WO2018004102A1 - Transparent conductor and display device including same - Google Patents

Abstract

Provided are a transparent conductor and a display device including the same, the transparent conductor comprising a base layer and a transparent conductive layer formed on the base layer, wherein the transparent conductive layer comprises a metal nanowire and a matrix impregnated with the metal nanowire, and the matrix is made of a matrix composition comprising inorganic hollow particles, a fluorine-containing monomer or oligomer thereof, a photosensitive resin, a crosslinking agent, and an initiator.

Description

Transparent conductor and display device including same

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

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

Metal nanowire-containing transparent conductors can be used in display devices such as touch panels by patterning. A pattern can be directly formed in a transparent conductive layer by laser irradiation. Alternatively, there is a method of wet etching by photolithography. Wet etching includes forming a photoresist over a transparent conductive layer and developing after UV irradiation. As the photoresist, a liquid photoresist or a film type photoresist may be used. Film type photoresists are expensive but have high productivity because they can etch transparent conductors in a roll-to-roll process. However, there are problems such as adhesion between the transparent conductive layer and the film type photoresist, adhesion depending on the composition of the etching solution during etching after development. There is a method of coating and developing a liquid photoresist on a transparent conductive layer, but there is a problem in that the productivity is significantly reduced compared to a roll-to-roll process.

Background art of the present invention is described in Korean Patent Laid-Open No. 2012-0053724.

The problem to be solved by the present invention is to provide a transparent conductor that can be patterned without the use of a separate photoresist, excellent in productivity, and excellent in pattern formation ability.

Another problem to be solved by the present invention is to provide a transparent conductor in which a pattern is formed only by development and cleaning without performing etching liquid treatment and cleaning.

Another problem to be solved by the present invention is to provide a transparent conductor including a transparent conductive layer that is excellent in adhesion to the substrate layer and is not affected by development and / or cleaning during patterning and does not peel off from the substrate layer. .

Another object of the present invention is to provide a transparent conductor having excellent optical transparency and low sheet resistance.

The transparent conductor of the present invention includes a base layer and a transparent conductive layer formed on the base layer, wherein the transparent conductive layer includes a metal nanowire and a matrix impregnated with the metal nanowire, and the matrix is an inorganic hollow particle. And a fluorine-containing monomer or an oligomer thereof, a photosensitive resin, a crosslinking agent and an initiator.

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

The present invention can be patterned without the use of a separate photoresist to provide a highly sensitive transparent conductor having excellent productivity and excellent pattern forming ability.

The present invention provides a transparent conductor in which a pattern is formed only by development and cleaning without performing etching liquid treatment and cleaning.

The present invention provides a transparent conductor including a transparent conductive layer that is excellent in adhesion to a substrate layer and is not affected by development or cleaning during patterning and is not peeled from the substrate layer.

The present invention provides a transparent conductor excellent in optical transparency and low in sheet resistance.

1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention.

2 is a schematic diagram of a patterning process of a transparent conductor according to an 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 display device according to an embodiment of the present invention.

5 is a cross-sectional view of a display device according to another embodiment of the present invention.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

In the present specification, "upper" and "lower" are defined based on the drawings, and according to a viewpoint, "upper" may be changed to "lower" and "lower" to "upper", and "on" or What is referred to as “on” may include not only the above but also intervening other structures in the middle. On the other hand, what is referred to as "directly on", "directly on" or "directly formed" means not intervening in the other structures.

As used herein, "(meth) acryl" refers to acrylic and / or methacryl.

As used herein, "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.

Hereinafter, a transparent conductor according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2. 1 is a cross-sectional view of a transparent conductor according to an embodiment of the present invention. 2 is a schematic view showing a patterning process of a transparent conductor according to an embodiment of the present invention.

Referring to FIG. 1, the transparent conductor 100 according to an 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 substrate layer 110 may include a resin film having a light transmittance of about 85% to about 100%, more specifically about 90% to about 99% at a wavelength of 550 nm. In this range, the optical properties of the transparent conductor can be improved. Specifically, the resin is a polyester, polyolefin, polysulfone, polyimide, silicone, polystyrene, polyacryl, polyvinyl chloride resin, including polycarbonate, cyclic olefin polymer, polyethylene terephthalate, polyethylene naphthalate, etc. It may include one or more, but is not limited thereto. The base layer 110 may have a thickness of about 10 μm to about 200 μm, specifically about 30 μm to about 150 μm, and more specifically about 30 μm to about 100 μm. In the above range, the base layer can be used for the transparent conductor. 1 shows that the base layer 110 is a single layer, but the base layer may be a multilayer, and although not shown in FIG. 1, a functional layer may be formed on the base layer 110. The functional layer provides hard coating, anti-corrosion, anti-reflection, adhesion enhancement, oligomer elution function, and the like, and may be formed as a separate layer independently of the base layer or one surface of the base layer to be a functional layer. .

