KR20150048042A - Transparent conductor, method for preparing the same and optical display apparatus comprising the same - Google Patents

Abstract

The present invention relates to a transparent conductor, a manufacturing method thereof, and an optical display device including the same. The transparent conductor includes a base layer and a conductive layer which is formed on the base layer and includes a metal nanowire and a matrix. A transmission b* value is 1.5 or less. The matrix includes a five or six functional monomer and a three functional monomer.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent conductor, a method of manufacturing the same, and an optical display device including the transparent conductor. [0002]

The present invention relates to a transparent conductor, a method of manufacturing the same, and an optical display device including the same.

The transparent conductor is used in many aspects such as a touch screen panel and a flexible display included in a display device. Transparent conductors should have good physical properties such as transparency and sheet resistance. Flexibility has also been required in recent years as the area of use extends to flexible displays. The transparent conductor including the transparent conductive layer including silver nanowires has excellent bending property. However, the transparent conductor including the silver nanowire includes an overcoating layer for enhancing adhesion with the base film. In general, the overcoat layer used has a high transmission b * value in the color difference coefficient, Color distortion may be exhibited, and optical characteristics such as transmittance and haze may be deteriorated. In addition, there is a problem that the transparent conductive layer including silver nanowires can be seen as yellow due to silver nanowires. Korean Patent Publication No. 2012-0053724 discloses a transparent conductive film and a manufacturing method thereof.

An object of the present invention is to provide a transparent conductor having good optical characteristics including transmittance, haze and the like by lowering the transmission b * value.

Another object of the present invention is to provide a transparent conductor having low surface resistance, reliability and durability as well as optical properties.

The transparent conductor of the present invention is a transparent conductor comprising a base layer and a conductive layer formed on the base layer and including metal nanowires and a matrix, wherein the transmission b * value is 1.5 or less, Can be formed from a composition comprising a hexafunctional monomer and a trifunctional monomer.

The method of manufacturing a transparent conductor of the present invention comprises forming a metal nanowire network layer on a substrate layer and including a pentafunctional or hexafunctional monomer, a trifunctional monomer, an adhesion promoter, an antioxidant and an initiator on the metal nanowire network layer To form a conductive layer with the composition for the matrix.

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

The present invention provides a transparent conductor having good optical characteristics including low transmittance and haze, low sheet resistance, and high reliability and durability.

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

The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. 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. In this specification, 'upper' and 'lower' are defined with reference to the drawings, and 'upper' may be changed to 'lower' and 'lower' Quot; rate " may mean acrylate and / or methacrylate.

In the present specification, the "transmission b * value" means a value obtained by multiplying the transparency obtained by laminating metal nanowires and a conductive layer (thickness: 10 nm to 1 m) on a polycarbonate base film (thickness: 50 m to 125 m) (Konica Minolta) at 400 to 700 nm. However, the material and thickness of the base film, the thickness and wavelength of the conductive layer may be changed, and the present invention can be included in the scope of the present invention.

In the present specification, "reliability" means that a transparent conductive film (Optically Clear Adhesives 8215, 3M) and a PET (polyethylene terephthalate) film having a thickness of 38 to 125 탆 are laminated on a transparent conductor at a temperature of 85 캜 and The resistance change rate is measured after standing at 85% relative humidity for 240 hours. When the resistance change rate is 10% or less, specifically 1 to 10%, it is determined that the resistance is reliable.

A transparent conductor according to embodiments of the present invention comprises a substrate layer, a conductive layer formed on the substrate layer and comprising metal nanowires and a matrix, wherein the matrix comprises five or six functional monomers and three functional monomers Or the like. As a result, it is possible to realize a transparent conductor having good optical characteristics including transmittance and haze, low surface resistance, and improved reliability and durability.

Hereinafter, a transparent conductor according to one embodiment of the present invention will be described with reference to FIG.

1, the transparent conductor 100 of this embodiment includes a base layer 110, a conductive layer 120 formed on the base layer 110 and including metal nanowires 121 and a matrix 122, And the transmission b * value is 1.5 or less, and the matrix 122 may be formed of a composition comprising a pentafunctional or hexafunctional monomer, and a trifunctional monomer. As a result, the matrix 122 is UV-cured, thereby increasing the transmittance of the transparent conductor and lowering the transmission b * value, minimizing the yellow appearance of the conductive layer and increasing the reliability of the conductive layer.

The transmission b * value may be 1.5 or less, specifically 0.50 to 1.50 or 1.00 to 1.30. Within the above range, the transparency of the transparent conductor 100 is high, the rate of change in resistance is low, and the transparent conductor 100 can be used as a transparent electrode film by patterning. Of course, the matrix 122 may have durability, chemical resistance, solvent resistance, etc. of the conventional transparent conductor.

