KR101405047B1 - Transparent electrode formed fine metal pattern and manufacturing method thereof - Google Patents

Abstract

The present invention includes a base film, a hard coating layer which has an anti-static property or the anti-static property and an anti-blocking property, and a metal layer which is formed on the upper surface of the hard coating layer. The metal layer has a mesh shape. The present invention relates to a transparent electrode with an ultra-fine metal pattern. The purpose of the present invention is to improve a conductive property by forming a hard coating layer which has an anti-static property or the anti-static property and an anti-blocking property in both sides of a base film and by forming an ultra-fine metal mesh pattern and to provide a transparent electrode with an ultra-fine metal pattern for lowering the visibility and a manufacturing method thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a transparent electrode having a very fine metal pattern and a method of manufacturing the transparent electrode.

More particularly, the present invention relates to a transparent electrode film having improved conductivity and visibility, and more particularly to a transparent electrode film having antistatic property, antistatic property and anti-blocking property, To improve the conductivity, while improving the visibility, and a method of manufacturing the transparent electrode film.

The transparent electrode means an oxide-based recessive semiconductor electrode having high light transmittance and high conductivity, high transmittance to light in the visible light region, and low resistivity.

Due to the bending nature of transparent electrodes, components used mainly in flexible displays, OLED TVs, solar cells, etc., the technology industry for touch screens has been actively expanding due to the recent surge in demand for smart phones.

Although these transparent electrodes are usually made of indium tin oxide (ITO), studies have been made on materials that replace indium tin oxide (ITO) in view of the high indium material cost and low flexibility of ITO. Carbon nanotubes (CNTs), graphene, metal (Ag) nanowires, and PEDOT-PSS. Particularly, the metal mesh method is advantageous for forming a thin fine pattern.

With respect to a conventional metal mesh implementation method, Korean Patent Laid-Open Publication No. 2013-0123232 discloses a capacitive touch panel and a manufacturing method thereof. This is a method in which a fine pattern is formed through an imprint process and a conductive material is filled in an engraved pattern, but there is a limit in miniaturizing a pattern to be formed.

In order to overcome such limitations, Korean Laid Open Patent Application No. 2013-0038538 discloses a method for producing a transparent electrode film, but it has a disadvantage in that a mesh is formed by a sputtering method so that the manufacturing cost is high and the adhesion between the metal mesh layer and the transparent PET film And a disconnection occurs due to a difference in shrinkage ratio between the transparent PET film and the metal mesh, and a high current flows due to static electricity.

Accordingly, there has been a need for a transparent electrode which can form a very fine metal pattern, is low in manufacturing cost, and has both anti-blocking property and antistatic property.

It is an object of the present invention to provide a method for forming a micro-metal mesh pattern, which comprises forming a hard coating layer having antistatic properties, antistatic properties and anti-blocking properties on both sides of a base film and improving the conductivity, And a method of manufacturing the same.

According to an aspect of the present invention, there is provided a transparent electrode having an extremely fine pattern formed thereon. The transparent electrode includes a base film, a hard coating layer having antistatic properties or antistatic properties and anti-blocking properties on both sides of the base film, And the metal layer is formed in a mesh shape.

At this time, the metal layer may include an aluminum (Al) component.

At this time, the hard coating layer may be composed of a hybrid type of the organic-inorganic hybrid type.

At this time, the hard coat layer may include a nano-metal oxide complex sol.

In this case, the nano-metal oxide composite sol may be one of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ having a particle size of 5 to 100 nm May be used alone or in combination of two or more.

At this time, the nano-metal oxide complex sol may be formed by surface-treating with a silane coupling agent.

In this case, the silane coupling agent may be at least one selected from the group consisting of 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- Triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxy 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para-styryltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride , 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane. By weight, or by hydrolysis.

In this case, the metal mesh may have a line width of 2 to 5 μm, a pitch of 100 to 700 μm, and a thickness of 50 to 500 nm.

At this time, the hard coat layer may contain a photo-curing resin.

In this case, the photo-curable resin is preferably a hydroxy or ethylene oxide-containing monomer, which is added with an ethylene oxide (2 to 8 mol) phenol (meth) acrylate, ethylene oxide (2 to 10 moles) 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 moles) neopentyl glycol diacrylate, tripropylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide addition polyethyleneglycol di (meth) acrylate, bifunctional urethane acrylate, Silicone urethane (meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 mol of ethylene oxide) di (meth) acrylate It may include a relay agent and a bisphenol A one or more components selected from the group consisting of epoxy acrylates.

