TWI613683B - Coating composition for transparent conductive film, transparent conductive film and method for fabricating the same - Google Patents

Abstract

The invention provides a transparent conductive film, a method for manufacturing the same, and a transparent conductive film coating composition. The transparent conductive film not only has the characteristics of excellent surface resistance, environmental resistance, full light transmittance, and haze, but also is in a wet type. It can also be easily etched during the etching process and the refractive index is easily adjusted, so it can be usefully used in liquid crystal display devices, plasma display devices, touch panels, electric field light-emitting devices, thin-film solar cells, dye-sensitized solar cells, and inorganic crystals Electrodes for solar cells, etc. The transparent conductive film coating composition of the present invention is characterized by including a primary conductive film coating composition and a protective layer coating composition, the primary conductive film coating composition includes a metal nanowire and a dispersion liquid, and the The coating composition of the protective layer includes at least one sol selected from the group consisting of a magnesium fluoride sol, an inorganic sol, an inorganic-inorganic composite sol, and an organic-inorganic composite sol, and the transparent conductive film of the present invention. The manufacturing method is to apply and dry the aforementioned conductive film coating composition and the protective layer coating composition to produce a transparent conductive film.

Description

Transparent conductive film coating composition, transparent conductive film, and method for manufacturing transparent conductive film Technical field

The present invention relates to a transparent conductive film coating composition, a transparent conductive film, and a method for manufacturing the same. More specifically, the present invention relates to a single-time conductive film coating composition comprising a metal nanowire and a dispersion liquid. And a transparent conductive film coating composition containing a protective layer coating composition of one or more sols selected from the group consisting of a magnesium fluoride sol, an inorganic sol, an inorganic-inorganic composite sol, and an organic-inorganic composite sol. A method for producing a transparent conductive film by coating and drying the aforementioned conductive film coating composition and protective layer coating composition simultaneously or sequentially, and a transparent conductive film made of the same.

Background technique

The transparent electrode means an electrode that condenses atoms, molecules, or ions on a transparent glass substrate or a thin polymer substrate by a method of physical chemistry, is transparent in the visible light region (380 ~ 780nm wavelength), and has high conductivity. More specifically, a transparent electrode means a thin film having a light transmittance of about 80% or more and a surface resistance of 500Ω / □ or less.

For materials used in transparent electrodes, excellent optics are required Material with characteristics and etching characteristics. ITO (indium tin oxide) which exhibits the most excellent physical properties has been widely used for the materials developed so far. However, ITO is based on indium, which is a rare metal with a high price, and therefore it is necessary to replace ITO as a transparent electrode material.

Therefore, some people have tried to sputter gold, silver, copper, etc. The thin film is used as a transparent electrode. Although the conductivity of the transparent electrode is good, there is a problem that the transmittance in the visible light region decreases and the adhesion with the lower substrate is poor.

In addition, although the ZnO thin film is a low-cost material, it has lower electrical conductivity than ITO, and there are problems that the ATO thin film in which a small amount of Sb is added to SnO ₂ cannot be etched and the firing temperature is high.

It is also formed by Sol-Gel synthesis. The method of oxidizing the film, however, still has the problems of low conductivity and requiring a high temperature step with a firing temperature exceeding 350 ° C.

In addition, there are also oxides made of ZnO, ITO, IZO, etc. A method of producing nano particles and using the nano particles to produce an ink or a paste and to produce a transparent electrode has problems in that the production of nano-sized oxides is difficult and a relatively high temperature step of 250 ° C or higher is required.

Therefore, there have been recent attempts to use metallic nanowires for transparency electrode.

When a transparent electrode is formed by a conductive ink for a transparent electrode Metal nanowires are densely formed and have a function of ensuring conductivity. The denser the metal nanowire network is, the higher the conductivity is to form the transparent electrode, but there are problems that the visible light transmittance decreases and the cost increases. Also, even with metallic nano Lines forming a conductive network must not only cause disconnection of the network, but the space between the networks is not conductive and remains as a non-conductive area. In addition, when metal nanowires are nanostructures, they are more active than existing materials, and when exposed to the atmosphere without a protective layer, they have a strong tendency to oxidize and corrode. Metal nanowires are particularly highly conductive and transparent in the visible light region, but it is known that the resistance rises by about 15 to 20% due to oxidation and corrosion in the atmosphere, and another antioxidant must be used to prevent this Or most protective layers. Therefore, there are also difficulties in wet etching and the use of high-priced lasers, and this has the problems of difficult process and low yield.