The transparent conductive layer 120 is formed on the base layer 110, and may provide conductivity and flexibility to the transparent conductor 100. The transparent conductive layer 120 may be formed directly on the base layer 110.

The transparent conductive layer 120 may include a metal nanowire 121 and a matrix 122 impregnated with the metal nanowire 121. 1 illustrates a case in which the metal nanowires are completely impregnated with the transparent conductive layer 120, but the present invention is not limited thereto. The metal nanowires may be partially exposed to the outside of the transparent conductive layer 120. When the metal nanowires 121 are completely impregnated with the transparent conductive layer 120 as shown in FIG. 1, the oxidation of the metal nanowires may be reduced, thereby lowering the sheet resistance of the transparent conductor 100.

The metal nanowires 121 may provide conductivity to the transparent conductor by forming a conductive network. Since the metal nanowires 121 have a nanowire shape, the metal nanowires 121 may provide flexibility and flexibility to the transparent conductor. The metal nanowires 121 may have an aspect ratio of about 10 to about 5,000. Within this range, a high conductive network can be realized even at low metal nanowire densities, and the sheet resistance of the transparent conductor can be lowered. Specifically, the metal nanowires may have an aspect ratio of about 500 to about 1,000, more specifically about 500 to about 700. The metal nanowires may have a cross-sectional diameter greater than about 0 nm and up to about 100 nm, specifically about 10 nm to about 100 nm, more specifically about 10 nm to about 30 nm. In the above range, 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 may have a longest length of about 10 μm or more, specifically about 10 μm to about 50 μm. In the above range, 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 may be formed of a metal comprising one or more of silver, copper, aluminum, nickel, and gold.

The metal nanowires 121 may contain about 40 wt% to about 80 wt%, specifically about 50 wt% to about 70 wt% of the transparent conductive layer 120, for example about 40, 45, 50, 55, 60, 65, 70, 75, 80% by weight may be included. Within this range, it is possible to increase the conductivity of the transparent conductor.

The matrix 122 may be formed on the base layer 110 to strengthen the bond between the base layer 110 and the metal nanowires 121. The matrix 122 may impregnate the conductive network of the metal nanowires 121 to prevent oxidation of the metal nanowires, thereby preventing an increase in the sheet resistance of the transparent conductor. In addition, the matrix 122 may increase optical characteristics, chemical resistance, solvent resistance, durability (reliability), etching resistance, and the like of the transparent conductor.

The matrix 122 may be a single layer formed of a composition for a matrix including an inorganic hollow particle, a fluorine-containing monomer or an oligomer thereof, a photosensitive resin, a crosslinking agent, and an initiator. The transparent conductor 100 according to the present embodiment may be patterned without using a separate photoresist and thus may have high productivity.

2 schematically shows a patterning process of the transparent conductor 100 according to the present embodiment. Referring to FIG. 2, a mask pattern having a desired pattern may be disposed on the transparent conductor 100 according to the present embodiment, and UV may be irradiated. The amount of UV radiation can be changed depending on the thickness of the matrix, the material of the matrix, and the like. UV irradiation can form a portion A to which UV is exposed and a portion B to which UV is not exposed in the matrix. After removing the mask pattern, the transparent conductor is developed and cleaned to remove the matrix of the unexposed portion. After the curing and the etching, the curing and the hard baking are performed to prepare a transparent conductor having a desired pattern. The etchant may be used as a mixture of nitric acid, acetic acid, phosphoric acid, Al etchant of Transene, but is not limited thereto. When the transparent conductor 100 is patterned by adding an etching solution treatment, the transparent conductor 100 may be well patterned even when the concentration of the etchant is diluted. However, pattern formation may be completed only by image development and cleaning, without performing etching liquid treatment and cleaning. In addition, the transparent conductive layer 120 is excellent in adhesion to the substrate layer 110 and is not affected by development, cleaning, etc. during patterning, and thus may not be peeled from the substrate layer.

Hereinafter, the composition for a matrix is explained in full detail.

The inorganic hollow particles and the fluorine-containing monomer or the oligomer thereof can improve the optical properties of the transparent conductive layer, lower the haze of the transparent conductor and increase the light transmittance. Specifically, the transparent conductor 100 may have a haze of about 1.5% or less, specifically about 0% to about 1.5% at a wavelength of 550nm. The transparent conductor 100 may have a total light transmittance of about 90% or more, specifically about 90% to about 99% in a visible light region, for example, a wavelength of 400 nm to 700 nm. In the above range, good transparency can be used as a transparent conductor. At the same time, the inorganic hollow particles and the fluorine-containing monomer or the oligomer thereof together with the following photosensitive resin affect the pattern formability of the transparent conductive layer, thereby improving the pattern forming ability of the transparent conductive layer and increasing the adhesion to the substrate layer. It is possible to prevent the transparent conductive layer from being peeled off from the base layer even by developing or washing.

