WO2015046843A1 - Conductive coating composition containing metal nanowire, and method of forming conductive film using same - Google Patents

Abstract

The present invention relates to a conductive coating composition containing metal nanowire, and a method of forming a conductive film using same and, more particularly, to a conductive coating composition including metal nanowire, ladder-type silsesquioxane polymer, organic binder resin, and dispersion liquid, so that the composition has good surface resistance, wear resistance, hardness, adhesion to a base material, and flexibility and is suitable for manufacturing a conductive film, and to a method of manufacturing a conductive film using same.

Description

Conductive coating composition containing metal nanowires and method for forming conductive film using same

The present invention relates to a conductive coating composition containing a metal nanowire and a method for forming a conductive film using the same, and more particularly, by including a metal nanowire, a ladder-type silsesquioxane polymer, an organic binder resin, and a dispersion liquid. The present invention relates to a conductive coating composition suitable for producing a conductive film having excellent sheet resistance, abrasion resistance, hardness, adhesion to a substrate, and flexibility, and a method of manufacturing the conductive film using the same.

ITO is generally applied to touch screen panels, OLED devices, and flexible devices as a transparent conductive film.However, as the substrate becomes larger, ITO desperately needs replacement materials due to the limitation of metal oxide to satisfy the required low sheet resistance and excellent flexibility. It is becoming.

As an alternative material to solve this problem, metal nanowire-based transparent conductive film is used, and it is used in various fields because it realizes low sheet resistance and has excellent flexibility while maintaining high optical properties of the film that ITO cannot solve. .

However, since the metal nanowire-based transparent conductive film has a structure in which resistance is realized by wire contact of nanowires unlike ITO, the wire contact is broken due to an external impact, ie, a scratch or peeling off by a high adhesion protective film, or a nanowire. The disadvantage is that the resistance can be easily increased due to breakage. This drawback is also an important factor in increasing the process margin in the process of manufacturing a metal nanowire-based transparent conductive film, and furthermore, durability must be secured because it directly affects the yield when the process is performed after implementing the pattern.

In order to increase the adhesion of the substrate in the durability of the film, US Patent Publication No. 2012-0097059 (NANOWIRE INK COMPOSITIONS AND PRINTING OF SAME) has tried to increase the adhesion to the lower substrate by applying a silane coupling agent as an adhesion promoter. Although many additives have been studied to increase the adhesion between the coating agent and the substrate film while increasing the adhesion between the substrate and the substrate, such as the silane coupling agent, sufficient measures must be secured to a certain extent not only to the substrate adhesion but also to the wear resistance and hardness to secure durability during the film process. I can not say.

In general, the durability requirements, which are physical characteristics of conductive films, include pencil hardness, anti-scratch, and adhesion strength. Yield can be secured.

In order to solve the above problems, the present invention has excellent sheet resistance, abrasion resistance, hardness, adhesiveness and flexibility to the substrate suitable for forming a conductive film, excellent optical properties and excellent dispersibility of metal nanowires An object of the present invention is to provide a conductive coating composition and a method for producing a conductive film using the same, which have solved problems such as clouding, phase separation, and gelation of the coating composition.

In addition, an object of the present invention is to provide a conductive film and an electronic device comprising the film is produced by the above method having excellent sheet resistance, wear resistance, hardness, adhesion to the substrate and flexibility.

The present invention to achieve the above object,

In conductive coating compositions,

1) metal nanowires;

2) ladder type silsesquioxane polymers;

3) organic binder resins; And

4) dispersion

It provides a conductive coating composition comprising a.

In another aspect, the present invention provides a method for forming a conductive film, characterized in that the conductive coating composition is coated on a substrate and dried.

In another aspect, the present invention provides a conductive film formed by the conductive film forming method.

In another aspect, the present invention provides an electronic device comprising the conductive film.

The conductive coating composition according to the present invention is excellent in optical properties and excellent dispersibility of metal nanowires can solve the problems such as whitening, phase separation, gelation of the coating composition, the conductive film according to the present invention has excellent sheet resistance, wear resistance It is suitable for use in electronic devices because of its hardness, adhesion to substrates and flexibility.

The conductive coating composition of the present invention comprises: 1) metal nanowires; 2) ladder type silsesquioxane polymers; 3) organic binder resins; And 4) a dispersion.