At this time, the base film is made of a material selected from the group consisting of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene Or more species.

At this time, the base film may have a thickness of 20 to 600 mu m.

In addition, the method includes the steps of forming a hard coat layer having antistatic properties, antistatic properties and anti-blocking properties on both sides of a base film, forming a metal layer on the surface of the hard coat layer, and forming the metal layer in a mesh shape .

At this time, the metal layer may include aluminum (Al).

At this time, the hard coating layer may be composed of a hybrid type of the organic-inorganic hybrid type.

At this time, the metal layer may be formed on the surface of the hard coat layer by a thermal vacuum deposition method.

At this time, the mesh can be formed through a photolithography process.

The method may further include forming a buffer layer on one surface of the hard coat layer.

At this time, the buffer layer may include at least one of CNT (Carbon Nano Tube), CB (Carbon Black), and Graphene.

At this time, it is possible to further include a coating step for preventing oxidation of the mesh.

At this time, it may further include a step of surface-treating the hard coat layer with a nano-metal oxide.

At this time, the nano-metal oxide may include one or more of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ and Y ₂ O ₃ have.

At this time, it may further include a step of surface-treating the nano-metal oxide with a silane coupling agent.

In this case, the silane coupling agent may be 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Ethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- glycidoxypropyl tri Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Ethylcyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para-styryltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- (Meth) acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propyl Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride , 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and the like. Can be used directly or by hydrolysis.

At this time, it may further include a step of blending a photocurable resin into the hard coat layer.

In this case, the photo-curable resin is preferably a hydroxy or ethylene oxide-containing monomer, which is added with an ethylene oxide (2 to 8 mol) phenol (meth) acrylate, ethylene oxide (2 to 10 moles) 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 moles) neopentyl glycol diacrylate, tripropylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide addition polyethyleneglycol di (meth) acrylate, bifunctional urethane acrylate, Silicone urethane (meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 mol of ethylene oxide) di (meth) acrylate It may include a relay agent and a bisphenol A one or more components selected from the group consisting of epoxy acrylates.

According to the present invention, a metal mesh can be realized from a base metal layer to have excellent conductivity, and a very fine line width of about 5 μm or less can be realized through a photolithography process, thereby greatly improving conductivity and visibility.

Further, the present invention can greatly reduce the production cost by forming the Al metal mesh, and the roll-to-roll process can be performed, so that the production speed and the sheet resistance can be further reduced.

In addition, the present invention can prevent charging by forming a hard coating layer on one side or both sides of a transparent electrode film, prevent blocking, prevent high current due to static electricity, reduce difference in shrinkage rate of film caused by heat So that disconnection of the metal mesh can be prevented.

The present invention also simplifies the manufacturing process and increases the mass production rate by forming the base metal layer through the thermal vacuum deposition method.

1 is a cross-sectional view of a transparent electrode in which a very fine metal pattern of the present invention is formed.
FIG. 2 is a photomicrograph and an enlarged micrograph of a metal pattern layer of a transparent electrode in which a very fine metal pattern is formed according to a first embodiment of the present invention.
FIG. 3 is a SEM photograph of a fracture surface of a transparent electrode having a very fine metal pattern, which is a first embodiment of the present invention.
4 is a plane micrograph of a transparent electrode prepared according to a second comparative example of the present invention.
5 is a flow chart of a manufacturing process for a first embodiment of a method of manufacturing a transparent electrode in which an ultrafine metal pattern of the present invention is formed.
6 is a flowchart of a manufacturing process for a second embodiment of a method for manufacturing a transparent electrode in which an ultrafine metal pattern of the present invention is formed.

The present invention will now be described in detail with reference to the accompanying drawings. Hereinafter, a repeated description, a known function that may obscure the gist of the present invention, and a detailed description of the configuration will be omitted. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art. Accordingly, the shapes and sizes of the elements in the drawings and the like can be exaggerated for clarity.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

2 is a micrograph and an enlarged micrograph of a metal pattern layer of a transparent electrode in which an ultrafine metal pattern according to the present invention is formed, and Fig. 3 is a micrograph of the ultrafine metal pattern of the present invention 2 is a SEM photograph of a cross section of a transparent electrode on which a metal pattern is formed. 4 is a plane micrograph of a transparent electrode prepared according to the second comparative example of the present invention.