The base layer 110 is a film having transparency and can be a film having a transmittance of 85% or more and 100% or less, for example, 90% to 99% at a wavelength of 550 nm. Specifically, the base layer 110 may be formed of a material selected from the group consisting of polyesters including polycarbonate, cycloolefin polymer, polyethylene terephthalate (PET), polyethylene naphthalate and the like, polyolefins polyolefine, polysulfone, polyimide, silicone, polystyrene, polyacryl, and polyvinylchloride, or a mixture thereof. However, , But is not limited thereto. The base layer 110 may be a single layer or a laminated type of two or more resin films. The thickness of the base layer 110 may be 10 占 퐉 to 200 占 퐉, specifically, 50 占 퐉 to 150 占 퐉. In this range, it can be used for display.

The conductive layer 120 includes metal nanowires 121 and a matrix 122.

The metal nanowires 121 form a network, and can have conductivity and good flexibility and flexibility. The metal nanowires 121 have better dispersibility than metal nanoparticles due to their nanowire shape. Further, the metal nanowires 121 can provide an effect of significantly lowering the sheet resistance of the transparent conductive film due to the difference in particle shape to nanowire shape. The metal nanowires 121 have a shape of a very fine line having a specific cross section. In an embodiment, the aspect ratio of the nanowire length L to the diameter d of the cross-section of the metal nanowire 121 may be 10 to 2,000. In this range, a high conductivity network can be realized even at a low nanowire density, and the sheet resistance can be lowered. For example, the aspect ratio may be 500 to 1,000, for example, 500 to 700. The diameter d of the cross section of the metal nanowires 121 may be greater than 0 and less than or equal to 100 nm. Within this range, a transparent conductor having high conductivity and low sheet resistance can be realized by securing high L / d. For example, 30 nm to 100 nm, for example, 60 nm to 100 nm. The metal nanowires 121 may have a length L of 20 mu m or more. Within this range, a high L / d can be ensured to realize a conductive film having a low conductivity and a low sheet resistance. For example, 20 占 퐉 to 50 占 퐉. The metal nanowires 121 may comprise nanowires made of any metal. For example, silver, copper, gold nanowires or mixtures thereof. Silver nanowires or mixtures containing them may be preferably used.

The metal nano wire 121 may be manufactured by a conventional method or a commercially available product may be used. For example, it can be synthesized through a reduction reaction of a metal salt (for example, silver nitrate, AgNO ₃ ) in the presence of a polyol and poly (vinylpyrrolidone). Alternatively, a commercially available product of Cambrios (e.g., ClearOhm Ink., A solution containing a metal nanowire) may be used. The metal nanowires 121 may include 13 wt% or more, for example, 13 wt% to 50 wt% of the conductive layer 120. Within this range, sufficient conductivity can be ensured and a conductive network can be formed.

The metal nanowires 121 may be used in a dispersed state in the liquid for easy application to the substrate layer 110 and adhesion to the substrate layer 110. Herein, a liquid composition in which metal nanowires are dispersed is referred to as a " metal nanowire composition ". The metal nanowire composition may include additives and binders for dispersing the metal nanowires. The binder is not particularly limited and includes, for example, carboxy methyl cellulose (CMC), 2-hydroxy ethyl cellulose (HEC), hydroxy propyl methyl cellulose HPMC, methylcellulose (MC), polyvinyl alcohol (PVA), tripropylene glycol (TPG), polyvinylpyrrolidone, xanthan gum (XG), ethoxylates Alkoxylate, ethylene oxide, propylene oxide, or copolymers thereof may be used.

The matrix 122 impregnates the metal nanowires 121. That is, the metal nanowires may be scattered or buried in the matrix 122. Also, some of the metal nanowires 121 may protrude from the surface of the matrix 122 and be exposed. The matrix 122 prevents oxidation and abrasion of the metal nanowires 121 that may be exposed on the top of the conductive layer 120 and provides adhesion between the conductive layer 120 and the substrate layer 110, The chemical resistance, the solvent resistance, and the like of the glass.

The matrix 122 may be formed of a composition for a matrix comprising a pentafunctional or hexafunctional monomer, and a trifunctional monomer. The pentafunctional or hexafunctional monomer may be a pentafunctional or hexafunctional (meth) acrylate monomer having a (meth) acrylate group, specifically a pentafunctional monomer or a hexafunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms. In particular, the inclusion of the non-urethane-based pentafunctional or hexafunctional monomer having no urethane group enables the laminate of the cured product to be densified in the network structure of the metal nanowires 121 and the adhesion to the base layer 110 can be improved. The pentafunctional or hexafunctional monomer may be selected from the group consisting of dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone denatured dipenta Modified caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa But are not limited thereto.