The inorganic hollow particles may have a refractive index of about 1.4 or less, specifically about 1.30 to about 1.40, about 1.33 to about 1.38. The average particle diameter (D50) of the inorganic hollow particles may be about 100 nm or less, specifically about 30 nm to about 100 nm, specifically about 40 nm to about 70 nm. It may be included in the matrix in the above range, it may be advantageous to apply as a transparent conductive layer. Inorganic hollow particles are 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 mixtures thereof, which may be surface treated. The fluorine-containing monomer or oligomer thereof may include a fluorine-containing (meth) acrylic monomer or an oligomer thereof. The fluorine-containing monomer may be Kyoeisha LINC series (example LINC-3A), and the oligomer may be DAIKIN Corporation OPTOOL series (example AR-100).

The inorganic hollow particles and the fluorine-containing monomers or oligomers thereof may each be included by themselves, or may be included in a solution containing both of them. The solution may further include an initiator, a (meth) acrylic monomer, and a solvent such as methyl isobutyl ketone. The solution containing the entire inorganic hollow particles and the fluorine-containing monomer or the oligomer thereof, or the entire inorganic hollow particles and the fluorine-containing monomer or the oligomer thereof may have a refractive index of about 1.42 or less, specifically about 1.33 to about 1.38. In the above range, the optical properties of the transparent conductive layer may be good. The solution may include, but is not limited to, a commercially available product such as A-2505 (Pelnox), OPSTAR TU series (JSR), and the like.

The inorganic hollow particles and the fluorine-containing monomer or the entirety of the oligomers thereof are from about 10% to about 50% by weight based on solids in the matrix composition, for example about 10, 11, 12, 13, 14, 15, 16, 17, 18 , 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43 , 44, 45, 46, 47, 48, 49, 50% by weight, specifically about 20% to about 40% or about 30% to about 50% by weight. In the above range, the transparency of the film is improved to increase the transmittance, there may be an effect of improving the adhesion of the matrix to the substrate layer. In the present specification, "solid content" means the entirety of the matrix composition except for the solvent.

The photosensitive resin can be cured to form a matrix and pattern the transparent conductor by UV exposure. The photosensitive resin may include a positive or negative photosensitive resin upon UV irradiation.

The photosensitive resin has a weight average molecular weight of about 5000 g / mol to about 10000 g / mol such as 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000 g / mol, specifically about 5500 g / mol About 9000 g / mol. In the above range, there may be an effect that the pattern formation is good and the adhesion of the matrix is improved. The photosensitive resin is a general photosensitive resin for photoresists, and includes novolacs such as phenol novolak resins, cresol novolak resins, naphthol novolak resins, novolak resins using various phenolic compounds, and alkoxy group-containing aromatic ring modified novolak resins Resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylolethane resin, biphenyl modified phenol resin, biphenyl modified naphthol Resins, aminotriazine-modified phenolic resins, and the like. Among these, a novolak resin may be preferable at the point which is excellent in pattern property at the time of mixing with an inorganic hollow particle and a fluorine-containing monomer or its oligomer.

The photosensitive resin is about 30% to about 65% by weight based on solids in the composition for the matrix, for example about 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43 , 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65% by weight, specifically about 40 wt% to about 60 wt%. In the above range, the pattern is formed by exposure, development, cleaning, etc., the adhesion of the matrix, the coating property can be excellent and there is no effect on the conductivity of the metal nanowires.

The crosslinking agent can cure the photosensitive resin, the fluorine-containing monomer or the oligomer thereof. The crosslinking agent is a compound containing a double bond such as melamine compound, guanamine compound, glycoluril compound, urea compound, resol resin, epoxy compound, isocyanate compound, azide compound, alkenyl ether group, acid Anhydride compounds, oxazoline compounds, and the like. Among these, the melamine-based compound can increase the curing rate of the composition for the matrix when mixed with the inorganic hollow particles and the fluorine-containing monomer or oligomer-containing solution, and facilitate the pattern formation of the transparent conductor.