1 to 4, a hard coating layer 200 having antistatic properties, antistatic properties and anti-blocking properties is formed on both surfaces of a base film 100, and a metal mesh layer (not shown) is formed on the other surface of the hard coating layer 200. [ (Not shown).

That is, the transparent electrode on which the ultrafine metal pattern according to the present invention is formed includes a base film 100, a hard coat layer 200 having antistatic properties, antistatic properties and anti-blocking properties on both sides of the base film 100, The metal layer 300 is formed in a mesh shape, and the mesh shape means a general net shape as shown in FIG. 2 to FIG.

More specifically, the hard coating layer 200 having antistatic properties, antistatic properties and anti-blocking properties is formed on both sides of the base film 100. The metal layer 300 is formed on the opposite side of the surface on which the base film 100 is formed, based on the hard coat layer 200 having antistatic properties and anti-blocking properties.

At this time, the base film 100 is formed from a group consisting of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene And may include at least one kind selected.

The thickness of the base film 100 may be 20 to 600 μm, preferably 25 to 250 μm. The thickness of the resin applied to the base film is preferably 0.01 to 10 mu m. When the coating thickness is less than 0.01 袖 m, it is difficult to secure the appearance of the coating surface. When the coating thickness is more than 10 袖 m, not only the manufacturing cost is increased but also cracking occurs when the coating film is bent.

Also, the hard coat layer is a coating layer of an organic-inorganic hybrid type, and comprises 3 to 70% by weight of a reaction mixture obtained by reacting an organic-inorganic hybrid nano-metal oxide complex sol with an ionic antistatic agent represented by the following formula (1); 5 to 80% of photocurable resin; Solvent 15 to 90%; And 1 to 10% by weight of a photoinitiator.

[Chemical Formula 1]

Wherein R1-N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole R 2 is a straight chain alkyl group having 1 to 18 carbon atoms and X is selected from the group consisting of CF 3 SO 3, CF 3 CO 2, FPO 3, CF 2 ═CFCO 2, PF 6, BF 4, N (CN) 2 and N (SO 2 CF 3) 2 Lt; / RTI >

At this time, the hard coat layer 200 can be manufactured according to Korean Patent Application No. 2011-0133209 or Korean Patent Application No. 2013-0069228 filed by the present inventor.

The hard coating layer 200 is prepared by surface-reacting a nano-metal oxide 400 with a silane coupling agent to prepare a surface-modified nano-metal oxide composite sol, and then reacting the nano-metal oxide complex sol with an ionic antistatic agent to form a cluster And the ionic bonding between the nanocomposite sol and the ionic antistatic agent prevented the generation of stains due to the adiabatic effect generated in the lamination process after the coating.

In addition, by using the nano-metal oxide 400 having a size of 20 to 100 nm, it is possible to obtain low haze and high transmittance characteristics. Further, in order to further improve the hardness of the hard coat layer 200, .

In this case, the nano-metal oxide 400 may be a nano-metal oxide having a particle size of 20 to 100 nm and may be SiO 2, TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , Y ₂ O ₃ < / RTI >

The ionic antistatic agent can be obtained by using a commercially available product (CHTA-402, KOY-101: KOY-101) or by using a heterocyclic compound containing nitrogen. The method for synthesizing an ionic antistatic agent will be described in detail as follows.

After the pyrrole was dissolved in toluene, 1.3 equivalents of bromomododecane to the pyrrole was added thereto, followed by refluxing overnight. When the reaction is complete, cool the reaction mixture to 40-50 ^° C. To the reaction mixture, water was added twice as much as the weight of the reactant, and the unreacted bromomododecane was removed by washing with diisopropyl ether several times to prepare a quaternary ammonium salt aqueous solution. Diisopropyl ether was added to the reaction solution in an amount of 50% based on the weight of the reaction solution, and 1 equivalent of lithium hexafluorophosphate was added to the pyrrole, followed by reaction at room temperature for 8 hours. After stopping the reaction, the reaction mixture was allowed to stand for 1 hour to separate the layers. The diisopropyl ether layer was dried under reduced pressure to obtain an anion PF ₆ ^- form. As a result of the reaction, the quaternary ammonium salt bromide is changed to the hexafluorophosphate form containing the fluorine by the anion substitution reaction, whereby the antistatic property can be improved.