The trifunctional monomer is a trifunctional (meth) acrylate monomer having a (meth) acrylate group and contains a non-urethane-based trifunctional monomer having no urethane group, so that the lamination of the cured product in the network structure of the metal nanowire 121 becomes dense The adhesion to the base layer 110 can be improved. The trifunctional monomer may include at least one of a trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms and a trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms modified with an alkoxy group. More specifically, the monomer may be selected from the group consisting of trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol (meth) acrylate, tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and the like. The trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms modified with an alkoxy group can further improve the transparency and reliability of the transparent conductor in comparison with the trifunctional monomer having no alkoxy group and lower the transmission b * value, It is possible to prevent visible phenomena. Specifically, the trifunctional monomer having an alkoxy group (for example, an alkoxy group having 1 to 5 carbon atoms) may be an ethoxylated trimethylolpropane tri (meth) acrylate, a propoxylated glyceryl But are not limited to, one or more of propoxylated glyceryl tri (meth) acrylate.

The above-mentioned five functional or six functional monomer: trifunctional monomer may be contained in a weight ratio of 2: 1 to 5: 1, specifically 2: 1 to 3.5: 1 in the composition for a matrix, Permeability and reliability of the liquid crystal display device can be enhanced. If the trifunctional monomer is larger than the five or six functional monomers, adhesion with the base layer 110 may be weakened and reliability may be lowered.

The matrix 122 may include an adhesion promoter. The adhesion promoter improves the adhesion of the metal nanowires 121 to the base layer 110 and improves the reliability of the transparent conductive material 100. The adhesion promoter may include a silane coupling agent, at least one of monofunctional to trifunctional monomers Can be used. As the silane coupling agent, a commonly known silane coupling agent can be used. When a silane coupling agent having an amino group or an epoxy group is used, adhesion and chemical resistance may be good. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane ( 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane); A polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, and (meth) acryloxypropyltrimethoxysilane; Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-aminopropyltrimethoxysilane) amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; And 3-chloropropyltrimethoxysilane may be used.

The monofunctional or trifunctional monomer may be an acid ester monomer. (Meth) acrylate monomer having a (meth) acrylate group, specifically, a monofunctional or trifunctional monomer of a polyhydric alcohol having 3 to 20 carbon atoms, more specifically a (meth) acrylate (meth) acrylate, isobornyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2) Glycerol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, glycerol tri Meth) acrylate Acrylate such as ethyleneglycol di (meth) acrylate, neopentylglycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclodecanedimethanol di But are not limited to, one or more of cyclodecane dimethanol di (meth) acrylate.

The adhesion promoting agent may be included in the composition for a matrix in an amount of 1 wt% to 15 wt%, specifically 5 wt% to 10 wt%. Adhesiveness can be improved while maintaining the reliability and conductivity of the transparent conductor within the above range.

The matrix 122 may comprise an antioxidant. The antioxidant can prevent the oxidation of the metal nanowire network of the conductive layer 120. The antioxidant can be used in combination with an antioxidant such as a triazole antioxidant, a triazine antioxidant, a phosphite- , HALS (Hinder amine light stabilizer) -based antioxidant, and phenol-based antioxidant, for example, by mixing two or more kinds of them, the oxidation of the metal nanowires 121 can be prevented and reliability can be improved. When two or more kinds of antioxidants are used, oxidation prevention and reliability can be more excellent. In one embodiment, the antioxidant may be a mixture of phosphorus and phenol, a mixture of phosphorus and HALS, or a mixture of phenol and HALS, especially phosphorus and HALS, or a triazole, Phosphorous, or a mixture of triazine, phenol, and phosphorous. The transparent conductor 100 includes a phosphorus antioxidant to reduce the transmission b * value without affecting the conductivity of the conductive layer 120. [

For example, tris (2,4-di-tert-butylphenyl) phosphite is used as the phosphorus antioxidant, pentaerythritol tetrakis Can be 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Pentaerythritol tetrakis , HALS 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) (2,2,6,6-tetramethyl-5-piperidinyl) sebacate), 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine (Copolymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol), 2,4-bis [N-butyl- Cyclohexyloxy-2,2,6,6-tetramethyl 4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine (N-butyl- , 6,6-tetramethylpiperidine-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine) and the like.

The antioxidant may be contained in the composition for a matrix in an amount of 0.01 wt% to 5 wt%, specifically 0.5 wt% to 2 wt%. Within this range, oxidation of the metal nanowire network can be prevented and the transmission b * value can be lowered.

The matrix 122 may include an initiator. The initiator may be an alpha-hydroxy ketone series as a conventional photopolymerization initiator, or a mixture containing 1-hydroxycyclohexyl phenyl ketone or a mixture thereof.

The initiator may be included in the matrix composition in an amount of 1 to 15% by weight, specifically 2 to 10% by weight.