In addition, when using a large number of protective layers, it is not necessary to use metal The process of the transparent conductive film of nanowires becomes complicated. It is better to say that the product quality and yield are lower than that of ITO film and it is difficult to use it for commercial purposes. Therefore, compared with such a multilayer protective film, securing the hardness, adhesion, and etching characteristics with a single layer or a plurality of layers is an important issue.

Therefore, optimized electrical, optical, and acid properties The etching does not directly affect the quality and manufacturing process of the transparent conductive film.

U.S. Patent No. 7,585,349 discloses transparency using silver nanowires Conductive film, and the substrate material, that is, the substrate uses a large amount of conductive organic resin resin components such as polyacrylate, and is coated with silver nanowires. When such a substrate material is used, optical characteristics and electrical characteristics can be realized, but etching with an acid is difficult, and a procedure for manufacturing a transparent conductive film becomes complicated and the quality deteriorates.

Here, the function of the substrate material is to protect the silver nanowire Layer, and means to provide a substance that prevents the silver nanowires from peeling off the substrate and easily etch the protective layer so that the silver nanowires existing in the lower layer or the same layer cannot be easily etched.

Summary of invention

In order to solve the aforementioned problems, an object of the present invention is to provide a sol (Sol) using a transparent metal oxide substrate as a base material of metal nanowires, which has electrical characteristics and optical characteristics and can be easily etched by an acid. A transparent conductive film coating composition.

It is another object of the present invention to provide a method for producing a transparent conductive film using the coating composition and a transparent conductive film produced therefrom.

In order to achieve the foregoing object, the present invention provides a transparent conductive film coating composition, comprising: 1) a primary conductive film coating composition including a metal nanowire and a dispersion liquid; and 2) including a component selected from the group consisting of A protective layer coating composition of one or more sols in a group consisting of a magnesium fluoride sol, an inorganic sol, an inorganic-inorganic composite sol, and an organic-inorganic composite sol.

The present invention also provides a method for producing a transparent conductive film using a primary conductive film coating composition and the protective layer coating composition on a substrate. 造 方法。 Manufacturing method.

The present invention also provides a transparent conductive film manufactured by a method for manufacturing a transparent conductive film.

The transparent conductive film manufactured by using the coating composition of the present invention includes metal nanowires, and includes a transparent metal oxide substrate selected from the group consisting of magnesium fluoride sol, inorganic sol, inorganic-inorganic composite sol, and organic-inorganic composite sol. One or more sols in the group as its base material, which not only has excellent surface resistance, environmental resistance, full light transmission, and haze, but also can be easily etched in the wet etching process and The refractive index is easy to adjust, and a wide range of transparent conductive films can be realized through concentration adjustment. Therefore, it can be usefully used in liquid crystal display devices, plasma display devices, touch panels, electric field light emitting devices, thin-film solar cells, and dye sensitization Electrodes for solar cells, inorganic crystalline solar cells, etc.

11‧‧‧ substrate

12‧‧‧ conductive film

13,15‧‧‧1 protective layer

14,16‧‧‧2 times protective layer

17‧‧‧3 times protective layer

18‧‧‧ transparent conductive film

FIG. 1 is an optical microscope photograph of a transparent conductive film manufactured by the present invention before a wet etching process.

FIG. 2 is a photomicrograph of a transparent conductive film produced by the present invention after wet etching.

FIG. 3 is a laminated structure according to an embodiment of the present invention.

FIG. 4 is a laminated structure according to another embodiment of the present invention.

FIG. 5 shows a laminated structure according to another embodiment of the present invention.

FIG. 6 is a laminated structure according to another embodiment of the present invention.

FIG. 7 shows a laminated structure according to another embodiment of the present invention.

Forms used to implement the invention

The transparent conductive film coating composition of the present invention is characterized by using one or more members selected from the group consisting of a magnesium fluoride sol, an inorganic sol, an inorganic-inorganic composite sol, and an organic-inorganic composite sol using a metal oxide substrate. The sol as a base material of the metal nanowires is specifically characterized by: 1) a primary conductive film coating composition including metal nanowires and a dispersion liquid; and 2) selected from the group consisting of fluorinated A protective layer coating composition of one or more sols in a group consisting of a magnesium sol, an inorganic sol, an inorganic-inorganic composite sol, and an organic-inorganic composite sol.

