KR102004026B1 - Transparent conductor and display apparatus comprising the same - Google Patents

Abstract

A first functional layer formed on one surface of the base layer, and a transparent conductive layer formed on the first functional layer, wherein the first functional layer comprises a (meth) acryl-based cured product and has a thickness of 1 And the transparent conductive layer includes a metal nanowire and a matrix, and a display device including the same.

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 transparent conductor includes a base layer, a transparent conductive layer formed on the base layer and including metal nanowires and a matrix. Wet etching of the transparent conductor may cause peeling or separation of the pattern portion of the transparent conductive layer from the base layer due to introduction of the wet etching agent and removal of metal nanowires, ) Formation, and / or electrode peeling. On the other hand, the touch screen panel can be laminated with another optical element by an adhesive layer in a display device, but can be laminated by an air gap without an adhesive layer. However, when the transparent conductor is pressed from the outside to the hand due to the air gap, a newton's ring may be generated and the visibility may be lowered.

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

SUMMARY OF THE INVENTION A problem to be solved by the present invention is to provide a transparent conductor free from delamination or dropout of a pattern portion after wet etching, air gap formation between a base layer and a transparent conductive layer, and electrode peeling.

Another problem to be solved by the present invention is to provide a transparent conductor having a low contact resistance and a low haze by increasing the degree of contact between metal nanowires.

Another problem to be solved by the present invention is to provide a transparent conductor which is free from occurrence of Newton rings and can realize excellent visibility even when laminated without a point / adhesive layer.

The transparent conductor of the present invention comprises a base layer, a first functional layer formed on one surface of the base layer, and a transparent conductive layer formed on the first functional layer, wherein the first functional layer is a (meth) acrylic light- And a thickness of 1 탆 or more, and the transparent conductive layer may include metal nanowires and a matrix.

The transparent conductor of the present invention comprises a base layer, a second functional layer formed on one surface of the base layer, and a transparent conductive layer formed on the other surface of the base layer, wherein the second functional layer is a (meth) freight; And particles having an average particle size (D50) of more than 50 nm but less than 200 nm, and the particles include inorganic particles, organic particles or a mixture thereof, and the transparent conductive layer may include metal nanowires and a matrix.

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

The present invention provides a transparent conductor free from delamination or dropout of a pattern portion, formation of an air gap between a base layer and a transparent conductive layer, and electrode peeling after wet etching.

The present invention provides a transparent conductor having low contact resistance and low haze by increasing the degree of contact between metal nanowires.

The present invention provides a transparent conductor capable of realizing excellent visibility without occurrence of Newton rings even when laminated without a point / adhesive layer.

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 transparent conductor according to another embodiment of the present invention.
4 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.
5 is a cross-sectional view of a display device according to an embodiment of the present invention.
6 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, "

In the present specification, "aspect ratio" means the ratio (L / d) of the longest length (L) of the metal nanowire to the shortest diameter (d) of the cross section of the metal nanowire, Quot; means acrylic and / or methacrylic. As used herein, the term " point / adhesive layer "includes a structure in which an adhesive layer, an adhesive layer alone or one or more adhesive layers and an adhesive layer are laminated.

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.

1, the transparent conductor 100 according to the present embodiment includes a base layer 110, a first functional layer 120, and a transparent conductive layer 130, and includes a base layer 110, The functional layer 120, and the transparent conductive layer 130 in this order.

The base layer 110 may support the first functional layer 120 and the transparent conductive layer 130. The base layer 110 is a resin film having a total light transmittance of 85% to 100%, more specifically 85% to 95% and a haze of 5.0% or less, specifically 0.1% to 1.0% at a wavelength of visible light, . ≪ / RTI > Within this range, the optical characteristics of the transparent conductor can be improved. Specifically, the resin is selected from the group consisting of a polyester resin including a polycarbonate resin, a cyclic olefin polymer resin, a polyethylene terephthalate resin, and a polyethylene naphthalate resin, a polyolefin resin, a polysulfone resin, a polyimide resin, a silicone resin, Resin, polyacrylic resin, polyvinyl chloride resin, but is not limited thereto. The base layer 110 may be a film having birefringence. The base layer 110 may have a thickness of 10 占 퐉 to 200 占 퐉, specifically, 20 占 퐉 to 150 占 퐉, more specifically, 20 占 퐉 to 80 占 퐉. Within this range, the substrate layer may be used for the transparent conductor.