The hard coating layer 200 may use a hard coating agent of the oil-and-inorganic hybrid type to increase adhesion with the metal mesh layer 300. In addition, this problem can be solved by lowering the surface roughness of the film through the hard coating treatment, which is a problem of disconnection of fine patterns that may occur after metal deposition by the film surface projections.

The high refractive index metal oxide is more effective for improving the scattering phenomenon caused by the difference in refractive index between the substrate and the hard coating surface after hard coating. Furthermore, in order to maintain a low roughness of the vapor-deposited coating surface, it is better to treat the metal oxide particle surface with a silane coupling agent with a small metal oxide particle size.

The adhesion between dissimilar materials can be classified into primary bonding (ionic bonding, covalent bonding and metal bonding) and secondary bonding (dispersion, organic, orientation, hydrogen bonding) depending on the chemical properties of the interface and the surface state of the adherend , The primary bond is 140-250 kcal / mol, the covalent bond is 15-170 kcal / mol, the metal bond is 27-83 kcal / mol, the hydrogen bond is 3-10 kcal / mol, the dispersive force (intermolecular force) / mol, and the organic force (Van der Waal's force) is less than 0.5 cal / mol. From the above results, it can be seen that the primary bonding is very large as compared with the secondary bonding.

Accordingly, the inventors of the present invention induced metal bonding between the metal mesh layer and the hard coating layer through a hard-coating of an organic-inorganic hybrid type in order to induce primary bonding with high bonding force to increase the bonding force between the different material layers.

At this time, as a metal material used for the organic-inorganic hybrid hard coating, a metal nano metal sol such as SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , and Y ₂ O ₃ may be mixed with one or more metal oxides. The nano-metal sol may be surface-modified with a coupling agent and mixed with an ultraviolet curable resin in an amount of 1 to 95% by weight based on the total solids. When the metal oxide is used in an amount of less than 1% based on the total solid content, the adhesion to the deposited metal layer is poor. When the metal oxide is used in an amount of 95% by weight or more, the surface roughness and appearance of the coating deteriorate.

Organic-inorganic hybrid synthesis of the nano-metal oxide composite sol is then put into a silane coupling agent in the contrast 5-200% by weight of solid content in the metal oxide dispersed in an organic solvent, stirred, 0 ~ 50 ^o hydrolysis catalyst in the C domain ( Acid or base) with 1 to 4 equivalents of water relative to the equivalent of the coupling agent.

Since the silane coupling agent used in the present invention contains a reactive group at the terminal group, the silane coupling agent can further react and increase the crosslinking density. Specific examples include 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) , 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxy (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, 3- 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, and one or more of these may be used. They can be used directly or by hydrolysis.

If the silane coupling agent is less than 5% by weight based on the solid content of the metal oxide, the storage stability and the coating film layer after the coating are inhomogeneous, and even if the haze value is less than 1%, the haze is totally caused.

A photocurable resin is added to increase the hardness of the hard coat layer 200. The photocurable resin that can be used in the present invention may be a polyfunctional monomer or a monofunctional or bifunctional monomer. The monofunctional or bifunctional monomer may be a hydroxyl group or an ethylene oxide moiety and acrylate in order to maintain the dispersibility with the organic-inorganic hybrid nano-metal oxide complex sol. For example, an ethylene oxide addition (2 to 8 mol) (2 to 10 moles) 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 moles) neopentyl glycol diacrylate (Meth) acrylate, ethylene glycol di (meth) acrylate, ethylene oxide di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di Polyfunctional urethane acrylate, silicone urethane (meth) acrylate and silicone polyester acrylate, bisphenol A ( (3 to 30 moles of ethylene oxide) di (meth) acrylate and bisphenol A epoxy acrylate can be used.

(Meth) acrylate, an ethylene oxide addition (3 to 15 moles), and a polyfunctional acrylate may be used in order to improve the adhesion to the transparent base film 100 and the hardness of the coating film. Trimethylolpropane tri (meth) acrylate, trifunctional urethane acrylate, glycerin triacrylate, pentaerythritol tri (meth) acrylate, propylene oxide addition (3 mol) trimethylolpropane tri (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (Meth) acrylate and dipentaerythritol hexa (meth) acrylate 6-functional urethane acryl Sites may be used one or more selected from a group consisting of a 10-functional aliphatic urethane acrylate.