Hereinafter, the present invention will be described in detail.

1.1 conductive film coating composition

a) Metal nanowire

In the present invention, a metal nanowire is used as the conductive substance of the primary conductive film coating composition.

The metal usable in the present invention is not particularly limited, but preferably selected from Group I, consisting of gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, magnesium, etc. One or more metals selected from the group consisting of IIA, IIIA, IVA, and VIIIB, and more preferably one or more metals selected from the group consisting of zinc, aluminum, copper, silver, and gold metal.

The diameter of the aforementioned metal nanowires is preferably 15 nm to 120 nm, and the length is 5 μm to 60 μm. Preferably, the concentration can be adjusted arbitrarily with respect to the dispersion liquid described below, and an amount of 0.05 to 0.5% by weight is used.

b) dispersion

The dispersion can be adjusted and smoothed by considering the viscosity of the metal nanowires Film formation, dispersion of metal nanowires, and the compatibility of one or more sols selected from the group consisting of magnesium fluoride sol, inorganic sol, inorganic-inorganic composite sol, and organic-inorganic composite sol Land selection.

For example, the aforementioned sol can be selected from the group consisting of water, methanol, and ethyl acetate. Alcohol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, octanol, 2-ethylhexanol, pentanol, benzyl alcohol, hexanol, 2-hexanol, cyclohexanol , Terpineol, nonanol, methyl glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-acetone, Diethylpyrene, ethylacetone, 1,2-diethylpyrene, dimethyl carbonate, diethyl carbonate, propylene glycol methyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl Ether, N-methyl-2-pyrrolidone, N-methylacetamidine, and mixtures of one or more solvents thereof. Preferably, ethanol, isopropanol, or alcohol-containing, A mixed solvent of isopropyl alcohol.

The dispersion liquid may further contain an organic binder resin. When the aforementioned organic binder resin is added, the viscosity of the dispersion liquid and the applicability of the metal nanowire dispersion liquid can be adjusted, and the adhesion to the substrate can be increased to further increase the flexibility of the film.

The organic binder resin may be polyimide or acrylic polymer. Polymer, epoxy resin, polyethylene glycol, polyester, polymethyl methacrylate, polyvinyl pyrrolidone, cellulose, polyvinyl alcohol, polyurethane, polyacrylonitrile, etc. Hydroxypropyl methylcellulose Vitamins, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose and the like. Preferably, the weight average molecular weight of the organic binder resin is 10,000 to 2,000,000.

The aforementioned organic binder resin is suitable for use in a coating composition 0.02 to 3% by weight. When it is within the aforementioned range, it is possible to simultaneously ensure the viscosity adjustment of the coating liquid, increase the coating property, increase the adhesion to the substrate, impart flexibility, and prevent the transparent metal film from detaching from the substrate when the bending is more than a certain amount. The uniformity forms a film having excellent conductivity, excellent contact resistance of a transparent conductive film, and excellent optical characteristics. When the content of the organic binder resin is too large, the thickness of the coating film may be too thick, and therefore the entire film may be yellowed, which may adversely affect the visibility.

2. Protective coating composition

In the present invention, the protective layer coating composition uses as the protective metal nanometer one or more sols selected from the group consisting of a magnesium fluoride sol, an inorganic sol, an inorganic-inorganic composite sol, and an organic-inorganic composite sol. Substrate material that is used to improve the visibility by adjusting the refractive index.

a) Magnesium fluoride sol

The magnesium fluoride sol can be produced by mixing and reacting a magnesium compound and a fluorine compound in a solvent. Specific examples of the magnesium compound include magnesium hydroxide, magnesium oxide, magnesium methoxide, magnesium ethoxide, magnesium acetate, magnesium sulfonate, magnesium nitrate, and the like, and the fluorine compound includes trifluoroacetic acid, fluoric acid, ammonium fluoride, Phosphorus fluoride and so on. The solvent can be selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, octanol, 2-ethylhexanol, pentanol, benzyl alcohol, Hexanol, 2-hexanol, cyclohexanol, pinoresinol, nonanol, Methylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-acetone, diethylhydrazone, 1,2 -One or more solvents of a group consisting of diethylammonium ethane, 2-methoxyethyl acetate, propylene glycol monomethyl ether, and mixtures thereof. Preferably, methanol or a mixed solvent containing methanol may be used alone.