The matrix 122 may be formed of a composition for a matrix comprising a bifunctional or hexafunctional monomer, a trifunctional monomer, an adhesion promoter, an antioxidant, and an initiator, wherein 50% to 70% by weight, Specifically from 55% by weight to 66% by weight, from 10% by weight to 30% by weight, in particular from 15% by weight to 25% by weight, of the trifunctional monomer, from 1% by weight to 15% by weight, From 0.01% to 5%, specifically from 0.5% to 2% by weight of an inhibitor, and from 1% to 15% by weight, and in particular from 2% to 10% by weight, of an initiator. In this range, it is possible to enhance the transparency and reliability of the transparent conductor 100 and prevent the conductive layer 120 from being distorted in yellow.

The matrix 122 may further include an additive for improving the performance, and the additive may include an ultraviolet stabilizer or the like.

The thickness of the conductive layer 120 may be 10 nm to 1 탆, specifically 20 nm to 200 nm, more specifically 30 nm to 130 nm, and 50 nm to 100 nm. In the above range, the transparent conductor 100 can be used as a film for a touch panel. Within this range, there may be an effect that the contact resistance is lowered and the durability and the chemical resistance are improved.

Although not shown in FIG. 1, a functional layer may be further laminated on one side or both sides of the base layer 110. The functional layer may be, but not limited to, a hard coating layer, a corrosion inhibiting layer, an anti-glare coating layer, an adhesion promoting layer, and an oligomer elution preventing layer.

The transparent conductor 100 may have a transmittance of 90% or more, specifically 90 to 99%, and a reliability of 10% or less, specifically 1 to 10%. Within the above range, the transparency of the transparent conductor 100 is high, the rate of change in resistance is low, and the transparent conductor 100 can be used as a transparent electrode film by patterning. Of course, the matrix 122 may have durability, chemical resistance, solvent resistance, etc. of the conventional transparent conductor.

The transparent conductor 100 may have transparency in a visible light region, for example, a wavelength of 400 nm to 700 nm. In embodiments, the transparent conductor 100 has a haze of 0 to 1.3%, such as 0.01% to 1.3%, measured with a haze meter at a wavelength of 400 nm to 700 nm, and a total light transmittance of 90% to 100% Can be from 90% to 95%. In this range, transparency is good and can be used for transparent conductor applications. The transparent conductor 100 may have a sheet resistance of 100 (Ω / □), specifically 50-100 (Ω / □), or 30-100 (Ω / □) as measured with a 4-probe. 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 占 퐉 to 250 占 퐉, for example, 50-200 占 퐉. In the above range, it can be used as a transparent electrode film including a film for a touch panel, and can be used as a transparent electrode film for a flexible touch panel. The transparent conductor 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.

FIG. 1 shows an embodiment in which a conductive layer including a metal nanowire and a matrix is formed on a top surface of a base layer. However, an embodiment in which a metal nanowire and a conductive layer including a matrix are further formed on a lower surface of the base layer And can be included in the scope of the invention.

Hereinafter, the transparent conductor of another embodiment of the present invention will be described with reference to FIG.

2, the transparent conductor 150 of another embodiment of the present invention includes a base layer 110, a metal layer 120 formed on the upper surface of the base layer 110 and including a metal nanowire 121 and a matrix 122 And a conductive layer 120 'patterned with a metal nanowire-free conductive layer 120b that does not include a metal nanowire and the matrix 122 has a five- or six- Monomers, trifunctional monomers, initiators, adhesion promoters, and antioxidants. Is substantially the same as the transparent conductor 100 of the embodiment of the present invention except that the conductive layer 120 'is patterned.

The conductive layer 120 'may be patterned by a predetermined method, for example, etching using an acidic solution, and the conductive layer 120' may be patterned to form x and y channels and used as a conductor. For example, as shown in FIG. 2, a conductive layer 120a including a metal nanowire 121 and a metal nanowire-free conductive layer 120b including only a matrix 122 without a metal nanowire 121 Pattern. ≪ / RTI >

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

A method of manufacturing a transparent conductor of an embodiment of the present invention includes forming a metal nanowire network layer on a substrate layer and forming a metal nanowire network layer on the metal nanowire network layer with a five- or six-functional monomer, a trifunctional monomer, an adhesion promoter, And coating with a composition for a matrix comprising an initiator. Another manufacturing method according to this embodiment is a method in which metal nanowires and a composition for a matrix are coated at the same time to form a conductive layer without coating the metal nanowires and then coated with a composition for a matrix, An excellent transparent conductor can be obtained.

The metal nanowire composition is a liquid composition in which metal nanowires are dispersed, and can be produced by including a binder for dispersing metal nanowires. The metal nanowire composition is specifically as described for the transparent conductor 100 of one embodiment of the present invention.

The method of coating the metal nanowire composition on the base layer is not particularly limited, but may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. The metal nanowires may be coated on the substrate layer and then dried to form metal nanowire network layers on the substrate layer. The drying can be carried out, for example, at about 80 캜 to 140 캜 for 1 minute to 30 minutes.