The melamine-based compound is, for example, hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, One to six of the methylol groups of hexamethylolmelamine may contain acyloxymethylated compounds and the like. The guanamine compound is a compound in which 1 to 4 methylol groups are methoxymethylated of tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, and tetramethylolguanamine. Methoxyethylguanamine, tetraacyloxyguanamine, tetramethylolguanamine, and the like. The compound may include acyloxymethylated one to four methylol groups. The glycoluril compound may be 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6- Tetrakis (hydroxymethyl) glycoluril and the like. The urea compound is 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea Etc. can be mentioned. The said resol resin is phenolic hydroxyl group containing compounds, such as bisphenol, naphthol, dihydroxy naphthalene, such as alkyl phenol, phenyl phenol, resorcinol, biphenyl, bisphenol A, bisphenol F, such as phenol, cresol, and xylenol; The polymer obtained by making an aldehyde compound react on alkaline catalyst conditions is mentioned. Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, trimethylol methane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylol ethane triglycidyl ether, and the like. Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate and the like. Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, 4,4'-oxybisazide and the like. Compounds containing double bonds such as alkenyl ether groups include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol di Vinyl ether, neopentyl glycol divinyl ether, trimethylol propane trivinyl ether, hexanediol divinyl ether, 1, 4- cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetra Vinyl ether, sorbitol pentavinyl ether, trimethylol propane trivinyl ether, etc. are mentioned. The acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'-(iso Aromatic acid anhydrides such as propylidene) diphthalic anhydride and 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride; And alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride anhydrous decenylic acid, and trialkyltetrahydrophthalic anhydride. .

Crosslinking agent is about 1% to about 10% by weight, for example about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight, specifically about 1% by weight, based on solids in the composition for the matrix To about 5% by weight. In the above range, the process margin of the pattern formation can be controlled by controlling the degree of crosslinking of the photosensitive resin and the pattern formation can be facilitated.

The initiator is a curing agent for the photosensitive resin, the fluorine-containing monomer or the oligomer thereof, and may include a conventional initiator known to those skilled in the art. For example, the initiator may include photosensitive initiators such as initiators that generate active radicals and initiators that initiate cationic polymerization. Initiators include oxime compounds such as halogenated hydrocarbon derivatives (for example, derivatives having a triazine skeleton, derivatives having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. , Organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenones, hydroxyacetophenones, and the like. Among these, an oxime derivative is preferable at the point which is easy to form a pattern at low exposure amount. Oxime derivatives include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime), 3-benzoyloxyimido Butan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane -1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenyl Propan-1-one and the like.

The initiator is about 1% to about 15% by weight based on solids in the composition for the matrix, for example about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 weight percent, specifically about 1 weight percent to about 10 weight percent. Within this range, there may be an effect of facilitating pattern formation even at low exposure doses and improving adhesion of the matrix layer in the post-curing process.

The composition for the matrix may further include at least one of an adhesion promoter and an antioxidant.

An adhesion promoter may increase the adhesion of the transparent conductive layer to the base layer to reduce the thickness of the transparent conductive layer and increase the reliability of the transparent conductor. The adhesion promoter may include one or more of a silane coupling agent, a monofunctional (meth) acrylic monomer, and a bifunctional (meth) acrylic monomer. These may be included alone or in combination of two or more. Silane coupling agents are commonly known silane coupling agents, such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycid Silane coupling agents having an epoxy group such as oxypropyltrimethoxysilane; Polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane; Amino group-containing silane coupling agents such as 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane; And 3-chloropropyltrimethoxysilane. Monofunctional or bifunctional (meth) acrylic monomers are mono- or difunctional (meth) acrylic monomers of C3 to C20 polyhydric alcohols, including isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, Cyclohexyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, ethylene glycol di (meth) acrylate, neopentylglycoldi (meth) acrylate, hexanedioldi (meth) acrylate, cyclodecane dimethanol And may comprise one or more of di (meth) acrylates. Preferably, the adhesion promoter may use a silane coupling agent having an epoxy group as the silane coupling agent. In this case, adhesiveness can be improved even in the thickness of thin transparent conductive layer (for example, transparent conductive layer thickness of about 2 micrometers or less). In particular, even after a transparent conductive layer is patterned, the adhesiveness of a transparent conductive layer can be improved.

Adhesion promoters are from about 5% to about 20% by weight in the composition for a solids based matrix for example about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20% by weight, specifically about 5% to about 15% by weight. Within this 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 at least one of triazole-based, triazine-based, phosphite-based phosphorus, HALS (Hinder amine light stabilizer), phenol-based, metal acetylacetonate-based antioxidant. These may be included alone or in combination of two or more. Specifically, the phosphorus antioxidant is tris (2,4-di-tert-butylphenyl) phosphite, and the phenolic antioxidant is pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydrate Oxyphenyl) propionate). HALS-based antioxidants include 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, dimethylsuccinate air with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol Coalescing, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxy Ethylamine) -1,3,5-triazine and the like, but is not limited thereto. Metal acetylacetonate-based antioxidants may include, but are not limited to, tris (acetylacetonato) iron (III), tris (acetylacetonato) chrome (III), and the like.