b) inorganic sol

The inorganic sol may be a metal oxide sol, and a metal oxide may be selected from the group consisting of ZnO, TiO ₂ , Al ₂ O ₃ , MgO, Al (OH) ₂ , SiO ₂ and Si (OH) ₂ . One or more of these groups, and polysiloxane, polydimethylsiloxane, polysilazane, polysilsesquioxane, polyhedral oligosilsesquioxane (POSS), etc. can be used together . The refractive index of the aforementioned metal oxide is preferably 1.3 to 2.0.

There are various choices of metal precursors used for the synthesis of metal oxides. More specifically, for the synthesis of Al ₂ O ₃ or Al (OH) ₂ metal oxide sols, aluminum acetate, aluminum acetone, ethyl Acetyl aluminum acetone, methyl ethyl acetone aluminum, isopropyl aluminum oxide, etc .; To synthesize ZnO metal oxide sol, zinc acetate, zinc acetoacetone, etc. can be used; for synthesizing MgO metal oxide sol, magnesium acetate, For the synthesis of TiO ₂ metal oxide sol, titanium acetate, titanium acetoacetate, titanium isopropoxide, etc. can be used for synthesis; for the synthesis of SiO ₂ metal oxide sol, ethyl tetraorthosilicate can be used. Esters (TEOS), tetramethoxysilane (TMOS), tetraethoxyethilanes (TEES), 1,2-bis (triethoxysilyl) ethane (BTSE), etc.

The solvent used for the inorganic sol may be the solvent used for the aforementioned magnesium fluoride sol.

c) Inorganic-inorganic composite sol

The inorganic-inorganic composite sol can be formed by sol-gel synthesis after mixing the magnesium fluoride sol and one or more metal oxides used in the inorganic sol. The mixing ratio can be adjusted arbitrarily. For example, for the manufacture of ZnO-MgF ₂ composite sol, may be added to the synthesized ZnO MgF ₂ sol when the sol synthesized, or synthesized separately mixed in a ratio of the sol used.

The inorganic-inorganic composite sol can easily adjust the refractive indices of the conductive film and the substrate.

As the solvent used for the inorganic-inorganic composite sol, the solvent used for the aforementioned magnesium fluoride sol can be used.

d) Organic-inorganic composite sol

The organic-inorganic composite sol can be introduced with an organic binder into one or more metal oxide sols composed of the magnesium fluoride sol, inorganic sol, and inorganic-inorganic composite sol to increase the flexibility of the protective layer or adjust the conductivity of the protective layer. The refractive index of the film.

The organic binder resin may be polyimide, acrylic polymer, epoxy resin, polyethylene glycol, polyester, polymethyl methacrylate, polyvinylpyrrolidone, cellulose, polyvinyl alcohol, or polymer. Urethane, polyacrylonitrile, etc., and in the cellulose resin, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl fiber can also be used Su et al. Preferably, the weight average molecular weight of the organic binder resin is 10,000 to 2,000,000.

The aforementioned organic binder resin is preferably used in an amount of 0.05 to 5 relative to the sol. Amount by weight. When it is within the aforementioned range, it is possible to simultaneously ensure refractive index and softness assurance, improve environmental resistance, improve viewing after etching, and good contact resistance of a transparent conductive film.

The solvent used in the inorganic-organic composite sol can use the aforementioned fluorine Solvent used in magnesium sol.

In the present invention, the coating composition may be arbitrarily formed by the aforementioned protective layer. The content of the magnesium fluoride sol, the inorganic sol, the inorganic-inorganic composite sol, and the organic-inorganic composite sol is appropriately adjusted, and it may be preferably used in an amount of 0.1 to 15% by weight, more preferably 1 to 10% by weight. When it is within the aforementioned range, it has the electrical characteristics and optical characteristics of the manufactured conductive film, and can be easily etched through an acid.

In the present invention, the aforementioned protective layer coating composition may be packaged as required. Contains additives commonly used in the art.

Preferably, the protective layer coating composition may further include fluorination. Magnesium sol. In this case, the magnesium fluoride sol may be contained alone, or the magnesium fluoride sol may be used in an inorganic-inorganic composite sol or an inorganic-organic composite sol. When a magnesium fluoride sol is used, it is particularly excellent in electrical characteristics and etching characteristics.