The composition for the matrix may comprise a binder, an initiator, and a solvent. The composition for a matrix is as described in detail for the transparent conductor 100 of the embodiment of the present invention.

The method for coating the matrix composition on the metal nanowire network layer is not particularly limited, but may be bar coating, spin coating, dip coating, roll coating, flow coating, die coating and the like. The metal nanowire network layer is formed by coating the metal nanowire composition on the substrate layer followed by drying, and the composition for the matrix coated on the metal nanowire network layer is permeated into the metal nanowire network layer. Thus, the metal nanowires are impregnated into the matrix composition to form a conductive layer containing the metal nanowires and the matrix. The metal nanowire may be present either as a whole impregnated in the matrix or partially exposed on the conductive layer surface.

Coating the composition for a matrix, and then drying the composition. For example, at 80 ° C to 120 ° C for 1 minute to 30 minutes.

After drying, one or more of photocuring and thermosetting may be performed. Photocuring can be carried out by irradiating light with a wavelength of from 300 mJ / cm 2 to about 1000 mJ / cm 2 at a wavelength of 400 nm or less, and thermal curing may include thermal curing at 50 to 200 ° C for 1 to 120 hours.

An apparatus according to an embodiment of the present invention includes a transparent conductor according to an embodiment of the present invention and specifically includes an optical display device including a touch panel, a touch screen panel, a flexible display, etc., an E-paper, And the like, but are not limited thereto.

3 to 5 are sectional views of an optical display device according to an embodiment of the present invention.

3, an optical display device 200 according to an embodiment of the present invention includes a substrate layer 110, a first electrode 255 and a second electrode 260 formed on the upper surface of the substrate layer 110, A transparent electrode body 230 including a third electrode 265 and a fourth electrode 270 formed on the lower surface of the layer 110 and a window formed on the upper portion of the first electrode 255 and the second electrode 260. [ A first polarizer 235 formed on the lower part of the third electrode 265 and the fourth electrode 270, a CF (COLOR FILTER) glass 240 formed on the lower surface of the first polarizer 235, A panel 245 formed on the lower surface of the CF glass 240 and including a TFT THIN FILM TRANSISTOR glass and a second polarizer 250 formed on the lower surface of the panel 245, May be formed of the transparent conductor of the embodiment of the present invention.

The transparent electrode member 230 can be manufactured by patterning the transparent conductive material by a predetermined method (e.g., etching) to form the first electrode, the second electrode, the third electrode, and the fourth electrode. The first electrode 255 and the second electrode 260 may be Rx electrodes, the third electrode 265 and the fourth electrode 270 may be Tx electrodes, and vice versa. have. The window glass 205 performs a screen display function in an optical display device, and can be made of a general glass material or a transparent plastic film. The first polarizing plate 235 and the second polarizing plate 250 are provided for imparting polarization capability to the optical display device and can polarize external light or internal light and include a polarizer or a laminate of a polarizer and a protective film The polarizer, and the protective film may include those conventionally known in the polarizer field. By attaching the adhesive films 210 and 212 between the window glass 205 and the transparent electrode body 230 and between the transparent electrode body 230 and the first polarizing plate 235 respectively to form the transparent electrode body 230, The first polarizer plate 205 and the first polarizer plate 235 can be maintained. The adhesive films 210 and 212 may be ordinary adhesive films, for example, OCA (optical clear adhesive) films.

3, the first polarizing plate 235 and the second polarizing plate 250 may be omitted, and the window glass 205 and the transparent electrode body (not shown) may be omitted. In the optical display device of FIG. 3, 230 may be positioned between the polarizer plates.

4, the optical display device 300 according to another embodiment of the present invention includes a base layer 110, a third electrode 265 and a fourth electrode 270 formed on the upper surface of the base layer 110 A window glass 205 formed on the third electrode 265 and the fourth electrode 270 and having a first electrode 255 and a second electrode 260 formed on the lower surface thereof, A color filter glass 240 formed on the lower surface of the first polarizer 235 and a TFT 240 formed on the lower surface of the CF glass 240. The first polarizer 235 is formed on the lower side of the transparent electrode unit 330, THIN FILM TRANSISTOR) glass and a second polarizer 250 formed on the lower surface of the panel 245. The transparent electrode body 330 may be formed of the transparent conductor of the embodiment of the present invention.

The transparent electrodes 330 are formed by patterning a transparent conductive material by a predetermined method to form a third electrode 265 and a fourth electrode 270. The first electrode 255 and the second electrode 260 It can be formed by employing a normal electrode forming method. By attaching the adhesive films 210 and 212 between the window glass 205 and the transparent electrode member 330 and between the transparent electrode member 330 and the first polarizer 235, The bonding between the polarizing plates can be maintained.