Each component is demonstrated below.

1) metal nanowires

The conductive coating composition of the present invention uses metal nanowires as the conductive material. As the metal nanowires used in the present invention, metal nanowires used for conventional conductive film formation may be used. More specifically, metals that can be used are not particularly limited, and are preferably gold, silver, copper, aluminum, and nickel. It is preferable to use at least one metal selected from the group consisting of Group I, IIA, IIIA, IVA and Group VIII B metals such as tin, palladium, platinum, zinc, iron, indium and magnesium, and more preferably. Preferably, at least one metal selected from the group consisting of zinc, aluminum, tin, copper, silver and gold is used.

The metal nanowires preferably have a diameter of 15 nm to 120 nm and a length of 5 μm to 60 μm, and are preferably used in an amount of 0.01 to 0.5 wt% in the conductive coating composition.

2 Ladder type silsesquioxane polymer

The silsesquioxane polymer used in the present invention is a ladder type silsesquioxane polymer, and a weight average molecular weight is preferably 10,000 to 200,000, more preferably 30,000 to 100,000. .

Preferably, the ladder silsesquioxane polymer has a structure of Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently a cyclic or acyclic aliphatic organic functional group, an alkyl group, an alkylhalogen, an aryl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group or a siol group connected by hydrogen, C ₁ to C ₂₀ In this case, all of R ¹ to R ⁴ may be substituted with the same or different organic functional groups;

R ⁵ to R ⁸ may each independently be selected from the group consisting of an alkyl group of C _1-5 , a cycloalkyl group of C _3-10 , an aryl group of C _6-12 , an alcohol, an alkoxy group, and a combination thereof;

n is 1 to 100,000.

In the above, the alcohol or alkoxy group is preferably -OCR 'or -CR' = N-OH, wherein R 'is an alkyl group of C _1-6 .

The ladder-type silsesquioxane polymer used in the present invention may be prepared by a known method or commercially available. Preferably, the silsesquioxane polymer of Formula 1 is a trifunctional silane into which an organic functional group is introduced. It can be prepared by the hydrolysis of the compound of formula 2 and subsequently condensation reaction:

[Formula 2]

In Chemical Formula 2,

R ⁹ is hydrogen, an organic functional group such as a cyclic or acyclic aliphatic organic functional group connected by C ₁ to C ₂₀ , an alkyl group, an alkylhalogen, an aryl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group or a siol group;

R ¹⁰ is selected from the group consisting of an alkyl group of C _1-5 , a cycloalkyl group of C _3-10 , an aryl group of C _6-12 , an alcohol, an alkoxy group, and a combination thereof,

Q is a C _1-6 alkylene group or C _1-6 alkyleneoxy group,

m is an integer from 0 to 4,

p is an integer of 0 or 1.

In the above, the alcohol or alkoxy group is preferably -OCR 'or -CR' = N-OH, wherein R 'is an alkyl group of C _1-6 .

In addition, in Formula 2, R ⁹ or R ¹⁰ may be an aromatic organic functional group such as a phenyl group, but when the content of the aromatic organic functional group among the R ¹ to R ⁴ , which is a side chain group, is low in the ladder silsesquioxane polymer, the transmittance is low. Since it tends to lose, it is preferable to adjust the content of phenyl in 100% of the total of the side chain groups R ¹ to R ⁴ to less than 80 mol%.

Reaction conditions in the preparation of the silsesquioxane polymer of the present invention may be carried out according to a method commonly used in the art, for example, the method described in Korean Patent Publication No. 10-2010-0131904.

In addition, the degree of condensation of the silsesquioxane polymer may be adjusted to 1 to 99.9%, and the -OH content of the silsesquioxane polymer terminal may be arbitrarily adjusted in various ways according to the polarity change of the cellulose-based resin used for mixing. When the content of -OH of the silsesquioxane polymer terminal is preferably 0.01 to 50% of the terminal group, a resin composition having excellent storage stability may be prepared.