In the present invention, the aforementioned conductive film coating composition and The coating composition of the protective layer can be used in combination; or a protective layer can be formed as a single layer or two or more layers on the lower or upper part of the metal nanowire conductive film. The aforementioned sol can also form a protective layer alone or mix two or more types. Form a protective layer. In particular, when a protective layer is provided on the upper portion of the conductive film, wet etching can be performed, so that the subsequent step can be further inexpensive.

The present invention also provides the use of the aforementioned primary conductive film on a substrate. The manufacturing method of the transparent conductive film of a coating composition and the said protective layer coating composition, and the transparent conductive film manufactured by the said method.

In the present invention, the production of the transparent conductive film includes protection of one or more sols selected from the group consisting of a magnesium fluoride sol, an inorganic sol, an inorganic-inorganic composite sol, and an inorganic-organic composite sol. The single-coat type composition in which the conductive film coating composition containing the metal nanowires and the dispersion liquid in the layer coating composition is dispersed once is coated on the substrate and then dried, or may include the steps of sequentially forming the coating on the substrate and sequentially coating the foregoing. A step of drying the conductive film coating composition and the protective layer coating composition and drying the multilayer film once.

Preferably, the method of forming a transparent conductive film through a multilayer film does not affect the contact resistance of the metal nanowires, so that the desired high conductivity can be easily obtained, and high transmission with excellent uniformity during coating can also be obtained. Conductive, highly reliable transparent conductive film.

By forming the multilayer film described above, one or more protective layers can be formed between the substrate and the conductive film as described in FIGS. 3 to 6, and one or more protective layers can be formed on the upper portion of the conductive film. Preferably, at least one of the protective layers may be formed using a magnesium fluoride sol. More preferably, a protective layer may be formed on the conductive film directly above the conductive film. In this case, the electrical characteristics, optical characteristics, and etching characteristics of the transparent conductive film can be further improved. In the present invention, it is particularly shown that the electrical characteristics are reduced by 30 to 70% compared to when the transparent conductive film is used alone. This is because when the protective layer is formed on the conductive film, the material of the protective layer shrinks, so that the metallic film forming the conductive film is formed. The contact between the meter lines increases and the contact resistance decreases. In addition, when used with a protective layer, the effect of increasing the total light transmittance by 0.5 to 5% and reducing the haze (haze, haze) by 2 to 50% compared to when the conductive film is used alone. This is due to the refractive index adjustment effect produced by the protective layer composition. In order to show such an effect, the protective layer of the present invention preferably has a thickness of 10 to 500 nm. If the protective layer is formed with a thickness of less than 10 nm out of the foregoing range, the conductive film is not sufficiently covered and a part of the conductive film is exposed. If so, the effects of reducing surface resistance, increasing total light transmittance, and reducing haze cannot be obtained. In contrast, if a protective layer is formed over 500 nm, there is no effect of reducing the surface resistance of the protective layer, and no increase in light transmittance or decrease in haze occurs.

In the present invention, the aforementioned coating and drying can be used in the related technology. Printing and drying methods commonly used in the field of surgery, for example, printing can be performed using gravure offset printing, direct gravure printing, micro gravure printing, screen printing, inkjet printing, spin coating, slit coating, slit coating, etc. Transparent substrates used, such as polyimide (PI) substrates, polyethylene terephthalate (PET) substrates, polycarbonate (PC) substrates, cycloolefin polymer (COP) substrates, poly2,6 Ethylene naphthalate (PEN) substrate and the like. The coating thickness can be appropriately adjusted depending on the application, and for example, it can be a thickness of 0.1 to 100 μm.

In the present invention, in order to dry the coated film, the The heat treatment is performed at a low temperature.

Most metal oxides formed by sol-gel synthesis The compound is generally fired at a high temperature to form a crystalline phase. but, In the present invention, if the metal oxide is used as a protective layer to improve the adhesion of the metal nanowires, the heat treatment may be performed at a temperature of less than 200 ° C, or preferably 60 to 180 ° C. The low-temperature heat treatment of such a metal oxide sol is an effect of transforming the amorphous phase into an amorphous phase or a polymerized sol phase having a large molecular weight to increase the protective layer or adhesion.