Preferably, the resin solution comprises at least one component selected from the group consisting of acrylic acrylate and urethane acrylate.

In order to cure the coating film after the coating, the resin composition may be used within 2 to 10% of the total amount of the resin composition.

Usable photoinitiators can be classified into chemical groups within the molecular structure. Examples of usable chemical structures include ketal series, acetophenone series, sulfide series, benzoate series, benzophenone series, phosphine series, and benzoylformate series. Specific examples include products of Ciba; Darocur 1173, MBF, TPO, 4265, or Double Bond Chemical Company: Doublecure BDK, TPO, TPO-L, 73W, 107, 173, 184, 200, 284, 560, 998, 1130, 1172, 1176, 1190, 1256 and the like. There is no particular limitation on the type of photoinitiator that can be used.

In addition, in order to improve the wettability and functionality of the coating film when the substrate is coated, additives may be added in an amount of 3% by weight or less based on the total composition.

Usable additives include antifoaming agents, wetting agents, dispersants, flow control agents, leveling agents, adhesion promoters, and the like.

A solvent may be used for the purpose of improving the compatibility and the coating property of the resin composition. As the usable solvent, an alcohol-based, a ketone-based, and an aromatic solvent are mixed and used. There is no particular limitation on the solvent to be used, and the total composition ratio can be used in the range of 10 to 99% by weight.

FIGS. 5 and 6 are diagrams showing manufacturing steps of the transparent electrodes according to the first and second embodiments of the present invention. FIG.

Referring to FIG. 5, the transparent electrode having the ultrafine pattern formed thereon according to the present invention includes a step of forming a two-sided hard coating layer of an organic-inorganic hybrid type having antistatic property and anti-blocking property on one surface of a base film, (S100); Forming a metal layer on a hard coat layer having antistatic properties by a thermal vacuum deposition method (S200); And forming a very fine mesh through the photolithography process (S300) on the formed metal layer.

At this time, the hard coating layer may be made of a hard coating film of a oil-inorganic hybrid type.

At this time, after forming the hard coat layer, a buffer layer is further formed (S400), and a metal layer is formed on the upper surface of the buffer layer.

At this time, the metal layer may be composed of an Al component. Al is cheaper than other metals such as Ag and Cu, which can lower the manufacturing cost and is advantageous for the roll-to-roll process in terms of processing.

The thermal deposition process (S200) is advantageous in that the manufacturing method is simple and the mass production rate is very high, thereby lowering the manufacturing cost. At this time, at least one of Au, Ag, Zn, Ni, Al, Sn, and In may be selected as the thermal vacuum deposition metal material, and the thickness of the metal layer is preferably 50 to 500 nm by thermal vacuum deposition .

In the photolithography process (S300), a metal mesh layer (300) having a fine pattern is formed on the metal deposition layer through photoresist coating, ultraviolet exposure, photoresist development, metal layer etching, photoresist stripping and cleaning process .

Specifically, a film thickness of 1 to 2 μm is formed by spin-coating a metal deposition surface using a photoresist, irradiated at 10 to 200 mJ using a parallel light exposure apparatus or a scattered light exposure apparatus, and developed at a temperature of 1 Develop the photoresist layer for ~ 100 seconds. The developed film is etched using a metal etchant in a temperature range of 10 to 70 ^° C for 1 to 100 seconds and is immersed in a range of 10 to 70 ^° C for 1 to 200 seconds using a stripper to form a photoresist layer . The photoresist peeling layer is cleaned using deionized water to form a fine pattern.

Forming a metal mesh after the photolithography process (S300), and performing a coating process for preventing oxidation of the metal mesh (S500).

At this time, the coating treatment step (S500) may be carried out by dry coating using a functional hard coating liquid or a waterproofing wet type anti-oxidation coating liquid and a plasma.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made.

≪ Embodiment 1 >

Step 1: Both sides Hard coating layer  Produce

[Production of one side hard coat layer]

(SiO ₂ content: 30% by weight, particle size: 40 to 50 nm, solvent: methyl ethyl ketone), 3 g of 3-acryloxypropyltrimethoxysilane (manufactured by Nissan Chemical Co., Ltd., product name: MEK-ST- KBM-5103) and acetic acid (1.2 g) were added to a round-bottomed flask. After completion of the reaction, the reaction mixture was diluted with methyl ethyl ketone to a solid content of 30% by weight, and then 7 g of water was slowly added dropwise at room temperature. Inorganic hybrid nanosilica composite sol was synthesized.