In addition, when the UV absorbers commonly known in the preparation of the compound of Formula 1 are introduced into R ¹ to R ⁸ , it may be used as an additive for imparting UV blocking properties in film production. As a specific example, a compound that can be used as an ultraviolet absorber is (2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl) -4-methyl-phenol (2- (5-chloro-2H-benzotriazole-2-yl) -6 (1,1-dimethylethyl) -4-methyl-phenol), octyl-3- [3-tert-butyl-4-hydroxy-5- (5 -Chloro-2H-benzotriazol-2-yl) phenyl] propionate (Octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl UV absorber containing a halogen element such as] propionate) and 2- (2H-benzotriazol-2-yl) -4,6-ditertylphenol (2- (2H-benzotriazol-2-yl) -4,6 -ditertylphenol), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (2- (2H-benzotriazol-2-yl) -4,6 -bis (1-methyl-1-phenylethyl) phenol), 2- (2H-benzotriazol-2-yl) -4 (1,1,3,3-tetramethylbutyl) phenol (2- (2H-benzotriazol -2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4 -(1,1,3,3-tetramethylbutyl) phenol (2- (2H-benzotriazol-2-yl) -6- ( 1-methyl1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxy Oxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (2- [4-[(2-Hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine), 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2 -Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine (2- [4-[(2-Hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl ] 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine) ultraviolet absorbers that do not contain a halogen element can be used.

In the conductive coating composition of the present invention, the silsesquioxane is preferably used in an amount of 0.01 to 1.0% by weight. If the content is less than 0.01% by weight, the original purpose for imparting durability through the silsesquioxane cannot be achieved. When the content exceeds 1.0% by weight, it inhibits the contact of the metal nanowires, thereby acting as an insulator to rapidly increase the contact resistance of the transparent conductive film, thereby preventing the desired conductivity.

3 A) organic binder resin

The conductive coating composition of the present invention comprises an organic binder resin. The organic binder resin controls the viscosity of the conductive coating composition of the present invention, improves the coating property of the composition, increases the adhesion with the substrate, and increases the flexibility of the thin film.

The organic binder resin usable in the present invention is polyimide, acrylic polymer, epoxy, polyethylene glycol, polyester, polymethyl methacrylate, polyvinylpyrrolidone, cellulose, polyvinyl alcohol, polyurethane, polyacrylonitrile And the like, and are preferably cellulose resins. Among the cellulose resins, triacetyl cellulose, diacetyl cellulose, acehydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, Cellulose acetate butyrate, cellulose acetate propionate, and the like.

The organic binder resin is preferably used in an amount of 0.02-10 wt% in the conductive coating composition of the present invention. When the content is less than 0.02% by weight, it is impossible to achieve the original purpose to control the viscosity, improve coating properties, increase adhesion with the substrate and give flexibility through the organic binder resin formed when the conductive film is bent more than a certain degree The metal nanowires may deviate from the substrate or the conductive coating composition may not be uniformly coated on the entire surface of the substrate, resulting in the inability to form a film having excellent electrical conductivity. In addition, when the content is 10% by weight or more, the organic binder resin inhibits contact with the metal nanowires to serve as an insulator to rapidly increase the contact resistance of the transparent conductive film, and the viscosity is rapidly increased to form a thick film to optically Problems may deteriorate. If the film thickness becomes too thick, the entire film becomes yellow, which adversely affects visibility.

4) dispersion

The conductive coating composition of the present invention comprises a dispersion in the remaining amount in addition to the 1) metal nanowires, 2) silsesquioxane polymer, and 3) organic binder resin, the dispersion is a viscosity control of the metal nanowire dispersion, a smooth film It can select suitably in consideration of formation, the dispersibility of a metal nanowire, etc.

Specific examples of the dispersion include water, methanol, ethanol, propanol, isopropanol, isopropyl acetate, butanol, 2-butanol, octanol, 2-ethylhexanol, pentanol, benzyl alcohol, hexanol, 2-hexanol, Cyclohexanol, terpineol, 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-propanone, diacetyl, acetylacetone, 1,2-diacetylethane, dimethyl carbonate, diethyl carbonate, propylene glycol methyl ether Tate, 2-methoxyethyl acetate, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone, N-methylacetamide, dimethylformamide, monomethylformamide, dimethylacetamide, methylene chloride, methylethylketone At least one solvent selected from the group consisting of methyl isobutyl ketone, methyl isopropyl ketone, diacetone alcohol and mixtures thereof may be used, and preferably ethanol, isopropanol alone or a mixed solvent including the same may be used. .