In addition, the metal whose crystalline phase increases only at a temperature above 400 ° C In terms of the characteristics of oxides, there is a high possibility that subsequent processes cannot be etched at high temperature firing. Therefore, the amorphous phase or the sol phase with a large molecular weight is preferred in the present invention.

The transparent conductive film obtained by the foregoing method can be obtained by It is common in the technical field to perform a photo process and an etching process to form a pattern.

The present invention also provides a transparent conductive material manufactured by the aforementioned method. Sex film. The transparent conductive film manufactured by using the composition and method of the present invention has a light transmittance of more than 90% and a surface resistance of 200 Ω / □ or less, and has not only excellent surface resistance, environmental resistance, full light transmittance, and haze. Characteristics, and can be easily etched in the wet etching process and can realize a wide range of transparent conductive films through concentration adjustment. Therefore, it is useful to use electrical devices or optical devices. A specific example is to use liquid crystal display devices and electrical devices. Plasma display devices, touch panels, electric field light-emitting devices, thin-film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells.

The light transmittance in the present invention is preferably 88%, more preferably Above 90%, and the surface resistance is preferably below 150Ω / □, more preferably 100Ω / □ or less, and most preferably 80Ω / □ or less.

In the following, a preferred embodiment is suggested for understanding the present invention, but the following The embodiments described are merely examples to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Synthesis Example 1: Synthesis of SiO ₂ Sol

0.5 g of oxalic acid was added to 30 g of a solvent in which water, ethanol and propylene glycol monoethyl ether were mixed at a ratio of 2: 5: 3, and then stirred while heating to 40 to 70 ° C. At the end of the temperature increase, 0.05 mol of tetra-orthosilicate (TEOS) was added and the reaction was carried out for more than 2 hours to synthesize a SiO ₂ sol.

Synthesis Example 2: Synthesis of TiO ₂ Sol

After mixing 0.005 moles of titanium tetrachloride, 0.094 moles of benzyl alcohol, and 0.034 moles of ethanol, the mixture was reacted at a temperature of 70 to 90 ° C. for more than 6 hours to form a white titanium dioxide powder. While the titanium dioxide powder was washed with diethyl ether, the titanium dioxide powder was separated by a centrifuge. After dispersing the separated titanium dioxide powder with 3 g of ethanol, it was stirred with 3 g of a solution of cesium carbonate dissolved in 2-ethoxyethanol at 0.2% by weight to synthesize a TiO ₂ sol.

Synthesis Example 3: Synthesis of MgF ₂ Sol

After dissolving 1 mole of magnesium methoxide or magnesium acetate in methanol and stirring as a magnesium precursor, in order to impart fluoride ions, the amount of magnesium precursor is 2 moles of fluoric acid or trifluoroacetic acid and is between 60 and 90 ° C After 12 hours of discrete reaction, an aging treatment was performed for more than 1 day and a MgF ₂ sol was synthesized.

Synthesis Example 4: Synthesis of ZnO Sol

After adding 0.5 mol of ZnO particles to a 5: 5 mixed solvent of methanol and ethanol as a zinc precursor, the temperature was raised to 50 ° C. Then, add 1 Mol acetone, methyl acetone or ethyl acetone and synthesize ZnO sol.

Synthesis Example 5: Synthesis of Al ₂ O ₃ Sol

After adding 0.5 mol of Al ₂ O ₃ particles in a 5: 5 mixed solvent of methanol and ethanol as an aluminum precursor, the temperature was raised to 50 ° C. Then, 1 mol of acetone, methyl acetone or ethyl acetone was added and an Al ₂ O ₃ sol was synthesized.

[Examples 1 to 20]

A laminated structure of the form shown in FIG. 3 was formed using the sol synthesized as described above. In order to manufacture a transparent conductive film, a flexible plastic substrate is used for the substrate 11 and PET is used. The conductive film 12 coating composition containing a metal nanowire and a dispersion liquid is prepared by diluting a silver nanowire in ethanol at 0.1 to 0.2% by weight. The primary protective layer 15 and the secondary protective layer 16 are manufactured by the sol synthesis method disclosed above, and after adding 0.5 g of hydroxypropyl cellulose to the sol synthesis, the organic-inorganic composite sol is completed through the same process, and will be prepared A good organic-inorganic composite sol was diluted at 7% by weight in ethanol to prepare a protective layer coating composition. In addition, the inorganic-inorganic composite sol is produced by mixing the sol produced by the disclosed sol synthesis method in a 1: 1 weight ratio.