The first functional layer 120 is formed on the substrate layer 110 and can be " formed directly " on the substrate layer 110. The first functional layer 120 enhances the adhesion of the transparent conductive layer 130 to the substrate layer 110 and the chemical resistance of the transparent conductive material 100. The first functional layer 120 is formed by repeating the basic solution and the acidic solution The patterned portion formed by the wet etching of the transparent conductive layer 130 can be prevented from peeling or coming off, thereby preventing peeling between the base layer 110 and the transparent conductive layer 130. The first functional layer 120 may be formed by planarizing the base layer 110 to lower the haze of the transparent conductor 100 and increase the contact between the metal nanowires 131 to increase the contact resistance of the transparent conductor 100 And the haze change of the transparent conductor 100 can be lowered even at a high-temperature heat treatment of 140 ° C or higher. Specifically, the transparent conductor 100 may have a haze of 1.5% or less, specifically 1.0% or less, more specifically 0.5% to 0.9% at a wavelength of 400 nm to 700 nm in a visible light region, 100) has a haze change amount of 1.0% or less, specifically 0% to 0.1%, and a haze change rate of 10% or less, specifically 1% to 5%, in the following formula 1 after heat treatment at a high temperature of 140 ° C Can:

<Formula 1>

Haze variation = H2 - H1

<Formula 2>

Haze change rate = (H2 - H1) / H1 x 100

(In the formula 1 and the formula 2, H1 is the haze (unit:%) of the transparent conductor in the visible light region, and H2 is the transmittance of the transparent conductor in the visible light region after being left at 140 DEG C for 30 minutes Haze (unit:%)).

The thickness of the first functional layer 120 may be 1 占 퐉 or more, specifically 1 占 퐉 to 5 占 퐉. In the above range, it can be used for a transparent conductor, and the adhesion of the transparent conductive layer 130 can be enhanced, a planarization effect can be obtained, and the pattern portion can be prevented from being peeled off after the wet etching of the transparent conductive layer.

The first functional layer 120 may comprise a (meth) acryl-based cured product. Specifically, the first functional layer 120 may be formed of a composition for a first functional layer containing a tetrafunctional or higher (meth) acrylic oligomer or resin, a crosslinking agent, and an initiator. The (meth) acryl-based oligomer or resin having four or more functional groups forms a matrix of the first functional layer 120 and may have from four to ten functionalities. The "oligomer" may have a weight average molecular weight of 10,000 or less, specifically 200 to 5,000, more specifically 400 to 3,000, and the adhesion to the base layer in the above range may be improved. The tetrafunctional or higher (meth) acrylic oligomer may include at least one of urethane (meth) acrylic oligomer, polyester (meth) acryl oligomer, epoxy (meth) acryl oligomer and silicone containing (meth) . The tetrafunctional or higher (meth) acrylic resin may include a resin formed from the above tetrafunctional or higher (meth) acrylic oligomer. Particularly, the urethane (meth) acryl-based oligomer having four to ten functionalities has a high degree of cross-linking of the first functional layer 120 to prevent penetration of the etching solution during the wet etching, thereby preventing peeling or peeling of the pattern portion and peeling of the electrode from wet high- . The crosslinking agent increases the degree of crosslinking of the first functional layer 120 and may include bifunctional to hexafunctional (meth) acrylic monomers. The (meth) acrylic monomer having two or more functional groups may be 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di Acrylate such as di (meth) acryloxyethyl isocyanurate, allyl cyclohexyl di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) (Meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate, Acrylate or 9,9-bis [4- (2-yl-acryloyl oxy) phenyl] Difunctional (meth) acrylates such as fluorene; (Meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional (meth) acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethylisocyanurate; Tetrafunctional (meth) acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; Pentafunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; (Meth) acrylate or dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (e.g., an isocyanate monomer and trimethylolpropane tri (Meth) acrylate having a trifunctional or a pentafunctional group may have at least one of trifunctional (meth) acrylates such as trifunctional (meth) acrylates, The composition for the first functional layer may contain 50 to 90% by weight, specifically 60 to 90% by weight, of the (meth) acrylic oligomer or resin having four or more functional groups. From 5 wt% to 40 wt%, specifically from 20 wt% to 30 wt%, of initiator 1 wt% to 10 wt%, more specifically from 2 wt% to 5 wt% In the above range, the effect of the first functional layer can be realized, and the transparency of the transparent conductor can be prevented from deteriorating due to the remaining amount of the initiator. The composition for the first functional layer is a solvent, for example, methyl ethyl ketone, The composition for the first functional layer further contains particles of at least one of inorganic particles and organic particles to prevent inter-film blocking and Newton ring. The inorganic particles include silica, aluminum oxide, zirconium oxide , And titanium oxide, and the organic particles may include at least one of siloxane particles, polycarbonate particles, and styrene particles. The particles may contain at least one of tetrafunctional or more (meth) acrylic oligomers and / or a crosslinking agent The particles may be non-hollow, hollow particles having a small particle size but without hollow, which may further enhance the hardness and chemical resistance of the first functional layer The particles may have a spherical shape or the like and may have an average particle diameter (D50) of less than 200 nm, specifically more than 50 nm and less than 200 nm, more specifically 100 nm to 190 nm, 50% by weight, specifically 5% by weight to 10% by weight. The first functional layer can be included in the particle diameter and the content range and the first functional layer can be planarized.

The transparent conductive layer 130 is formed on the first functional layer 120 and is formed directly on the first functional layer 120. The transparent conductive layer 130 can provide conductivity and flexibility to the transparent conductive material 100. [ The transparent conductive layer 130 may include a metal nanowire 131 and a matrix 132.