In addition, the conductive coating composition of the present invention may further include a functional additive, which may be conventionally included in a curing agent, a plasticizer, a sunscreen or a coating composition for forming a conductive film, if necessary, within a conventional range.

The present invention also provides a method for forming a conductive film, characterized in that the present invention is coated with a conductive coating composition on a substrate and dried.

The conductive coating composition according to the present invention can be used in various printing processes commonly used in the art, for example, gravure off-set printing, gravure direct printing, micro gravure printing. Screen printing, imprinting method, reverse off-set, spin coating, slit coating, slot die coating, etc. Transparent substrates used may be printed, for example, polyimide (PI) substrates, polyethylene terephthalate (PET) substrates, polycarbonate (PC) substrates, cycloolefin polymer (COP) substrates, polyethylene naphthalate (PEN) substrates, and the like. have. In addition, the coating thickness may be appropriately adjusted according to the use, and a general drying process and a low temperature heat treatment process may be applied for film formation, if necessary.

In addition, the conductive film forming method of the present invention may further form a protective layer on the film formed after the drying process.

As the composition for forming the protective layer, a composition including 2) silsesquioxane polymer, 3) organic binder resin, and 4) dispersion of the conductive coating composition may be used.

In the composition for forming the protective layer, the organic binder resin is preferably used in an amount of 0.05-4% by weight of the composition. When the content is less than 0.05% by weight, it is difficult to achieve the original purpose to impart viscosity control, improve coating properties, increase adhesion and flexibility through the organic binder resin, it is difficult to expect the reinforcing effect and optical reinforcing effect, the When the content exceeds 4% by weight, the contact resistance of the film is sharply increased, the viscosity is rapidly increased, and the thickness of the coating film is formed thick, resulting in a problem of deteriorating the optical properties. As the film thickness becomes too thick, the optical reinforcing effect cannot be realized.

In addition, the silsesquioxane in the composition for forming the protective layer is preferably used in an amount of 0.1 to 1.0% by weight in the composition. When the content is less than 0.1% by weight, it may be difficult to expect improved durability, and when the content exceeds 1.0% by weight, it may be difficult to achieve the desired conductivity.

In the conductive film forming method of the present invention, a conventional printing method, a drying method, and a low temperature heat treatment method may be applied when the conductive film is formed using the conductive coating composition when the protective layer is formed. In the case of forming a resistance reinforcement effect, optical reinforcement effect, durability reinforcement effect can be further enhanced, and the wet etching, etc. can be possible to facilitate the convenience in subsequent processes.

The present invention also provides a transparent conductive film formed according to the above method. The transparent conductive film prepared by using the composition and method of the present invention has a light transmittance of 90% or more, a sheet resistance of 200 Ω / □ or less, excellent sheet resistance, environmental resistance, warfare transients, and haze, as well as wetness. Etching can be easily performed in the etching process and a wide range of transparent conductive films can be realized by adjusting the concentration, so that liquid crystal displays, plasma displays, touch panels, electroluminescent devices, thin film solar cells, dye-sensitized solar cells, and inorganic crystalline solar cells It can be usefully used for electrodes, such as a battery.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Synthesis Example 1 : Preparation of Cellulose Solution

1 part by weight of triacetyl cellulose (Sigma Aldrich, Fluka) was prepared by mixing at least one solvent of methylene chloride and methyl ethyl ketone, diacetone alcohol, dimethyl formamide, dimethyl sulfoxide, methyl isobutyl ketone for 24 hours.