The antioxidant is about 0.01% to about 10% by weight in the composition for a matrix based on solids, for example about 0.01, 0.05, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10% by weight, specifically About 0.5% to about 7% by weight. In the above range, it is possible to prevent the oxidation of the metal nanowire, high pattern uniformity of the patterned transparent conductor and may be advantageous for the implementation of a fine pattern.

The matrix composition may further include a solvent. The solvent may include one or more of ketone solvents such as propylene glycol monomethyl ether acetate (PGEMA) and methyl isobutyl ketone, and alcohol solvents such as isopropyl alcohol and ethanol.

The composition for the matrix may further include an additive. The additives may include surfactants such as fluorine-based surfactants, antistatic agents, ultraviolet absorbers, viscosity modifiers, heat stabilizers, dispersants, thickeners and the like.

The composition for the matrix may have a viscosity of about 0.1 cP to about 20 cP at 25 ° C. In the above range, it is possible to improve the coating property of the composition for the matrix, and to be uniformly coated with a thin film so that the transparent conductive layer has uniform physical and chemical properties.

The transparent conductive layer 120 has a thickness of about 1 μm or more and about 2 μm or less, for example, about 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2 μm, more specifically about 1 μm. And about 1.7 μm or less. In the above range, it can be used in the optical display device, the pattern forming ability is good, the adhesion to the substrate layer is good and the optical properties are excellent.

The transparent conductor 100 may have a sheet resistance of about 100 μs / □ or less, specifically about 50 μs / □ or less, and more specifically about 20 μs / □ to about 50 μs / □, measured by a 4-probe or non-contact sheet resistance meter. have. In the above range, the sheet resistance is low, it can be used as an electrode film for a touch panel, it can be applied to a large area touch panel. The thickness of the transparent conductor 100 may be about 10 μm to about 250 μm, specifically about 50 μm to about 200 μm. In the above range, it can be used as a transparent electrode film including a film for a touch panel, it can be used as a transparent electrode film for a flexible touch panel. The transparent conductor 100 may be used as a transparent electrode film of a touch panel, an E-paper, or a solar cell, in the form of a film, and patterned by etching or the like.

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

Referring to FIG. 3, the transparent conductor 100 ′ of the present embodiment is except that the transparent conductive layer 120 ′ is patterned into a transparent conductive layer 120 a and a non-conductive layer 120 b having no conductivity. It is substantially the same as the transparent conductor 100 of one 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. Specifically, patterning is the same as described above with reference to FIG. 2. Further, in order to prevent the metal nanowires of the pattern layer cured from the etching solution during etching, the etching solution may be used at low concentration or the etching time may be shortened.

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

Referring to FIG. 4, the optical display device 200 according to an exemplary embodiment of the present invention may include a display unit 210, a polarizer 220, a transparent electrode body 230, a window film 240, and an adhesive layer 250. It includes, the transparent electrode body 230 may be formed of a transparent conductor according to embodiments of the present invention. 4 illustrates a structure in which the display unit 210, the polarizing plate 220, the transparent electrode body 230, and the window film 240 are stacked in this order, but the display unit 210, the transparent electrode body 230, The polarizer 220 and the window film 240 may be stacked in the order of the structure.

The display unit 210 is for driving the optical display device 200 and may include an optical element including a substrate and an OLED, an LED, or an LCD element formed on the substrate. In one embodiment, the display unit 210 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective film, an insulating film. In another embodiment, the display unit 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. 4 illustrates a structure in which the display unit 210 and the transparent electrode body 230 are separately stacked, but the transparent electrode body 230 may be formed inside the display unit.

The polarizing plate 220 may be formed on the display unit 210 to implement polarization of internal light or prevent reflection of external light to implement a display or improve contrast ratio of the display. The polarizer 220 may be a polarizer alone. Alternatively, the polarizing plate 220 may include a polarizer and a protective film formed on one or both sides of the polarizer. Although not shown in FIG. 4, a polarizer may be further formed below the display unit 210 to further improve the contrast ratio of the display. In this case, the polarizer may be formed on the display unit 210 by an adhesive layer.

The transparent electrode body 230 may be formed on the polarizing plate 220, and may generate an electrical signal by detecting a change in capacitance generated when the transparent electrode body 230 is touched by contact or the like. The transparent electrode body 230 may include a base electrode 110, a first electrode 231 formed on one surface of the base layer 110, a second electrode 232, and a third electrode formed on the other side of the base layer 110 ( 233 and the fourth electrode 234. 4 illustrates a structure in which the third electrode 233, the fourth electrode 234, the base layer 110, the first electrode 231, and the second electrode 232 are stacked in the order of the substrate layer 110. ) / Third electrode 233 and fourth electrode 234 / base layer 110 / first electrode 231 and second electrode 232 in this order.