The metal nanowires 131 may be impregnated into the matrix 132 to form a conductive network and provide conductivity and flexibility. The metal nanowires 131 may be partially exposed to the outside of the transparent conductive layer 130 and the metal nanowires 131 may be completely impregnated in the transparent conductive layer 130 as shown in FIG. The sheet resistance of the conductor can be lowered. The metal nanowires 131 may have an aspect ratio of 10 to 5,000, specifically 500 to 1,000, more specifically 500 to 700. Within this range, a conductive network can be realized even at low metal nanowire densities. The metal nanowires 131 may have a shortest diameter of 100 nm or less, specifically 10 nm to 100 nm, more specifically 10 nm to 30 nm, and a longest length of 20 m or more, specifically 20 to 50 m. In the range of the diameter and the longest length, it is possible to have a high aspect ratio to increase the conductivity of the transparent conductor and lower the sheet resistance. The metal nanowires 131 may be included in the transparent conductive layer 130 in an amount of 7 wt% or more, specifically 8 wt% to 50 wt%. In the above range, by forming the conductive network sufficiently, the conductivity of the transparent conductor can be high. The metal nanowire 131 may be formed of a metal, specifically, silver, including at least one of silver, copper, aluminum, nickel, and gold.

The matrix 132 is formed on the first functional layer 120 to strengthen the bonding between the first functional layer 120 and the transparent conductive layer 130 to prevent oxidation of the metal nanowires 131, It is possible to prevent the surface resistance of the body 100 from rising and to improve the chemical resistance, solvent resistance, durability (reliability), etc. of the transparent conductor 100.

The matrix 132 may be formed of a composition for a matrix comprising a (meth) acrylic compound having at least five functional groups, a bifunctional or trifunctional (meth) acrylic compound, an initiator, and a solvent. The (meth) acrylic compound having five or more functionalities forms the matrix 132, and may include at least one of a (meth) acrylic monomer and a (meth) acrylic oligomer having five to ten functionalities. The "oligomer" may have a repeating unit number of at least 2 and a weight average molecular weight of 10,000 or less, specifically 200 to 5,000, more specifically 400 to 3,000. Within this range, the adhesion between the base layer and the electrode material, the optical characteristics and the chemical resistance can be improved by the matrix of the transparent conductive layer. The (meth) acrylic monomer having 5 or more functional groups may be a pentafunctional to a 10-functional (meth) acrylic monomer of C3 to C20 polyhydric alcohols such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ) Acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. The (meth) acrylic oligomer having five to ten functional groups may be a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, Lt; RTI ID = 0.0 &gt; oligomeric &lt; / RTI &gt; The bifunctional or trifunctional (meth) acrylic compound can form the matrix 132 and improve the appearance of the matrix 132. (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, (Meth) acrylic monomers of non-modified C3 to C20 polyhydric alcohols containing at least one of pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate, ethoxylated trimethylol propane tri (Meth) acrylate containing at least one of (meth) acrylic monomers of C3 to C20 polyhydric alcohols modified with an alkoxy group containing at least one of (meth) acrylate and propoxylated glyceryl tri (meth) : A (meth) acrylic group of a C3 to C20 polyhydric alcohol modified with a C1 to C5 alkoxy group such as an ethoxy group, a propoxy group, or a butoxy group) It may include one or more hairpins. The (meth) acrylic monomer of C3 to C20 polyhydric alcohol modified with an alkoxy group can further improve the light transmittance and reliability of the transparent conductor relative to the (meth) acrylic monomer of the unmodified C3 to C20 polyhydric alcohol, It can be more advantageous in anger. The (meth) acrylic compound having 5 or more functional groups may be contained in an amount of 10 wt% to 90 wt%, specifically 60 wt% to 85 wt%, or 15 wt% to 40 wt% in the solid matrix composition. The bifunctional or trifunctional (meth) acrylic compound is used in an amount of 10 to 90 wt%, specifically 15 to 40 wt%, more specifically 20 to 30 wt%, or 60 wt% % To 85% by weight. When the transparent conductor is patterned in the above range, the pattern uniformity is high and a fine pattern can be realized, so that the transparency of the transparent conductor and the reliability can be high. As used herein, "solids basis" refers to the entirety of the composition for a matrix except for the solvent. The initiator may include a photopolymerization initiator having an absorption wavelength of 150 nm to 500 nm. Specifically, the initiator may be one or more of an alpha-hydroxy ketone type or alpha-amino ketone type, for example, 1-hydroxycyclohexyl phenyl ketone. The initiator may be included in the composition for solid matrix-based matrices in an amount of 1 wt% to 10 wt%, specifically 2 wt% to 5 wt%. Within the above range, the composition for a matrix can be completely cured, and the remaining amount of initiator can prevent deterioration of optical properties of the transparent conductive layer. The solvent can lower the viscosity of the matrix composition to improve the coating property and improve the appearance of the transparent conductive layer. The solvent may include at least one of methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol, ethanol, propylene glycol monomethyl ether acetate. The solvent may be contained in the matrix composition in an amount of at least 80% by weight. Within the above range, the coating property of the matrix composition can be improved and the appearance of the transparent conductive layer can be improved. The composition for a matrix may further include at least one of an adhesion promoter and an antioxidant. 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, and a monofunctional or bifunctional (meth) acrylic monomer. As the silane coupling agent, a commonly known silane coupling agent may be used. Specifically, the silane coupling agent is a silane coupling agent having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Coupling agents; Silane coupling agents containing a polymerizable unsaturated group such as vinyltrimethoxysilane, vinyltriethoxysilane and (meth) acryloxypropyltrimethoxysilane; Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) And an amino group-containing silane coupling agent such as dimethoxy silane. 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 the solid matrix-based matrix in an amount of 0.1 to 10% by weight, specifically 0.5 to 10% by weight. 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 includes at least one of phosphorus-based antioxidants such as triazole-based antioxidants, triazine-based antioxidants and phosphites, Hindered amine light stabilizer (HALS) -based antioxidants, phenol-based antioxidants and metal acetyl acetonate- can do. Specifically, the phosphorus antioxidant is tris (2,4-di-tert-butylphenyl) phosphite and the phenol antioxidant is pentaerythritol tetrakis (3- (3,5- The antioxidant for HALS may be 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, 4-hydroxy-2,2,6,6-tetramethyl- Dimethylsuccinate copolymer with piperidine-ethanol, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- ) Amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, etc. The metal acetylacetonate antioxidant may be tris (acetylacetonato) Iron (III), tris (acetylacetonato) chromium (III), and the like, The antioxidant may be contained in an amount of 0.01% by weight to 10% by weight, specifically 0.05% by weight to 10% by weight, based on the weight of the solid matrix composition. In this range, oxidation of the metal nanowires is prevented, The composition for a matrix may further include an additive. The additive may include an antistatic agent, an ultraviolet absorber, a viscosity modifier, a heat stabilizer, a dispersant, a thickener, and the like. The composition for a matrix may have a viscosity of from 0.1 cP to 20 cP at 25 ° C. In the above range, the coating property of the matrix composition is improved and the coating is uniformly coated with a thin film so that the transparent conductive layer is uniformly physically and chemically Characteristics can be obtained.