Synthesis Example 2 Preparation of Silsesquioxane Polymer

In a dried flask equipped with a cooling tube and a stirrer, 15% by weight of distilled water, 4% by weight of methanol (99.86% purity), and 1% by weight of tetramethyl ammonium hydroxide (25% in water) were mixed to include a catalyst. After preparing the reaction solvent in advance, 80% by weight of the silane monomer was added to the prepared mixed reaction solvent. At this time, the mixing ratio of the silane monomer is 10 mol% of trimethoxyphenylsilane (DOW CORNING, trade name DOW CORNING (R) Z-6124 SILANE) and gamma-methacryloxypropyltrimethoxysilane (DOW CORNING, trade name DOW CORNING (R) Z-6030 SILANE) was adjusted to 90 mol%. Thereafter, the mixture was slowly stirred for 8 hours in a nitrogen atmosphere, and then the stirring of the reaction solution was stopped and allowed to stand at room temperature for 24 hours. Then, the reaction solution including the precipitate was vacuum filtered to separate the precipitate. The separated precipitate was washed and filtered several times with a mixture of distilled water and methanol to remove impurities, and finally washed with methanol, and then dried by vacuum drying at room temperature for 20 hours to 1 part by weight of methylene chloride and methanol 9: 1. 9 weight part of mixed solvents mixed by (weight ratio) were dripped, and the target polyaliphatic aromatic silsesquioxane polymer resin was manufactured. The weight average molecular weight of the obtained polyaliphatic aromatic silsesquioxane polymer was 40,000. In this case, the weight average molecular weight is a polystyrene reduced average molecular weight measured using gel permeation chromatography.

Synthesis Examples 3 to 9 : Preparation of Silsesquioxane Polymer

15% by weight of distilled water, 4% by weight of methanol (99.86% purity), and 80% by weight of silane monomer were added dropwise to 1% by weight of tetramethyl ammonium hydroxide (25% in water) in the molar ratio as shown in Table 1 below. The polymer silsesquioxane resin was prepared in the same manner as in Synthesis example 2.

Table 1 Gamma-methacryloxypropyltrimethoxysilane (mol%) Trimethoxyphenylsilane (mol%) Synthesis Example 3 80 20 Synthesis Example 4 70 30 Synthesis Example 5 60 40 Synthesis Example 6 50 50 Synthesis Example 7 40 60 Synthesis Example 8 30 70 Synthesis Example 9 20 80

Example 1-4

Example 1

0.5 wt% ethanol dispersion of 2 wt% silver nanowires having an aspect ratio of 600 or more with a conductive coating composition, wherein 1 wt% of hydroxypropylcellulose and polysilsesquioxane synthesized in Synthesis Example 2 are mixed at a weight ratio of 3: 7. Wasopropyl alcohol dispersion was added to 1.06 g and dispersed for 1 hour or more. In addition, 8.44 g of ethanol was added to control the content of the silver nanowire, thereby completing the conductive coating composition.

As a secondary protective layer, 0.3 g of triacetyl cellulose (Sigma Aldrich, Fluka) was added to 14.85 g of methylene chloride and dissolved at room temperature for 24 hours. 14.85 g of methyl ethyl ketone was added to the triacetyl cellulose solution dispersed in the methylene chloride, followed by stirring at 1000 rpm for 2 hours to prepare a cellulose solution. 29.7 g of polysilsesquioxane diluted in methyl ethyl ketone at 1% by weight was added thereto, mixed at 1000 rpm for 6 hours, and then commercially available thermosetting additive (Asahi Kasei chemical) was added at 1000 rpm for 6 hours. After the viscosity was adjusted while stirring to finish.

Each prepared coating composition was coated on a PET film so as to have a dry coating thickness of 130 nm, and then the coated specimen was dried for 90 seconds in a 140 ° C. drying furnace to evaluate physical properties and performance, and is shown in [Table 2].

Example 2

0.5 wt% ethanol dispersion of 2 wt% silver nanowires having an aspect ratio of 600 or more with a conductive coating composition, 1 wt% of cellulose acetate butate and polysilsesquioxane synthesized in Synthesis Example 2 at a weight ratio of 5: 5 Wasopropyl alcohol dispersion was added to 1.06 g and dispersed for 1 hour or more. In addition, 8.44 g of ethanol was added to control the content of the silver nanowire, thereby completing the conductive coating composition.

0.36 g of triacetylcellulose (Sigma Aldrich, Fluka) was added to 17.82 g of methylene chloride and dissolved at room temperature for 24 hours. 17.82 g of methyl ethyl ketone was added to the triacetyl cellulose solution dispersed in methylene chloride, followed by stirring at 1000 rpm for 2 hours to prepare a cellulose solution. 24 g of polysilsesquioxane diluted in methyl ethyl ketone at 1% by weight was added thereto, followed by mixing at 1000 rpm for 6 hours, followed by addition of a commercial thermosetting additive (Asahi Kasei Chemical Co., Ltd.) for 6 hours at 1000 rpm. After the viscosity was adjusted while stirring to finish.