The ionic antistatic agent KOY-101 (manufactured by Koizu) was dissolved in methyl ethyl ketone to a concentration of 20% by weight based on solid solids of the composite sol, and then the stirring speed Was slowly added dropwise with stirring at a high rate of 500 rpm or more to allow the ion-binding reaction between the organic-inorganic hybrid nano-metal oxide complex sol and the ionic antistatic agent to react at room temperature for 3 hours. This photocurable resin in MU9500 200g (Aliphatic multifunctional acrylate, Miwon firm product), M3190 100g (Trimetylolpropane (PO ) 9 triacrylate, Miwon firm product), PU664 300g (Aliphatic hexafunctional acrylate , Miwon firm product) and the photoinitiator Irgacure 184 40g (Manufactured by Ciba), diluted with methyl ethyl ketone so that the total solid content became 40% by weight, and then stirred for 1 hour to prepare a resin composition for hard coating having anti-blocking and antistatic properties.

(Manufactured by Mitsubishi, product name: T910E) having a thickness of 125um was coated with the hard coating composition at a coating rate of 10M per minute using microgravure (mesh # 150) using a hard coating composition, and the coating was dried, .

[Production of double-sided hard coat layer]

A two-side hard coat layer was prepared by preparing and coating a coating solution in the same manner, except that the size of the silica nanosol used in the hard coating layer was 10 to 15 nm.

Step 2: Conductive metal thermal vacuum deposition

Aluminum was heat-treated at a speed of 100 m / min and a film thickness of 150 nm using a thermal vacuum deposition apparatus (EW series, Korea) on the antistatic hard coating film (without blocking property) prepared in the first step Respectively.

Step 3: Photolithography  Fabrication of micro patterned film

Using the aluminum evaporated film produced in the second step, a photoresist coating was performed on the aluminum coated surface using a negative photoresist DNR-L300-30 (manufactured by Dongjin Semichem Co.) using a spin coater so as to have a film thickness of 2 μm Respectively.

The PR coated surface was irradiated with a mask using a parallel light exposure machine to a light amount of 70 mJ, and then immersed in water at room temperature for 30 seconds using developer CTD-238 (manufactured by Dongjin Semichem Co., Ltd.).

PR The developed film was used to etch the metal layer by immersing and washing with Etan DAN-200N (manufactured by Dongjin Semichem Co., Ltd.) at 50 ^° C for 30 seconds.

A stripper DPS-7300 (manufactured by Dongjin Semichem Co., Ltd.) was immersed in a metal-etched film for peeling the PR layer at 40 ^° C for 1 minute and then immersed for 30 seconds in deionized water, A transparent electrode film having a pattern formed thereon was produced.

The evaluation of the optical characteristics is shown in Table 1.

≪ Embodiment 2 >

Except that a positive PR DSAM-300SK (manufactured by Dongjin Semichem Co., Ltd.) was used instead of the negative PR in the third-step photolithography process after forming a carbon black buffer layer (product name: Conductex SC Ultra) And a transparent electrode film was produced in the same manner as in the first embodiment.

≪ Comparative Example 1 >

A transparent electrode film was prepared in the same manner as in Example 1, except that an antistatic hard coating solution (trade name: LGB-04, oligomer type resin) was used. Table 1 shows the evaluation of optical properties of the transparent electrode film thus prepared.

≪ Comparative Example 2 >

A transparent electrode film was produced in the same manner as in the first embodiment except for the formation of the double-faced hard coating layer as the first step. Table 1 shows the evaluation of optical properties of the transparent electrode film thus prepared.

≪ Evaluation of physical properties &

① Haze and Transmittance

The haze and transmittance of the transparent substrate film surface were measured by using a spectrophotometer (Nakamura Co., Ltd., HM 150) to direct the surface of the transparent base film to a light source.

② Pencil Hardness

Pencil hardness was measured at 500 g load using a pencil hardness tester (PTH, Korea Science and Engineering). The pencil was made five times per pencil hardness using the product of Mitsubishi. If two or more pieces of gas were judged to be defective.