5, an optical display device 400 according to another embodiment of the present invention includes a first base layer 110a, a first electrode 255 formed on a top surface of a first base layer 110a, 260 formed on the upper surface of the second base layer 110b and a third transparent electrode body 430b formed below the first transparent electrode body 430a and formed on the upper surface of the second base layer 110b and the second base layer 110b, A second transparent electrode body 430b including an electrode 265 and a fourth electrode 270, a first polarizer 235 formed below the second transparent electrode body 430b, a lower portion of the first polarizer 235, A panel 245 including a TFT (THIN FILM TRANSISTOR) glass formed on the lower surface of the CF glass 240, a second polarizer plate 244 formed on the lower surface of the panel 245 250, and the first transparent electrode member 430a and the second transparent electrode member 430b may be formed of the transparent conductive material of the embodiment of the present invention.

The first transparent electrode member 430a and the second transparent electrode member 430b may be manufactured by forming a first electrode, a second electrode, a third electrode, and a fourth electrode by patterning a transparent conductor by a predetermined method .

The first transparent electrode body 430a and the window glass 205 and between the first transparent electrode body 430a and the second transparent electrode body 430b and between the second transparent electrode body 430b and the first polarizing plate 235 The adhesion between the transparent electrode body, the window glass, and the first polarizer can be maintained by adding the adhesive films 210, 212, and 214, respectively. The adhesive films 210, 212, and 214 may be ordinary adhesive films, for example, OCA (optical clear adhesive) films. Although not shown in Figs. 3 to 5, the substrate layer may be in the form of a resin film laminated with an adhesive or the like.

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

Example 1

37 weight parts of a metal nanowire-containing solution (product name: Clearohm ink (Cambrios), 2.45 weight% of metal nanowire and binder) was added to 63 weight parts of ultrapure distilled water and stirred to prepare a metal nanowire composition. , 65.4 parts by weight of dipentaerythritol hexaacrylate (SK CYTEC), 20.8 parts by weight of ethoxylated trimethylolpropane triacrylate (SARTOMER), a mixture of phenolic antioxidant Irganox 1010 and phosphorus-based antioxidant Irgafos 168 (BASF) , 0.9 parts by weight of an adhesion promoter KBE-903 (SHIN-ETSU), and 4.3 parts by weight of an initiator Irgacure 184 (CIBA) were added to 1 part by weight of isopropyl alcohol and 49.5 parts by weight of propylene glycol monomethyl And 49.5 parts by weight of ether acetate to prepare a composition for a matrix.

The metal nanowire composition was coated on a polycarbonate film (Teijin, thickness 50 탆) with a spin coater, dried in an oven at 80 캜 for 2 minutes, and the composition for a matrix was coated again with a spin coater to form a conductive layer to a thickness of 85 nm , Dried in an oven at 80 캜 for 2 minutes, and UV-cured at 300 mJ / cm ² to prepare a transparent conductor.

Example 2

Except that 20.8 parts by weight of ethoxylated trimethylolpropane triacrylate was replaced by 20.8 parts by weight of propoxylated glycerol triacrylate (SARTOMER) in Example 1, and a transparent conductor was prepared in the same manner.

Example 3

A transparent conductor was prepared in the same manner as in Example 1, except that 20.8 parts by weight of trimethylolpropane triacrylate (SK CYTEC) was used instead of 20.8 parts by weight of ethoxylated trimethylolpropane triacrylate.

Example 4

A transparent conductor was prepared in the same manner as in Example 1, except that 65.4 parts by weight of dipentaerythritol pentaacrylate (Sartomer) was used instead of 65.4 parts by weight of dipentaerythritol hexaacrylate (SK CYTEC).

Example 5

A transparent conductor was prepared in the same manner as in Example 1, except that 0.9 part by weight of a mixture of a HALS-based antioxidant TINUVIN 152 (BASF) and a phosphorus-based antioxidant Irgafos 168 was used.

Example 6

A transparent conductor was prepared in the same manner as in Example 1, except that 0.9 parts by weight of a mixture of triazole-based antioxidant BTA (antimicrobial), phenol antioxidant Irganox 1010 and phosphorus antioxidant Irgafos 168 (BASF) .

Example 7

A transparent conductor was prepared in the same manner as in Example 1 except that 0.9 parts by weight of a mixture of a HALS-based antioxidant TINUVIN 152 (BASF) and a phosphorus-based antioxidant Irgafos 168 (BASF) was used.

Comparative Example 1

A transparent conductor was prepared in the same manner as in Example 1, except that the composition for a matrix was not coated.

Comparative Example 2

A transparent conductor was prepared in the same manner as in Example 1, except that 20.8 parts by weight of glycerol dimethacrylate (TCI) was used instead of 20.8 parts by weight of ethoxylated trimethylolpropane triacrylate.