Example 3

0.5 wt% ethanol dispersion of 2 wt% silver nanowires having an aspect ratio of 600 or more with a conductive coating composition containing 1 wt% of cellulose acetate propionate and polysilsesquioxane synthesized in Synthesis Example 2 at a weight ratio of 7: 3 % Isopropyl alcohol dispersion was added to 1.06 g and dispersed for 1 hour or more. In addition, 8.44 g of ethanol was added to control the content of the silver nanowire, thereby completing the conductive coating composition.

0.48 g of triacetyl cellulose (Sigma Aldrich, Fluka) was added to 23.76 g of methylene chloride and dissolved at room temperature for 24 hours. 23.76 g of methyl ethyl ketone was added to the triacetyl cellulose solution dispersed in the methylene chloride, followed by stirring at 1000 rpm for 2 hours to prepare a cellulose solution. 12 g of polysilsesquioxane diluted in methyl ethyl ketone at 1% by weight was added thereto, followed by mixing at 1000 rpm for 6 hours, followed by addition of a commercial thermosetting additive (Asahi Kasei Chemical Co., Ltd.) at 6 rpm at 1000 rpm. After the viscosity was adjusted with stirring for hours.

Example 4

0.5 g of an ethanol dispersion of 2 wt% silver nanowire having an aspect ratio of 600 or more was mixed with the cellulose acetate propionate and the polysilsesquioxane synthesized in Synthesis Example 2 at a weight ratio of 9: 1. Isopropyl alcohol dispersion by weight was added to 1.06 g and slightly dispersed for 1 hour or more. In addition, 8.44 g of ethanol was added to control the content of the silver nanowire, thereby completing the conductive coating composition.

0.54 g of triacetylcellulose (Sigma Aldrich, Fluka) was added to 26.73 g of methylene chloride and dissolved at room temperature for 24 hours. 26.73 g of methyl ethyl ketone was added to the triacetyl cellulose solution dispersed in the methylene chloride, followed by stirring at 1000 rpm for 2 hours to prepare a cellulose solution. 6 g of polysilsesquioxane diluted in methyl ethyl ketone at 1% by weight was added thereto, followed by mixing at 1000 rpm for 6 hours, followed by addition of a commercial thermosetting additive (Asahi Kasei Chemical Co., Ltd.) at 6 rpm at 1000 rpm. After the viscosity was adjusted with stirring for hours.

Comparative Example 1

0.5 g of silver nanowire 2-weight ethanol dispersion having an aspect ratio of 600 or more was added to 1.06 g of 0.5 wt% of hydroxypropyl cellulose in an isopropyl alcohol dispersion. In addition, 8.44 g of ethanol was added to control the content of the silver nanowire, thereby completing the conductive coating composition.

0.54 g of triacetylcellulose (Sigma Aldrich, Fluka) was added to 26.73 g of methylene chloride and dissolved at room temperature for 24 hours. 26.73 g of methyl ethyl ketone was added to the triacetyl cellulose solution dispersed in the methylene chloride, followed by stirring at 1000 rpm for 2 hours to prepare a cellulose solution. A thermosetting additive (Asahi Kasei chemical Co., Ltd.) commercially available was added thereto, followed by finishing the viscosity control while stirring at 1000 rpm for 6 hours.

Performance evaluation was performed as follows for the conductive coating compositions prepared in Examples 1 to 4 and Comparative Example 1, and the results are shown in Table 2 below.

1) Primary sheet resistance: The surface resistance per unit area was measured by a sheet resistance meter.

2) Secondary sheet resistance: After coating and drying the secondary membrane, the sheet resistance was measured and the effect of resistance reinforcement was observed.

3) Total transmittance: In the wavelength range of 400 nm to 800 nm, visible light transmittance was measured after applying and drying the secondary membrane using a spectrophotometer, and the optical reinforcing effect was observed.

4) Haze: Measured after coating and drying the secondary film using a haze meter COH 400 of NIPPON DENSHOKU, and observed the optical reinforcing effect.

5) Hardness: After the primary membrane and the secondary membrane was applied and dried, it was measured using a pencil hardness tester, and determined to be less than the hardness at which disconnection occurred.

6) Substrate adhesion: The substrate adhesion was evaluated according to the measuring method of ASTM-D3359.