③ Adhesiveness

11 straight lines were drawn at intervals of 1 mm on the coated surface of the film to form 100 squares, and the peeling test was carried out using a tape. Three 100 squares were tested and the average value recorded.

Adhesion = n / 100

100: total number of rectangles

n: Indicates the number of squares that are not peeled off.

④ Anti-blocking property

Two coated backs are arranged facing each other, then pressed with a roller under a load of 2 kg, and after 10 minutes, whether or not the coated surface falls is observed.

If two floors fall: OK

When two layers are in close contact: NG

⑤ Rear surface resistance

The surface resistance value was measured five times using a surface resistance meter (SIMCO, ST-3) to give an average value.

⑥ Sheet resistance of metal mesh layer

The average value was measured five times using Loresta-GP (Mitsubishi, Model: MCP-T610) as a 4-terminal measurement method.

⑦ My metastatic

The transparent electrode film is sandwiched between two mirror-polished mirrors and compressed with a clip. The film is kept at 60 ^° C and 90% relative humidity for 12 hours, and left at room temperature for 30 minutes. The presence of staining was confirmed by visual inspection of the mirror surface with the naked eye.

If you can not see the mirror surface: OK

When the mirror surface is visible: NG

⑧ shrinkage rate

The transparent electrode film was precisely cut to 20 x 20 cm, and then kept in a thermostat at 150 ^° C for 1 hour and left at room temperature for 30 minutes. The film maintained at room temperature was measured by using a vernier caliper to measure the difference in shrinkage percentage in the TD direction before and after the reliability, and expressed as a percentage.

example Front of transparent electrode Transparent electrode backing Shrinkage rate
(TD%) Line width (μm) Pitch (μm) Transmittance (%) Haze (%) Sheet resistance
(Ω / □) Adhesiveness blocking
Preventiveness surface
resistance
(Ω / cm) pencil
Hardness Metastatic First Embodiment 4.8 400 89 1.5 68 100 OK 10 ^11.4 H OK 0.52 Second Embodiment 4.5 400 90 1.4 85 100 OK 10 ^11.0 H OK 0.56 Comparative Example 1 4.8 400 88 1.8 262 94 NG 10 ^12.4 H NG 0.68 Comparative Example 2 5.5 400 85 2.5 918 88 NG 10 ^14.5 4B OK 0.82

As shown in the above results, the transparent electrode film produced according to the present invention provides a transparent electrode film having low resistance, high transmittance and low haze as well as excellent antistatic property, anti-blocking property, shrinkage rate, do. The transparent electrode film is a transparent conductive metal mesh film having a transmittance of 89% or more, a haze of 1.5% or less and an antistatic property of 10 ¹² or less. The transparent conductive film is used for a touch sensor electrode of a touch screen for a display and an organic solar cell, It can be used as a transparent film.

100: base film
200: hard coat layer
300: metal mesh layer
400: nano metal oxide

Claims (28)

A base film;
A hard coating layer formed on both sides of the base film; And
And a metal layer formed on a surface of the hard coat layer on which the base film is not formed,
The metal layer is formed in a mesh shape,
The hard coat layer is a organic-inorganic hybrid type, and comprises 3 to 70% by weight of a reaction mixture obtained by reacting a nano-metal oxide complex sol with an ionic antistatic agent represented by the following formula (1); 5 to 80% of photocurable resin; Solvent 15 to 90%; And 1 to 10% by weight of a photoinitiator.
[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole R 2 is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ = CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , and N (SO ₂ CF ₃ ) ₂ ) The method according to claim 1,
Wherein the metal layer comprises an aluminum (Al) component. delete delete The method according to claim 1,
The nano-metal oxide composite sol may be one or more of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , and Y ₂ O ₃ having a particle size of 5 to 100 nm Wherein the transparent electrode is formed by mixing at least two kinds of metal. delete The method according to claim 1,
Wherein the nano metal oxide complex sol is surface-treated with a silane coupling agent. The method of claim 7,
The silane coupling agent may be selected from the group consisting of 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Cyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane. A transparent electrode that is directly used, or ultra-fine metal pattern characterized by using hydrolysis is formed. The method according to claim 1,
Wherein the mesh has a line width of 2 to 5 탆, a pitch of 100 to 700 탆, and a thickness of 50 to 500 nm. The method according to claim 1,
Wherein the hard coat layer comprises a photocurable resin. The method according to claim 1,
In order to maintain dispersibility with the organic-inorganic hybrid nano-metal oxide complex sol, the photo-curing resin is added with a hydroxy or ethylene oxide monomer, and an ethylene oxide addition (2-8 mol) phenol (meth) acrylate, an ethylene oxide addition 2 to 10 moles), 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 mol) neopentyl glycol diacrylate, tripropylene glycol di (meth) , Diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide addition polyethylene glycol di (Meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 mol of ethylene oxide) di (meth) acrylate Acrylate and bisphenol A epoxy acrylate group the first transparent electrode having a very fine pattern, characterized in that includes at least one component selected from the consisting of. The method according to claim 1,
Wherein the base film is at least one selected from the group consisting of polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE), and polystyrene And a transparent electrode formed on the transparent electrode. The method according to claim 1,
Wherein the base film has a thickness of 20 to 600 占 퐉. Forming a hard coat layer on both sides of the base film;
Forming a metal layer on a surface of the hard coat layer;
Surface-treating the hard coat layer with a nano-metal oxide; And
And forming the metal layer in a mesh shape,
The hard coat layer comprises 3 to 70% by weight of a reaction mixture obtained by reacting a complex sol containing the nano-metal oxide with an ionic antistatic agent represented by Formula 1; 5 to 80% of photocurable resin; Solvent 15 to 90%; And 1 to 10% by weight of a photoinitiator.
[Chemical Formula 1]