The metal nanowire conductive film is coated by slit coating or microgravure coating, gravure coating, rod coating, etc., so that the coating thickness is 18 to 25 μm, and dried in an oven at 100 to 130 ° C. which is smooth by convection.

1 The protective layer and the secondary protective layer are similarly applied through a coating method of a metal nanowire conductive film so as to have a coating thickness of 15 to 20 μm, and dried by a drying method of the primary conductive film.

Primary and secondary guarantees for evaluating and manufacturing transparent conductive films The properties of the transparent conductive film after the protective coating composition is completed are described in Table 1 below, and the etching characteristics are grasped through a series of photo-substance coating-exposure-development-etching procedures.

The performance of each other item is performed as follows.

1) Surface resistance: Measure the surface resistance per unit area through a surface resistance measuring device.

2) Environmental resistance: Measure the time that the surface resistance does not change under the conditions of temperature 85 ° C and humidity 85%.

3) Total light transmittance: Measure the visible light transmittance using a spectrophotometer in a wavelength region of 400 to 800 nm.

4) Haze: Measured with a turbidimeter COH400 from (NIPPON DENSHOKU).

5) Wet etching time: use hydrogen peroxide and nitric acid mixed solution as the etching solution, and measure the time without electrical conductivity.

[Examples 21 to 42]

A layered structure as shown in FIG. 4 was formed using the sol synthesized as described above. Except that the secondary protective layer 17 was additionally formed on the secondary protective layer 16, the same method as in Examples 1 to 20 described above was performed and transparent conductive was obtained. The physical properties and performance evaluations are described in Table 2 below.

[Examples 43 to 64]

The sol formed by the aforementioned synthesis is used to form the form shown in FIG. 5. Laminated structure. Except that the conductive film 12 is formed on the substrate 11 and the protective layer 13 is formed on the metallic nanowire conductive film 12, the same method as in the foregoing Examples 1 to 20 is performed to obtain a transparent conductive film, and the physical properties and The performance evaluation is described in Table 3 below.

[Examples 65 to 84]

A laminated structure having the form shown in FIG. 6 was formed using the sol synthesized as described above. In addition to the secondary protective layer 14 being additionally formed on the primary protective layer 13 Other than that, the same method as in Examples 1 to 20 was performed to obtain a transparent conductive film, and the physical properties and performance evaluations are shown in Table 4 below.

[Examples 85 to 92]

The sol formed by the aforementioned synthesis is used to form the form shown in FIG. Laminated structure. A transparent conductive film 18 is formed on the substrate 11 by coating the composition with a single liquid metal nanowire.

Each sol is manufactured by the sol synthesis method disclosed above, and An organic-inorganic composite sol was produced through the same process after adding 0.5 g of hydroxypropyl cellulose to sol synthesis. In addition, the inorganic-inorganic composite sol is produced by mixing a sol made by the disclosed sol synthesis method by a 1: 1 weight ratio. Each composite sol is added to the silver nanowire at 7% by weight and diluted with 0.1 to 0.2% by weight of ethanol, and then stirred to prevent the sol from agglomerating together to produce a single-liquid metal nanowire coating composition. This coating composition was subjected to the same method as in Examples 1 to 20 to obtain a transparent conductive film, and physical properties and performance evaluations are described in Table 5 below.

[Comparative Example 1] Production of a multilayer film using a polyurethane polymer

In addition to diluting silver nanowires in water at 0.1 to 0.2% by weight, and dissolving a polyurethane polymer in methyl ethyl ketone at 7% by weight to form a protective layer-forming composition, A multilayer transparent conductive film was formed by the same method as in Examples 1 to 20, and physical properties and performance evaluations are described in Table 5 below.

[Comparative Example 2] Production of a single-layer film using a polyurethane polymer

In addition to diluting silver nanowires in water at 0.2 to 0.4% by weight, and simultaneously dissolving a polyurethane polymer at 14% by weight in methyl ethyl ketone to produce a composition for forming a protective layer, and A single-layer transparent conductive film was formed by the same method as in Examples 85 to 92 except that the composition for forming a protective layer was mixed with a silver nanowire dispersion liquid at a ratio of 1: 1, and physical properties and performance evaluations were described in It is shown in Table 5 below.