Comparative Example 3

A transparent conductor was prepared in the same manner as in Example 1, except that 65.4 parts by weight of 2-ethylhexyl acrylate was used instead of 65.4 parts by weight of dipentaerythritol hexaacrylate.

Comparative Example 4

A transparent conductor was prepared in the same manner as in Example 1 except that 86.2 parts by weight of dipentaerythritol hexaacrylate and 0 part by weight of ethoxylated trimethylolpropane triacrylate were used.

Comparative Example 5

A transparent conductor was prepared in the same manner as in Example 1 except that 0 parts by weight of dipentaerythritol hexaacrylate and 86.2 parts by weight of ethoxylated trimethylolpropane triacrylate were used.

Comparative Example 6

A transparent conductor was prepared in the same manner as in Example 1, except that a mixture of the metal nanowire composition and the matrix composition was coated on the polycarbonate film.

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

(1) Surface Resistance (Ω / □): The sheet resistance of the transparent conductor (not patterned) surface was measured using a contact type surface resistance measuring device R-CHEK RC2175 (EDTM).

(2) Haze and total light transmittance (%): The haze and total light transmittance were measured using a haze meter (NDH-9000) at a wavelength of 400-700 nm with a transparent conductive film directed toward a light source for the transparent conductor.

(3) Transmission b *: A transparent conductive material (polycarbonate film: thickness 50 탆, conductive layer including metal nanowire and matrix: thickness 85 nm) in Examples and Comparative Examples was irradiated with a UV spectrometer (illuminant 65 (Observer 2 degrees) The transmission color coordinates were measured using a CM6000D (Konica Minolta).

(4) Reliability: Reliability was evaluated by the rate of change in resistance. Transparent adhesion with a thickness of 125 占 퐉 was performed on a transparent conductive layer (polycarbonate film: thickness 50 占 퐉, conductive layer comprising metal nanowire and matrix: The initial sheet resistance (a) was measured in the same manner as in the above (1) while sequentially laminating a film (3M Company, Optically Clear Adhesives 8215) and a 100 μm thick PET film (Toyobo, A4300) After allowing to stand for 240 hours under relative humidity conditions, the sheet resistance (b) was measured in the same manner and calculated as │ba│ / ax 100.

(5) IPA rubbing: Isopropanol was sprayed as a sphere on the conductive layer and rubbed with a wiper 10 times, and appearance change and resistance change were confirmed. &Quot; Good "when the external appearance by the naked eye was not changed, " Bad" when the resistance change rate was 10% or less, and / or when the resistance change rate exceeded 10%.

(6) Cross-cut test: The conductive layer prepared in the above Examples and Comparative Examples was scratched with a knife in the form of 100 cells in a size of 10 mm x 10 mm and then stuck with a tape (3M company, Scotch magic tape) The number of repeated peelings was measured to evaluate the adhesion to the substrate. The peaks shown in Table 1 and Table 2 are the number of cells that did not fall apart among 100 peelings.

(Unit: parts by weight) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Example
7 Dipentaerythritol hexaacrylate 65.4 65.4 65.4 - 65.4 65.4 65.4 Dipentaerythritol pentaacrylate - - - 65.4 - - - Ethoxylated
Trimethylolpropane triacrylate 20.8 - - 20.8 20.8 20.8 20.8 Propoxylated glycerol triacrylate - 20.8 - - - - - Trimethylolpropane trimethacrylate - - 20.8 - - - - Irganox 1010 0.5 0.5 0.5 0.5 0.5 0.3 - Irgafos 168 0.4 0.4 0.4 0.4 - 0.3 0.5 TINUVIN 152 - - - - 0.4 - 0.4 BTA (Benzotriazole) - - - - - 0.3 - Adhesion promoter 8.6 8.6 8.6 8.6 8.6 8.6 8.6 Initiator 4.3 4.3 4.3 4.3 4.3 4.3 4.3 Haze (%) 1.07 1.08 1.09 1.06 1.02 1.09 1.09 Total light transmittance (%) 90.12 90.39 90.10 90.46 90.25 90.21 90.12 Sheet resistance
(Ω / □) 47.02 47.34 47.40 47.10 48.12 48.61 48.06 Transmission b * 1.10 1.13 1.17 1.10 1.09 1.08 1.07 IPA rubbing Good Good Good Good Good Good Good Cross-cut 100/100 100/100 100/100 100/100 100/100 100/100 100/100 responsibility(%) 4 5 4 4 2 3 3