The window film 240 may be formed on the outermost side 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 polarizing plate 220, between the polarizing plate 220 and the transparent electrode body 230, and between the transparent electrode body 230 and the window film 240. The bonding between the 210, the polarizing plate 220, the transparent electrode body 230, and the window film 240 may be strengthened. The adhesive layer 250 may be formed of a conventional optically transparent adhesive.

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

Referring to FIG. 5, in the optical display device 300 according to another exemplary embodiment, the transparent electrode body 230 ′ is formed of the base layer 110 and the third electrode 233 formed on one surface of the base layer 110. And a fourth electrode 234, except that the first electrode 231 and the second electrode 232 are further formed on the window film 240 ′ according to the exemplary embodiment of the present invention. Substantially the same as 200).

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

In the method of manufacturing a transparent conductor according to an embodiment of the present invention, a metal nanowire dispersion is coated on a base layer to form a metal nanowire dispersion layer, a composition for a matrix is coated on the metal nanowire dispersion layer, It may include curing the metal nanowire dispersion layer and the composition for the matrix.

The metal nanowire dispersion may contain metal nanowires. The metal nanowire dispersion may further include a solvent to further increase the coating property of the metal nanowire. The solvent may include an organic solvent such as water and alcohol, but is not limited thereto. The metal nanowire dispersion may further include a binder, an initiator, an additive, and the like. The additives can be dispersants, thickeners and the like. The binder may include one or more of a (meth) acrylate-based monofunctional monomer and a (meth) acrylate-based polyfunctional monomer. The dispersant can increase the dispersion of the metal nanowires and the binder. Thickeners can increase the viscosity of the metal nanowire dispersion. The binder, initiator, and additives as a whole can be included from about 0.1% to about 50% by weight, specifically from about 5% to about 45% by weight solids in the metal nanowire dispersion. In the above range, the optical properties of the transparent conductor may be improved, the contact resistance may be prevented from increasing, and the durability and chemical resistance may be improved. Metal nanowire dispersions can be prepared by mixing the solvent in a metal nanowire-containing solution, such as a commercially available product of Cambrios (eg ClearOhm Ink).

The composition for a matrix can be formed from the composition for a matrix containing an inorganic hollow particle, a fluorine-containing monomer or an oligomer, photosensitive resin, a crosslinking agent, and an initiator.

Then, by coating the metal nanowire dispersion on the substrate layer to form a metal nanowire dispersion layer, coating the composition for the matrix on the metal nanowire dispersion layer, and curing the metal nanowire dispersion layer and the composition for the matrix A transparent conductive layer can be formed. Coating may be performed by bar coating, slot die coating, gravure coating, roll-to-roll coating, but is not limited thereto. The coating thickness may be about 1 μm or more and about 2 μm or less, more specifically about 1 μm or more and about 1.7 μm or less. Curing can form a transparent conductive layer and can raise the intensity | strength of a transparent conductive layer. Curing may include one or more of thermal curing, light curing. Thermal curing may be performed for about 40 ° C. to about 180 ° C., about 1 minute to about 48 hours. Light curing may be performed with a UV dose of about 50 mJ / cm ² to about 1,000 mJ / cm ² . Before hardening the coating film for transparent conductive layers, the coating film for transparent conductive layers can be dried, and hardening time can be shortened. Drying may be performed for about 40 ° C. to about 180 ° C., for about 1 minute to about 48 hours.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Example  One

A silver nanowire dispersion was prepared by adding 45 parts by weight of a silver nanowire-containing solution (2 wt% solid content such as Clearohm ink, Cambrios, silver nanowires, etc.) to 55 parts by weight of ultrapure distilled water.

Hollow silica and fluorine-containing monomer containing solution (Pelnox, A-2505, hollow silica, containing fluorine-containing monomer and initiator, refractive index: 1.33) 37 parts by weight, solution containing novolak resin with photosensitive resin (Showa Denko, RY-25 ) 13 parts by weight, 34 parts by weight of a solution containing hexamethoxymethyl melamine as a crosslinking agent, a solution containing an oxime ester initiator PBG304 as an initiator (DKSH, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-car 16 parts by weight of bazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)) and a solvent propylene glycol monomethyl ether acetate were added to the composition for the matrix having a solid content concentration of 1.6% by weight. Prepared. The composition for the matrix included 37% by weight of the total of the hollow silica and the fluorine-containing monomer, 52% by weight of the novolak resin, 3% by weight of hexamethoxymethyl melamine, and 8% by weight of the oxime ester initiator.

On the substrate layer (polycarbonate film, Teijin, thickness: 50㎛), the prepared silver nanowire dispersion was coated with a spin coater, dried for 90 seconds in an oven at 140 ℃, and then the composition for the matrix was coated with a bar coater Thereafter, the transparent conductor was manufactured by drying in an oven at 80 ° C. for 120 seconds to form a transparent conductive layer having a thickness of 1.2 μm.