The transparent conductive layer 130 may have a thickness of 10 nm to 1 μm, specifically 10 nm to 200 nm, more specifically 20 nm to 150 nm, or 50 nm to 130 nm. Within the above range, the transparent conductor can be used for the touch panel, the contact resistance is lowered, and the optical characteristics and etching property of the transparent conductor can be improved.

The transparent conductor 100 may have a total light transmittance of 90% to 100%, specifically 90% to 95% in the visible light region. Within this range, transparency is good and can be used as a transparent conductor. The transparent conductor 100 may have a sheet resistance of 100 Ω / □ or less, specifically 30 Ω / □ to 100 Ω / □, more specifically 40 Ω / □ to 80 Ω / □, as measured by a 4-probe or a non-contact sheet resistance meter . In the above range, since the sheet resistance is low, it 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 is not limited, but may be 10 탆 to 250 탆, specifically 50 탆 to 200 탆. 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.

1 shows a film in which the base layer 110 is made of a resin of a single layer, but the base layer 110 may further include a surface treatment layer on one or both sides. The surface treatment layer may provide additional functions such as improved slip properties, providing this adhesion, increasing adhesion, hard coating, antireflection, anti-glare and the like. In one embodiment, the surface treatment layer may be a primer layer comprising silica, a (meth) acrylic oligomer, or the like as a separate, independent layer from the substrate layer 110. In other embodiments, the surface treatment layer may be formed by plasma treatment, corona treatment, primer treatment, etc. so that one surface of the substrate layer 110 becomes a surface treatment layer. Particularly, the substrate layer formed with the adhesive surface treatment layer migrates to the surface of the oligomer or the like in the surface treatment layer during the high-temperature heat treatment at 140 ° C or higher, so that the haze of the substrate layer increases from 0.5% to 1.5% The haze change can be suppressed by including the first functional layer 120 in the transparent conductor 100 of the present embodiment.

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, a transparent conductor 200 according to another embodiment of the present invention may further include a second functional layer 140 formed on the other surface of the base layer 110 to form a second functional layer 140, Is substantially the same as the transparent conductor 100 according to the embodiment of the present invention except that the base layer 110, the first functional layer 120 and the transparent conductive layer 130 are laminated in this order. Hereinafter, the second functional layer 140 will be mainly described, and substantially the same constituent elements as those of the embodiment of the present invention will be denoted by the same reference numerals, and detailed description will be omitted.

The second functional layer 140 is formed on the base layer 110, that is, the base layer 110, and may be formed directly on the base layer 110. Since the second functional layer 140 includes particles as described below, even if the transparent conductor 200 is laminated on the optical element without the point / adhesive layer, the occurrence of Newton rings can be suppressed and the visibility can be improved. Further, similarly to the first functional layer 120 described above, the second functional layer 140 can suppress the amount of haze change and the rate of change even when the substrate layer having the adhesive surface treatment layer is heat-treated at a high temperature of 140 캜 or higher.