As shown in the aforementioned Tables 1 to 5, the transparent conductive film of the present invention is not only It has excellent surface resistance, environmental resistance, full light transmittance and haze characteristics, and can be easily etched in wet etching procedures, and especially shows excellent physical properties when using magnesium fluoride to form another protective layer.

11‧‧‧ substrate

12‧‧‧ conductive film

15‧‧‧1 protective layer

16‧‧‧2 times protective layer

Claims (18)

A transparent conductive film coating composition, comprising: 1) a primary conductive film coating composition including metal nanowires and a dispersion liquid; and 2) a protective layer coating composition including fluorinated Magnesium sol. The transparent conductive film coating composition according to claim 1, wherein the aforementioned metal nanowire is used in an amount of 0.05 to 0.5% by weight based on the aforementioned dispersion. The transparent conductive film coating composition according to claim 1, wherein the aforementioned first conductive film coating composition further includes an organic binder. The transparent conductive film coating composition according to claim 1, wherein the metal of the aforementioned metal nanowire is selected from the group consisting of gold, silver, copper, aluminum, nickel, tin, palladium, platinum, zinc, iron, indium, and magnesium One or more metals in the group. The transparent conductive film coating composition according to claim 1, wherein the diameter of the metal nanowire is 15 nm to 120 nm, and the length is 5 μm to 60 μm. The transparent conductive film coating composition according to claim 1, wherein the dispersion is selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, and octanol , 2-ethylhexanol, pentanol, benzyl alcohol, hexanol, 2-hexanol, cyclohexanol, pinoresinol, nonanol, methyl glycol, ethylene glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, three Ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-acetone, diethylhydrazone, acetamidine acetone, 1,2-diethylammonium ethane, dimethyl carbonate, Diethyl carbon Group consisting of acid esters, propylene glycol methyl ether acetate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone, N-methylacetamide, and mixtures thereof One or more solvents. The transparent conductive film coating composition according to claim 1, wherein the protective layer coating composition further comprises a material selected from the group consisting of ZnO, TiO ₂ , MgO, CaF ₂ , Al ₂ O ₃ , Al (OH) ₂ , SiO ₂ and One or more of the groups consisting of Si (OH) ₂ . The transparent conductive film coating composition according to claim 1, wherein the protective layer coating composition further comprises a material selected from the group consisting of polyimide, acrylic polymer, epoxy resin, polyethylene glycol, polyester, and polymethyl One or more organic binder resin groups consisting of methyl acrylate, polyvinyl pyrrolidone, cellulose, polyvinyl alcohol, polyurethane, and polyacrylonitrile. The transparent conductive film coating composition according to claim 8, wherein the organic binder resin is used in an amount of 0.05 to 5% by weight based on the metal oxide sol. A method for manufacturing a transparent conductive film, comprising a step of applying a protective layer coating composition as described in claim 1 and a single-time conductive film coating composition on a substrate, followed by drying. The method for manufacturing a transparent conductive film according to claim 10, comprising coating a single-liquid type composition in which a primary conductive film coating composition including a metal nanowire and a dispersion liquid is dispersed in the protective layer coating composition. Post drying step on the substrate. The method for manufacturing a transparent conductive film according to claim 10, comprising: coating the aforementioned conductive film coating composition on a substrate; A step of drying; and a step of drying after applying the protective layer coating composition of claim 1 to the aforementioned primary conductive film. The method for manufacturing a transparent conductive film according to claim 10, comprising the steps of: coating the protective layer coating composition on a substrate, and drying; and coating the protective layer film with the conductive film coating composition once, A step of drying; and a step of drying after coating the protective layer coating composition on the primary conductive film. The method for manufacturing a transparent conductive film according to claim 10, wherein the drying is heat-treated at a temperature of less than 200 ° C. The method for manufacturing a transparent conductive film according to claim 10, wherein the transmittance of the transparent conductive film is 90% or more. The method for manufacturing a transparent conductive film according to claim 10, wherein the surface resistance of the transparent conductive film is 100 Ω / □ or less. The method for manufacturing a transparent conductive film according to claim 10, wherein the transparent conductive film is an electrode. The method for manufacturing a transparent conductive film according to claim 10, wherein the thickness of the protective layer of the transparent conductive film is 10 to 500 nm.