7) Anti-scratch: Measure the rate of change of resistance using a friction force gauge

TABLE 2 Primary surface resistance (Ω / sq) Secondary surface resistance / resistance reinforcement effect (%) Combat Transition / Optical Enhancement (%) Haze / optical reinforcing effect (%) Hardness Adhesion Scratch resistance (Ω / cm ² ) Example 1 355.5 61.4 2.05 44.3 1H 未 peeling 44 Example 2 265.0 55.9 2.31 47.4 1H 未 peeling 26 Example 3 239.7 69.4 2.45 48.4 HB 未 peeling 8 Example 4 195.8 66.6 2.64 52.5 B 未 peeling -22 Comparative Example 1 190.5 58.9 0.66 10.5 6B Peeling More than 400

As shown in the table, in Examples 1 to 4, the primary sheet resistance was formed high depending on the content of polysilsesquioxane, but it was observed that excellent sheet resistance could be maintained by the resistance reinforcing effect of the secondary protective layer. . In addition, as the content increased in proportion to the hardness of the polysilsesquioxane content, the hardness also increased.

When forming a transparent conductive film with a composition to which polysilsquioxane is not added as in Comparative Example 1, resistance reinforcing effect can be secured, but it is inferior to optical reinforcement, and stains and haze are severe, and hardness and adhesion to the substrate cannot be secured. Disconnection occurred in the process.

The conductive coating composition according to the present invention is excellent in optical properties and excellent dispersibility of metal nanowires can solve the problems such as whitening, phase separation, gelation of the coating composition, the conductive film according to the present invention has excellent sheet resistance, wear resistance It is suitable for use in electronic devices because of its hardness, adhesion to substrates and flexibility.

Claims (14)

In conductive coating compositions, 1) metal nanowires; 2) ladder type silsesquioxane polymers; 3) organic binder resins; And 4) dispersion Conductive coating composition comprising a. The method of claim 1, 1) 0.01-0.5 wt% metal nanowires; 2) 0.01-1% by weight of the ladder silsesquioxane polymer; 3) 0.02-10 weight percent of organic binder resin; And 4) remaining amount of dispersion Conductive coating composition comprising a. The method of claim 1, The ladder-type silsesquioxane polymer has a conductive coating composition, characterized in that it has a structure of formula (1). [Formula 1]

In Chemical Formula 1, R ¹ to R ⁴ are each independently a cyclic or acyclic aliphatic organic functional group, an alkyl group, an alkylhalogen, an aryl group, an amino group, a (meth) acryl group, a vinyl group, an epoxy group or a siol group connected by hydrogen, C ₁ to C ₂₀ Wherein, R ¹ to R ⁴ are all the same or all are substituted with different organic functional groups; R ⁵ to R ⁸ are each independently selected from the group consisting of an alkyl group of C _1-5 , a cycloalkyl group of C _3-10 , an aryl group of C _6-12 , an alcohol, an alkoxy group and combinations thereof; n is 1 to 100,000. The method of claim 3, Conductive coating composition, characterized in that the content of the aromatic organic functional group in the total of 100% of the R ¹ to R ⁴ in the formula (1). The method of claim 3, The conductive coating composition, characterized in that the content of -OH of the terminal in the formula (1) is 0.01 to 50% of the terminal group. The method of claim 1, The organic binder resin is triacetyl cellulose, diacetyl cellulose, acetyl Conductive coating composition, characterized in that at least one selected from the group consisting of hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate. The method of claim 1, The conductive coating composition, characterized in that the organic binder resin is triacetyl cellulose. The method of claim 1, Conductive coating composition, characterized in that the resin composition further comprises a curing agent, plasticizer, functional additives or sunscreen. A method of forming a conductive film, comprising coating the conductive coating composition according to claim 1 on a substrate and drying it. The method of claim 9, 0.1 to 1.0% by weight of a ladder-type silsesquioxane polymer on the dried conductive film; Organic binder resin 0.05-4 wt%; And a second coating and drying of the composition for forming a protective layer comprising the remaining amount of the dispersion. A conductive film prepared according to the method of claim 9 or 10. The method of claim 11, The conductive film has a transmittance of at least 90% and a sheet resistance of 200 Ω / □ or less. An electronic device comprising the conductive film of claim 11. The method of claim 13, The conductive film is a conductive film, characterized in that acts as an electrode.