The second functional layer 140 may have a thickness of less than 2 占 퐉, specifically 1 占 퐉 or less, 0.1 占 퐉 to 0.9 占 퐉, more specifically 0.1 占 퐉 to 0.5 占 퐉. Within this range, there can be anti-blocking, anti-scratch and haze-reducing effects while suppressing the occurrence of Newton rings.

The second functional layer 140 may be formed of the same composition as that of the first functional layer 120, but the second functional layer 140 may be formed of the inorganic particles, the second functional layer It is possible to further enhance the Newton ring generation inhibiting effect. The composition for the second functional layer may include the above-mentioned (meth) acrylic oligomer or resin having four or more functional groups, a crosslinking agent, an initiator and particles. The composition for the second functional layer may further contain the solvent, additives described above. The composition for the second functional layer preferably contains 30 to 90% by weight, specifically 30 to 70% by weight of the (meth) acrylic oligomer or resin having 4 or more functional groups based on solids, 5 to 40% From 1 wt% to 10 wt%, specifically from 2 wt% to 5 wt%, and from 3 wt% to 50 wt%, and specifically from 5 wt% to 50 wt% of the initiator. When the transparent conductor is laminated with another optical film or the like in the above range, there may be an effect of suppressing occurrence of Newton rings.

Hereinafter, a transparent conductor according to another embodiment of the present invention will be described with reference to FIG. 3 is a cross-sectional view of a transparent conductor according to another embodiment of the present invention.

3, the transparent conductor 300 according to the present embodiment includes the second functional layer 140, the base layer 110, and the transparent conductive layer 130 except for the first functional layer 120 The transparent conductor 200 according to another embodiment of the present invention is substantially the same as that of FIG. The transparent conductor according to this embodiment includes the second functional layer, so that when the transparent conductor is laminated with another optical film or the like, the effect of suppressing the occurrence of Newton rings can be obtained.

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

4, the transparent conductor 400 of this embodiment is formed by patterning the transparent conductive layer 130 'into a conductive layer 130a' and a non-conductive layer 130b 'including only the matrix 132 Except that it is substantially the same as the transparent conductor 100 of the embodiment of the present invention. The conductive layer 130a 'is the same as the transparent conductive layer 130 of FIG. 1, and the non-conductive layer 130b' includes only the matrix 132 without the metal nanowires 131. The transparent conductive layer 130b 'may be formed by patterning the transparent conductive layer 130 according to an embodiment of the present invention in a conventional manner.

Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIG. 5 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

5, the optical display device 500 according to the present embodiment includes a display portion 510, a polarizing plate 520, a transparent electrode member 530, a window film 540, and an adhesive layer 550 And the transparent electrode member 530 may be formed of a transparent conductor according to embodiments of the present invention. 5 illustrates a structure in which a display portion 510, a polarizing plate 520, a transparent electrode body 530, and a window film 540 are stacked in this order. The display portion 510, the transparent electrode body 530, The polarizing plate 520, and the window film 540 may be stacked in this order.

The display unit 510 is for driving the optical display device 500 and may include an optical element including an OLED, an LED, or an LCD device formed on the substrate and the substrate. In one embodiment, the display portion 510 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective film, and an insulating film. In other embodiments, the display portion 510 may include a top filter, a bottom filter, a liquid crystal layer positioned between the top and bottom substrates, and a color filter formed on at least one of the top and bottom substrates. 5 illustrates a structure in which the display unit 510 and the transparent electrode unit 530 are independently layered, but the transparent electrode unit 530 may be formed inside the display unit.

The polarizing plate 520 is formed on the display unit 510 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 520 may be a polarizer alone. Alternatively, the polarizing plate 520 may include a polarizing film and a protective film formed on one or both sides of the polarizing film. Although not shown in FIG. 5, a polarizing plate may be further formed on the lower portion of the display unit 510 to improve the contrast ratio of the display. At this time, the polarizing plate may be formed on the display portion 510 by an adhesive layer.

The transparent electrode member 530 is formed on the polarizing plate 520 and can generate an electrical signal by detecting a change in capacitance generated when the transparent electrode member 530 is touched by contact or the like. The transparent electrode member 530 includes a base layer 110, a first functional layer 120 formed on one surface of the base layer 110, a first electrode 531 formed on one surface of the first functional layer 120, A third electrode 533 and a fourth electrode 534 formed on one surface of the second functional layer 140 may be formed on the other surface of the substrate layer 110, have. 5 shows a structure in which the third electrode 533 and the fourth electrode 534 / the substrate layer 110 / the first electrode 531 and the second electrode 532 are stacked in this order. However, the substrate layer 110 The third electrode 533 and the fourth electrode 534 / the base layer 110 / the first electrode 531 and the second electrode 532 may be stacked in this order.