Example  2

In Example 1, a transparent conductor was manufactured in the same manner except that the thickness of the transparent conductive layer was changed to 1.7 μm.

Example  3

A silver nanowire-containing solution was prepared in the same manner as in Example 1.

Hollow silica and fluorine-containing monomer containing solution (Pelnox, A-2505, hollow silica, containing fluorine-containing monomer and initiator, refractive index: 1.33) 33 parts by weight, solution containing novolak resin with photosensitive resin (Showa Denko, RY-25 ) 11 parts by weight, solution containing hexamethoxymethyl melamine as crosslinking agent, 16 parts by weight, solution containing oxime ester initiator PBG304 as initiator (DKSH, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-car 16 parts by weight of bazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime)), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Shin Yetsu Co., Ltd.) as an adhesion promoter. KBM-303) 10 parts by weight and a solvent propylene glycol monomethyl ether acetate were added to prepare a composition for the matrix having a solid content concentration of 1.6% by weight. Composition for the matrix is 33% by weight hollow silica and fluorine-containing monomer, 46% by weight novolak resin, 3% by weight hexamethoxymethyl melamine, 8% by weight oxime ester initiator, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane at 10% by weight.

A transparent conductor having a transparent conductive layer with a thickness of 1.1 μm was prepared in the same manner as in Example 1 using the prepared silver nanowire-containing solution and the composition for a matrix.

Comparative example  One

A silver nanowire-containing solution was prepared in the same manner as in Example 1.

37 parts by weight of dipentaerythritol hexaacrylate (DPHA, Entis), 13 parts by weight of a novolak resin-containing solution (Showa Denko, RY-25) as a photosensitive resin, 34 parts by weight of a solution containing hexamethoxymethyl melamine as a crosslinking agent Solution containing an oxime ester-based initiator PBG304 as an initiator (DKSH, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- ( 16 parts by weight of O-acetyl oxime)) and a solvent propylene glycol monomethyl ether acetate were added to prepare a composition for a matrix having a solid content concentration of 1.6% by weight. The composition for the matrix contained 37% by weight of dipentaerythritol hexaacrylate, 52% by weight of novolak resin, 3% by weight of hexamethoxymethyl melamine, and 8% by weight of oxime ester initiator.

A transparent conductor having a transparent conductive layer with a thickness of 1.2 μm was prepared in the same manner as in Example 1 using the prepared silver nanowire-containing solution and the composition for a matrix.

Comparative example  2

A silver nanowire-containing solution was prepared in the same manner as in Example 1.

30 parts by weight of a novolak resin-containing solution (Showa Denko, RY-25) as a photosensitive resin, 47 parts by weight of a solution containing hexamethoxymethyl melamine as a crosslinking agent, a solution containing an oxime ester initiator PBG304 as a initiator (DKSH, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropaneone-1- (O-acetyloxime)) 23 parts by weight, and solvent propylene glycol monomethyl Etheracetate was added to prepare a matrix composition having a solid concentration of 1.6% by weight. The composition for the matrix contained 89% by weight of novolak resin, 3% by weight of hexamethoxymethyl melamine, and 8% by weight of oxime ester initiator.

A transparent conductor having a transparent conductive layer with a thickness of 1.2 μm was prepared in the same manner as in Example 1 using the prepared silver nanowire-containing solution and the composition for a matrix.

The physical properties of the transparent conductors of Examples and Comparative Examples were evaluated, and the results are shown in Table 1 below.

(1) Pattern Formability and Adhesiveness: 50 mJ / cm ² using a pattern mask (line width of 30 μm / line width of non-etching part) having a pattern having a line width of 30 μm on the transparent conductors of Examples and Comparative Examples. Ultraviolet light exposure was performed. The exposed sample was placed in a 5% aqueous solution of trimethylammonium hydroxide as a developer, developed for 30 seconds, first washed, baked for 3 minutes in a 120 ° C. oven, and then exposed to ultraviolet light at 200 mJ / cm ² to form a pattern. A layer was formed. The transparent conductor on which the pattern layer was formed was etched at 25 ° C. (Al etchant, 75% to 85% by weight of an aqueous solution of phosphoric acid at a concentration of 85% by weight, 3% to 10% by weight of a nitric acid solution at a concentration of 70% by weight, 99.7% by weight It was immersed in a mixed solution (Aluminum etchant type A of Transene) of 5% to 20% by weight of an acetic acid solution at a concentration, and etched and washed secondly. The line width of the etching portion of the second washed transparent conductor was observed with an optical microscope (MX-50, Olympus), and the standard deviation of the line width of the formed etching portion was determined. ◎ when the standard deviation is 10% or less and the pattern formation shape is good ◎, when the standard deviation is more than 10% and 20% or less and the pattern formation shape is good ○, when the standard deviation is more than 20% and the pattern is not partially formed △, If no pattern was formed, it was evaluated as x. After the development and the first washing, the case where the transparent conductive layer was not peeled off from the substrate layer at all, was evaluated as x when the transparent conductive layer was partially peeled off and the transparent conductive layer was completely peeled off.