(Unit: parts by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Dipentaerythritol hexaacrylate - 65.4 - 86.2 - 65.4 Ethoxylated
Trimethylolpropane triacrylate - - 20.8 - 86.2 20.8 Glycerol dimethacrylate - 20.8 - - - - 2-ethylhexyl acrylate - - 65.4 - - - Irganox 1010 - 0.5 0.5 0.5 0.5 0.5 Irgafos 168 - 0.4 0.4 0.4 0.4 0.4 TINUVIN 152 - - - - - - Adhesion promoter - 8.6 8.6 8.6 8.6 8.6 Initiator - 4.3 4.3 4.3 4.3 4.3 Haze (%) 1.03 1.12 1.49 1.29 1.54 0.9 Total light transmittance (%) 88.17 90.05 89.77 90.13 90.3 88.98 Sheet resistance
(Ω / □) 50.1 50.7 57.91 54.41 53.92 749.8 Transmission b * 0.86 1.31 1.54 1.21 1.12 0.94 IPA rubbing Bad Bad Bad Good Bad Bad Cross cut 0/100 50/100 50/100 100/100 50/100 0/100 responsibility(%) 300 22 29 18 52 129

As shown in Table 1, the transparent conductors of Examples 1 to 7 have high transparency and reliability of the transparent conductor and have a low transmission b * value, which can prevent the color distortion of the conductive layer, The resistance change rate and appearance change were small and it was confirmed that chemical resistance and adhesion were good.

On the other hand, Comparative Example 1, which did not include a matrix, had a problem that the transmittance was less than 90% and adhesion and durability were poor. Comparative Example 2 using bifunctional monomers instead of trifunctional monomers showed adhesion at IPA rubbing and cross- Comparative Example 3 using bifunctional monomers instead of hexafunctional monomers showed poor improvement in optical characteristics, poor adhesion and durability, and contained neither 6-functional monomers nor 3-functional monomers Comparative Examples 4 to 5 in which Comparative Examples 4 to 5 had insufficient optical characteristics, adhesion and durability, and Comparative Example 6 in which a metal nanowire composition and a composition for a matrix were simultaneously coated had problems such as increase in sheet resistance, deteriorated optical characteristics, .

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 (17)

A transparent conductor comprising a base layer and a conductive layer formed on the base layer and including metal nanowires and a matrix,
The transparent conductor has a transmission b * value of 1.5 or less,
Wherein the matrix is formed of a composition comprising a pentafunctional or hexafunctional monomer, and a trifunctional monomer. The transparent conductor according to claim 1, wherein the trifunctional monomer comprises a (meth) acrylate-based monomer. The transparent conductor according to claim 1, wherein the trifunctional monomer comprises a (meth) acrylate-based monomer modified with an alkoxy group. The transparent conductor according to claim 1, wherein the transparent conductor is a transparent conductor having a resistance change ratio of 10%
<Formula 1>
Rate of change in resistance = | ba | / a x 100
(Where a is the initial sheet resistance of a specimen in which a transparent adhesive film having a thickness of 125 占 퐉 and a PET film having a thickness of 100 占 퐉 are sequentially formed on a transparent conductor and b is a temperature at which the specimen is left at 85 占 폚 and 85% Which is the sheet resistance. The transparent conductor of claim 1, wherein the matrix further comprises at least one of an initiator, an adhesion promoter, and an antioxidant. 6. The transparent conductor according to claim 5, wherein the content of the solids-based adhesion promoter in the matrix is 1 to 15% by weight. 6. The transparent conductor according to claim 5, wherein the content of the antioxidant on a solid basis in the matrix is 0.01 to 5% by weight. The composition according to claim 5, wherein the composition comprises 50 to 70% by weight of the hexafunctional monomer, 10 to 30% by weight of the trifunctional monomer, 1 to 15% by weight of the initiator, 1 to 15% And 0.01 to 5% by weight of an inhibitor. 6. The transparent conductor according to claim 5, wherein the adhesion promoter comprises at least one of a silane coupling agent, and a bifunctional monomer. 6. The transparent conductor according to claim 5, wherein the antioxidant comprises a Hinder amine light stabilizer (HALS) -based antioxidant and a phosphorus-based antioxidant. 6. The transparent conductor according to claim 5, wherein the antioxidant comprises a triazole-based antioxidant, a phenol-based antioxidant and a phosphorus-based antioxidant. 6. The transparent conductor according to claim 5, wherein the antioxidant comprises a triazine-based antioxidant, a phenol-based antioxidant and a phosphorus-based antioxidant. The transparent conductor according to claim 1, wherein the metal nanowire comprises silver nanowires. The transparent conductor according to claim 1, wherein at least one of a hard coating layer, a corrosion preventing layer, an anti-glare coating layer, an adhesion promoting layer, and an oligomer elution preventing layer is further formed on the upper surface or the lower surface of the substrate layer. The transparent conductor according to claim 1, wherein the conductive layer is patterned. Forming a metal nanowire network layer on the substrate layer,
Forming a conductive layer on the metal nanowire network layer with a composition for a matrix comprising a pentafunctional or hexafunctional monomer, a trifunctional monomer, an adhesion promoter, an antioxidant and an initiator. An optical display device comprising the entire transparency of any one of claims 1 to 15.

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