The window film 540 may be formed at the outermost portion of the optical display device 500 to protect the optical display device 500. The window film 540 may be formed of a glass substrate or a flexible plastic substrate.

The adhesive layer 550 is formed between the display part 510 and the polarizer 520 and between the transparent electrode 530 and the window film 540 to form a display part 510, a polarizer 520, 530 and the window film 540 can be strengthened. The adhesive layer 550 may be formed of a conventional optically transparent adhesive. Although not shown in FIG. 5, an adhesive layer may also be formed between the polarizing plate 520 and the transparent electrode member 530.

Hereinafter, an optical display device according to another embodiment of the present invention will be described with reference to FIG. 6 is a cross-sectional view of an optical display device according to another embodiment of the present invention.

6, the transparent electrode member 530 'includes a base layer 110, a first functional layer 120 formed on one surface of the base layer 110, The first electrode 531 and the second electrode 532 are formed on the window film 540 'and the third electrode 533 and the fourth electrode 534 formed on one surface of the first functional layer 120 Is substantially the same as the optical display device 500 according to an embodiment of the present invention.

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 embodiment of the present invention includes the steps of forming a first functional layer on one surface of a base layer, forming a metal nanowire dispersion layer on the first functional layer, And then curing the metal nanowire dispersion layer and the matrix composition to form a transparent conductive layer.

The first functional layer can be formed by applying the composition for the first functional layer on the base layer and photo-curing the composition. The metal nanowire dispersion layer may be formed by applying a dispersion of metal nanowires on the first functional layer. Metal nanowires may be included as metal nanowires themselves, but may be included as metal nanowire-containing solutions. The metal nanowire-containing solution can be, but is not limited to, commercially available products from Cambrios, such as ClearOhm Ink G4-04 or G4-05. The metal nanowire-containing solution may further contain additives such as a binder, an initiator, a dispersant, a thickener, 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 binder, initiator, and additive may be included in the metal nanowire-containing solution in an amount of 0.1 wt% to 50 wt%, specifically 1 wt% to 45 wt%. Within the above range, the optical characteristics of the transparent conductor, prevention of increase in contact resistance, durability, and chemical resistance can be improved. The solvent may include water including ultrapure water and the like, an organic solvent such as alcohol, and the like, but is not limited thereto. Coating may be performed by, but not limited to, bar coating, slot die coating, gravure coating, and roll-to-roll coating. 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, light 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.

A method for manufacturing a transparent conductor according to another embodiment of the present invention includes the steps of forming a second functional layer on one surface of a base layer, forming a metal nanowire dispersion layer on the other surface of the base layer, Except that a transparent conductive layer is formed by applying a composition for a matrix and curing the metal nanowire dispersion layer and the composition for a matrix to form a transparent conductive layer.

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.

The ingredients used in the following examples and comparative examples are as follows:

(A) Base layer: A primer treated polyethylene terephthalate film (Teijin Co., thickness: 23 탆)

(B) Metal nanowire-containing solution: Clearohm ink (Cambrios, 2.45% by weight of metal nanowire and binder)

Example  One

37 parts by weight of the metal nanowire-containing solution was added to 63 parts by weight of distilled water for ultra pure water and stirred to prepare a metal nanowire dispersion.

63 parts by weight of dipentaerythritol hexaacrylate (DPHA, Entis), 21 parts by weight of propoxylated glyceryl triacrylate (SR9020, Sartomer), 3 parts by weight of adhesion promoter 3-aminopropyltriethoxysilane (KBE-903 , Shin-Etsu Co., Ltd.), 4 parts by weight of a mixture of phenolic antioxidant Irganox 1010 and phosphorus-based antioxidant Irgafos 168 (BASF), and 4 parts by weight of initiator Irgacure 184 (CIBA) Was added to 98.5 parts by weight of methyl isobutyl ketone to prepare a composition for a matrix.

70 parts by weight of a (meth) acrylic resin UP111 (Entis), 25 parts by weight of a crosslinking agent trimethylolpropane triacrylate (TMPTA), and 5 parts by weight of an initiator Irgacure 184 (CIBA) To prepare a composition for a first functional layer.

By applying the first function layer composition on a surface of a base material layer and dried at a high temperature above 60 ℃ 80 ℃ and UV curing to 150mJ / cm ² in a nitrogen atmosphere to form a first functional layer with a thickness 1㎛. The dispersion of the metal nanowires was coated on the first functional layer by a spin coater and dried at 140 DEG C for 90 seconds. The composition for a matrix was coated by a spin coater and dried at 80 DEG C for 90 seconds and 120 DEG C for 90 seconds Thereafter, the resultant was UV-cured at 200 mJ / cm ² to form a transparent conductive layer having a thickness of 90 nm. Thus, a transparent conductor was produced.

Example  2 to Example  6

A transparent conductor was prepared in the same manner as in Example 1, except that the first functional layer was changed as shown in Table 1 below.

Example  7

A metal nanowire dispersion and a composition for a matrix were prepared in the same manner as in Example 1.