(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 for the transparent conductors of Examples and Comparative Examples with the conductive layer facing the light source. .

(3) Sheet resistance: The sheet resistance was measured using the non-contact sheet resistance measuring instrument (EC-80P, NAPSON) about the transparent conductor of an Example and a comparative example. Sheet resistance was measured for the unpatterned transparent conductive layer.

	Hollow silica and fluorine-containing monomer solution	Photosensitive resin	DPHA	Adhesion promoter	Transparent conductive layer thickness (㎛)	Pattern formability	Adhesion	Haze (%)	Total light transmittance (%)	Sheet resistance (Ω / □)
Example 1	include	include	Without	Without	1.2	○	○	1.37	91.23	25.90
Example 2	include	include	Without	Without	1.7	○	○	1.33	91.16	25.69
Example 3	include	include	Without	include	1.1	○	○	1.39	91.19	26.26
Comparative Example 1	Without	include	include	Without	1.2	△	△	1.60	89.21	24.90
Comparative Example 2	Without	include	Without	Without	1.2	△	X	1.59	88.92	25.50

As shown in Table 1, the transparent conductor according to the present embodiment can be patterned without a photoresist, thereby providing excellent productivity, excellent pattern forming ability, and excellent adhesion to the substrate layer. It was not affected by the back and the like and did not peel off from the substrate layer. In addition, the transparent conductor according to the present embodiment was excellent in optical characteristics and low in sheet resistance, thereby being excellent in conductivity.

However, the comparative example which does not contain a hollow silica particle and a fluorine-containing monomer was inferior in pattern formation property, and after patterning, the transparent conductive layer peeled off from the base material layer, and was not good in adhesiveness.

Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (14)

1. A base layer and a transparent conductive layer formed on the base layer;

   The transparent conductive layer includes a metal nanowire and a matrix impregnated with the metal nanowire,

   The matrix is formed of a composition for a matrix containing an inorganic hollow particle, a fluorine-containing monomer or an oligomer thereof, a photosensitive resin, a crosslinking agent and an initiator.
2. The transparent conductor of claim 1, wherein the transparent conductive layer has a thickness of about 1 μm or more and about 2 μm or less.
3. The transparent conductor of claim 1, wherein the metal nanowires are fully impregnated with the matrix.
4. The transparent conductor of claim 1, wherein the metal nanowires comprise silver nanowires.
5. The transparent conductor according to claim 1, wherein the solution containing all of the inorganic hollow particles and the fluorine-containing monomer or the oligomer thereof or all of the inorganic hollow particles and the fluorine-containing monomer or the oligomer thereof has a refractive index of about 1.42 or less.
6. The method of claim 1, wherein the photosensitive resin is novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane A transparent conductor comprising at least one of a resin, a biphenyl-modified phenol resin, a biphenyl-modified naphthol resin, and an aminotriazine-modified phenol resin.
7. The compound of claim 1, wherein the crosslinking agent includes a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, a resol resin, an epoxy compound, an isocyanate compound, an azide compound, and an alkenyl ether group. A transparent conductor comprising at least one of an acid anhydride compound and an oxazoline compound.
8. The composition of claim 1, wherein the composition for the matrix is about 20% to about 40% by weight of the inorganic hollow particles and the fluorine-containing monomer or oligomer thereof, and about 40% to 60% by weight of the photosensitive resin. And about 1% to about 5% by weight crosslinking agent, and about 1% to about 10% by weight of the initiator.
9. The transparent conductor of claim 1, wherein the matrix composition further comprises at least one of an adhesion promoter and an antioxidant.
10. The composition of claim 9, wherein the composition for the matrix is about 20 wt% to about 40 wt% of the inorganic hollow particles and the fluorine-containing monomer or oligomer thereof, and about 40 wt% to 60 wt% of the photosensitive resin. About 1% to about 5% by weight of the crosslinking agent, about 1% to about 10% by weight of the initiator, and about 5% to about 15% by weight of the adhesion promoter.
11. The transparent conductor of claim 1, wherein the transparent conductor has a total light transmittance of about 90% or more at a wavelength of 400 nm to 700 nm.
12. The transparent conductor of claim 1, wherein the base layer further comprises a functional layer.
13. The transparent conductor of claim 1, wherein the transparent conductive layer is patterned.
14. A display device comprising the transparent conductor of claim 1.

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