Wherein R ₁ -N is a heterocyclic compound selected from the group consisting of imidazole, pyridine, pyrrole, benzopyrrole, pyrazole, isothiazole, thiazole, indole, indazole, isoindole, indolizine and carbazole R 2 is a straight chain alkyl group having 1 to 18 carbon atoms and X is CF ₃ SO ₃ , CF ₃ CO ₂ , FPO ₃ , CF ₂ = CFCO ₂ , PF ₆ , BF ₄ , N (CN) ₂ , and N (SO ₂ CF ₃ ) ₂ ) 15. The method of claim 14,
Wherein the metal layer comprises aluminum (Al). 15. The method of claim 14,
Wherein the hard coating layer is a organic-inorganic hybrid type. 15. The method of claim 14,
Wherein the metal layer is formed on the surface of the hard coat layer by a thermal vacuum deposition method. 15. The method of claim 14,
Wherein the mesh is formed through a photolithography process. 15. The method of claim 14,
And forming a buffer layer on one side of the hard coating layer. The method of claim 19,
Wherein the buffer layer comprises at least one of carbon nanotube (CNT), carbon black (CB), and graphene (CNT). 15. The method of claim 14,
The method of claim 1, further comprising the step of applying a coating treatment to prevent oxidation of the mesh. delete 15. The method of claim 14,
The nano-metal oxide includes one or more of SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Nb ₂ O ₃ , and Y ₂ O ₃ Wherein the transparent electrode is formed of a transparent electrode. delete 15. The method of claim 14,
Further comprising the step of surface-treating the nano-metal oxide with a silane coupling agent. 26. The method of claim 25,
The silane coupling agent may be selected from the group consisting of 3-methacryloxypropylmethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (Aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2- (3,4-epoxide Cyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, para-styryltrimethoxysilane, para- Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl- 3-chloropropyltrimethoxysilane, and 3-chloropropyltriethoxysilane. A transparent electrode manufacturing method is very fine pattern, characterized in that use or used directly formed by hydrolysis that. 15. The method of claim 14,
Further comprising the step of blending a photo-curable resin in the hard coat layer. 28. The method of claim 27,
In order to maintain dispersibility with the organic-inorganic hybrid nano-metal oxide complex sol, the photo-curing resin is added with a hydroxy or ethylene oxide monomer, and an ethylene oxide addition (2-8 mol) phenol (meth) acrylate, an ethylene oxide addition 2 to 10 moles), 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, propylene oxide addition (2 to 4 mol) neopentyl glycol diacrylate, tripropylene glycol di (meth) , Diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene oxide addition polyethylene glycol di (Meth) acrylate and silicone polyester acrylate, bisphenol A (3 to 30 mol of ethylene oxide) di (meth) acrylate The method for producing a transparent electrode, and the rate of bisphenol A very fine pattern comprising the one or more components selected from the group consisting of an epoxy acrylate formed.

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