66.5 parts by weight of a (meth) acrylic resin UP111 (Entis), 28.5 parts by weight of a crosslinking agent trimethylolpropane triacrylate (TMPTA), and 5 parts by weight of an initiator Irgacure 184 (CIBA) were added to 150 parts by weight of methyl ethyl ketone To prepare a composition for a first functional layer.

(Average particle size (D50): 110 nm, SST550U (50% by weight in Butyl Acetate), 63 parts by weight of an acrylic resin UP111 (Entis), 27 parts by weight of a crosslinking agent TMPTA, 5 parts by weight of an initiator Irgacure 184 Ranco Co., Ltd.) was mixed with 150 parts by weight of methyl ethyl ketone to prepare a composition for a second functional layer.

A first functional layer having a thickness of 1.5 占 퐉 and a transparent conductive layer were sequentially formed on one surface of the base layer in the same manner as in Example 1. [ The composition for the second functional layer was applied to the other surface of the substrate layer, dried at a high temperature of 80 캜 or higher at 60 캜 or higher, and UV-cured at 150 mJ / cm ² in a nitrogen atmosphere to form a second functional layer having a thickness of 0.5 탆, .

Example  8th and Example  9

A transparent conductor was prepared in the same manner as in Example 7, except that the second functional layer was changed as shown in Table 2 below.

Example  10

A metal nanowire dispersion and a composition for a matrix were prepared in the same manner as in Example 1. A composition for a second functional layer was prepared in the same manner as in Example 7.

The composition for the second functional layer was applied to one surface of the substrate layer, dried at a high temperature of 80 캜 or higher at 60 캜 or higher, and UV-cured at 150 mJ / cm ² in a nitrogen atmosphere to form a second functional layer having a thickness of 0.5 탆.

A transparent conductive layer was formed on the other surface of the base layer by the same method as in Example 1, using the metal nanowire dispersion and the matrix composition, to prepare a transparent conductor.

Comparative Example  One

A transparent conductor was prepared in the same manner as in Example 1, except that the first functional layer was not formed.

Comparative Example  2 to Comparative Example  5

A transparent conductor was prepared in the same manner as in Example 1 except that the first functional layer was changed as shown in Table 1 below.

Comparative Example  6

A transparent conductor was prepared in the same manner as in Example 7 except that the second functional layer was changed as shown in Table 2 and silica was not used.

Comparative Example  7 to Comparative Example  8

In Example 7, the first functional layer and the second functional layer were changed as shown in Table 2, and in Comparative Example 7, silica having an average diameter (D50) of 50 nm was used. In Comparative Example 8, an average diameter (D50) A transparent conductor was prepared in the same manner except that phosphorus silicate was used.

The following properties were evaluated for the transparent conductor prepared in Examples and Comparative Examples, and the results are shown in Table 1 below.

(1) Pattern dropout: A photoresist film (Dongwo Fine-Chem, SS-03A9) was spin-coated on a transparent conductive layer of a transparent conductor and dried in an oven at 120 캜 for 3 minutes. Using a pattern mask having a pattern formed, cm ² , and the exposed sample was placed in a 5% aqueous solution of trimethylammonium hydroxide (Han Duk Chemical) as a developing solution and developed for 10 seconds, and baked in an oven at 120 ° C for 1 minute to form a pattern layer. The transparent conductor on which the pattern layer was formed was immersed in an etching solution (Al etchant, 75 wt% to 85 wt% aqueous solution of phosphoric acid at 85 wt% concentration, 3 wt% to 10 wt%, 99.7 wt% (Transgenic aluminum etchant type A) of 5% by weight to 20% by weight of acetic acid aqueous solution at a concentration of 0.5% by weight for 180 seconds, and the photoresist film was removed with a stripper solution to prepare a patterned transparent conductor. Was evaluated by using an optical microscope to determine whether or not the pattern portion from which the nanowires were removed was removed.

(2) Haze and total light transmittance: The transparent conductor in Examples and Comparative Examples was oriented with a transparent conductive layer toward a light source and a haze meter (NDH-2000, NIPPON DENSHOKU) was used at a wavelength of 400 to 700 nm to measure the initial haze And total light transmittance were measured.

(3) Surface resistance: The sheet resistances of the transparent conductors of Examples and Comparative Examples were measured using a non-contact type sheet resistance measuring instrument EC-80P (NAPSON).

(4) Haze Change Amount and Haze Change Rate After the transparent conductor was left at 140 ° C for 30 minutes, the haze was measured in the same manner as in (2), and the haze change amount and the haze change rate were calculated according to the above- .

(5) Newton ring: Transparent conductive film on glass The electrode surface is facing up. After 1 cm tip 500gf pressure is maintained for 10 sec, check for the occurrence of Newton ring.

