Table 1, the transparent conductor according to the embodiment of the present invention has low channel resistance deviation value, high channel resistance uniformity, low haze, good optical characteristics, and low sheet resistance.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

A transparent conductor comprising a base layer and a transparent conductive layer formed on the base layer,
The transparent conductive layer includes a first group of nanowires including at least one nanowire having a length of 1 mu m or more and less than 20 mu m and a second group of nanowires containing at least one nanowire having a length of 20 mu m or more and 40 mu m or less and,
Wherein the ratio of the average length of the nanowires of the first nanowire group to the second nanowire group is 1: 2 to 1: 4,
The first nanowire group and the second nanowire group may include 10 wt% to 30 wt% and 70 wt% to 90 wt%, respectively, of the first nanowire group and the second nanowire group,
Wherein the transparent conductor has a channel resistance deviation value of 100% or less,
<Formula 1>
Channel resistance deviation value = (R y - R x ) / R x x 100
(Where R x and R y are the x axis in one direction among the transparent conductors or the patterned transparent conductors and the y axis in the direction perpendicular to the x axis, Direction, respectively),
The transparent conductor has a haze of 1.0% or less at a wavelength of 550 nm,
Wherein the first nanowire group and the second nanowire group are mixed with each other in the transparent conductive layer.
delete delete 2. The transparent conductor of claim 1, wherein the nanowire comprises silver nanowires.
The method of claim 1, wherein the transparent conductive layer comprises a matrix,
Wherein the matrix is formed of a composition for a matrix comprising a (meth) acrylic compound, a bifunctional or trifunctional (meth) acrylic compound, and an initiator having five or more functionalities.
6. The transparent conductor according to claim 5, wherein the composition for a matrix further comprises at least one of an adhesion promoter, an antioxidant, and inorganic hollow particles.
delete delete The transparent conductor according to claim 1, wherein the base layer further comprises a functional layer.
9. A display device comprising the transparent conductor according to any one of claims 1, 4, 5, 6 and 9.
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US8018563B2 (en) * 2007-04-20 2011-09-13 Cambrios Technologies Corporation Composite transparent conductors and methods of forming the same
EP2748827A4 (en) * 2011-08-24 2015-05-27 Innova Dynamics Inc Patterned transparent conductors and related manufacturing methods
KR20150013292A (en) * 2012-05-18 2015-02-04 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Corona patterning of overcoated nanowire transparent conducting coatings
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