Example Comparative Example One 2 3 4 5 6 One 2 3 4 5 1st
Functional layer
(Parts by weight) thickness
(탆) One One 2 1.5 2.0 3.0 - 0.5 0.5 0.5 0.2 UP111 ^* 70 - - 70 70 70 - 70 - - 70 UP135 ^** - 70 - - - - - - 70 - - UP118 ^*** - - 70 - - - - - - 70 - TMPTA 25 25 25 25 25 25 - 25 25 25 25 Irgacure 184 5 5 5 5 5 5 - 5 5 5 5 Pattern missing none none none none none none has exist has exist has exist has exist has exist Hayes
(%) Initial haze 0.74 0.74 0.80 0.73 0.72 0.73 1.88 0.73 0.75 0.77 1.35 Leave at 140 ℃ for 30 minutes
Hueyes 0.75 0.76 0.80 0.74 0.75 0.75 10.80 0.75 0.75 0.85 7.03 Total light transmittance
(%) Initial total light transmittance 92.1 92.1 92.0 92.1 92.1 92.1 91.9 92.1 92.1 92.1 92.0 Leave at 140 ℃ for 30 minutes
Post-total light transmittance 92.1 92.0 92.1 92.1 92.1 92.1 91.9 92.1 92.2 92.1 92.0 Sheet resistance (□ / Ω) 49 48 49 50 49 49 49 48 48 50 49 Haze Change (%) 0.01 0.02 0 0.01 0.03 0.02 8.92 0.02 0 0.08 5.68 Change in Haze (%) 1.35 2.70 0.00 1.37 4.17 2.74 474.5 2.74 0.00 10.39 420.7

* UP111: 10-functional (meth) acrylic resin

** UP135: tetrafunctional (meth) acrylic resin

*** UP118: 6-functional (meth) acrylic resin

Example Comparative Example 7 8 9 10 6 7 8 The first functional layer
(Parts by weight) Thickness (㎛) 1.5 1.5 1.5 - 1.5 3 3 UP111 66.5 66.5 66.5 - 66.5 66.5 66.5 TMPTA 28.5 28.5 28.5 - 28.5 28.5 28.5 Irgacure 184 5 5 5 - 5 5 5 The second functional layer
(Parts by weight) Thickness (㎛) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 UP111 63 59.5 31.5 63 66.5 63 63 TMPTA 27 25.5 13.5 27 28.5 27 27 Irgacure 184 5 5 5 5 5 5 5 Silica 5 10 50 5 - 5 5 The average particle diameter (nm) 110 110 110 110 - 50 200 Initial Haze (%) 0.74 0.74 0.76 1.25 0.73 0.75 5.61 Initial total light transmittance (%) 92.1 92.1 92.1 92.1 92.1 92.1 91.8 Sheet resistance (□ / Ω) 49 50 49 53 49 48 49 Newton Ring none none none none Occur Occur Occur

As shown in Table 1, the transparent conductor according to the present example had a first functional layer formed on the substrate layer, so that wet etching did not cause pattern dropout, good optical characteristics, low sheet resistance, and low haze change rate and haze change amount. In addition, as shown in Table 2, when the second functional layer is formed on the base layer, the transparent conductor according to the present embodiment has no visibility and no visibility.

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 (15)

Substrate layer,
A first functional layer formed on one surface of the substrate layer, and
And a transparent conductive layer formed on the first functional layer,
Wherein the first functional layer comprises a (meth) acryl-based cured product and has a thickness of 1 탆 or more,
Wherein the transparent conductive layer is a transparent conductor comprising metal nanowires and a matrix,
Wherein the transparent conductor further comprises a second functional layer formed on the other surface of the substrate layer,
Wherein the second functional layer comprises 30 wt% to 90 wt% of urethane (meth) acrylic oligomer or resin having 4 or more solids-based functional groups, 5 wt% to 40 wt% of a crosslinking agent, 1 wt% to 10 wt% To 50% by weight,
Said particles being silica which is non-hollow and has an average particle size (D50) greater than 50 nm but less than 200 nm,
Wherein the first functional layer comprises a composition for a first functional layer comprising a urethane (meth) acrylate oligomer or a urethane (meth) acrylate oligomer having a functionality of 4 to 50 wt% to 90 wt%, a crosslinking agent 5 wt% to 40 wt%, and an initiator 1 wt% to 10 wt% Respectively,
Wherein the second functional layer has a thickness of more than 0 [mu] m but less than 2 [mu] m.
delete The transparent conductor according to claim 1, 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.
delete delete delete 2. The transparent conductor of claim 1, wherein the metal nanowire comprises silver nanowires.
The transparent conductor according to claim 1, wherein the transparent conductor has a haze change rate of 10%
<Formula 2>
Haze change rate = (H2 - H1) / H1 x 100
(In the formula (2), H1 is the haze (unit:%) of the transparent conductor in the visible light region, H2 is the haze in the visible light region after leaving the transparent conductor in the above H1 at 140 DEG C for 30 minutes unit:%)).
The transparent conductor according to claim 1, wherein the transparent conductor has a haze of 1.0% or less in a visible light region.
delete delete delete delete delete A display device comprising the transparent conductor according to any one of claims 1, 3, 7, 8 and 9.

Images