KR20160038444A

KR20160038444A - Coating Composition Containing Acrylic Monomer and AgNW and Conducting Film Coated with the Same

Info

Publication number: KR20160038444A
Application number: KR1020140131543A
Authority: KR
Inventors: 문광길; 박종화; 이용상; 이상훈; 서혁수; 이효정
Original assignee: 주식회사 나노픽시스
Priority date: 2014-09-30
Filing date: 2014-09-30
Publication date: 2016-04-07

Abstract

The present invention relates to a coating composition comprising an acrylic monomer and silver nanowires and a conductive film coated thereby. The coating composition for the protective coating may comprise from 0.05 to 5.0 wt% of an acrylic monomer or oligomer relative to the total composition weight; And 0.005 to 0.05 wt% of silver nanowires.

Description

[0001] The present invention relates to a coating composition comprising an acrylic monomer and a silver nanowire, and a conductive film coated thereon (Coating Composition Containing Acrylic Monomer and AgNW and Conducting Film Coated with the Same)

The present invention relates to a coating composition comprising an acrylic monomer and silver nanowires and a conductive film coated thereby.

Transparent electrodes are electronic components that have a high transparency of 80% or more and a surface resistance of 500 Ω / sqm or less and are widely used in various electronic fields including displays or touch screens. Indium Tin Oxide (ITO) film prepared by adding tin oxide to a transparent electrode of known indium oxide is used to improve conductivity. However, alternative materials have been developed due to flexibility or scarcity of resources themselves. Alternative materials for ITO films used as transparent electrodes include graphene, carbon nanotubes or silver nanowires. Among these materials, the nanowire can be made into a wire having a long length by utilizing the difference in reactivity of the crystal surface, and has a merit that a printing process can be applied instead of a deposition process while a resistance value is relatively small.

Patent Publication No. 10-2013-0026921 discloses a transparent conductive film comprising a transparent film and a conductive thin film formed on one side of a transparent film, and the conductive thin film comprises a silver nanowire thin film and a PEDOP conductive polymer thin film.

Patent Publication No. 10-2013-0048333 discloses a transparent substrate; A silver nanowire network layer formed on the transparent substrate; Wherein the silver nanowire network layer comprises a network of silver nanowires having an aspect ratio of 200 to 1,000,000 and wherein the silver nanowires are at least one point different from the other silver nanowires, Wherein the silver nanowires are exposed on the surface of the silver nanoparticles having a diameter of 1 to 10 nm and the silver nanowires are connected to each other by the visible A pulse light of 3 to 70 J / cm < 2 > in the light ray region is welded by local melting of silver nanowires by light sintering for 0.001 to 1 second.

The prior art does not disclose coating compositions that are resistant to external environments, while at the same time transparency and electrical conductivity can be maintained.

The present invention has been made to solve the problems of the prior art and has the following purpose.

Prior Art 1: Patent Publication No. 10-2013-0026921 (published by El Niñec Co., Ltd., Mar. 14, 2013) Transparent conductive film, method of manufacturing the same, and touch panel Prior Art 2: Patent Publication No. 10-2013-0048333 (published by KAIST, May 10, 2013) Transparent electrode including a polymer protective film and a silver nanowire network and a manufacturing method thereof

It is an object of the present invention to provide a coating composition for a protective coating capable of protecting silver nanowires and a conductive film coated therewith.

According to a preferred embodiment of the present invention, the coating composition for the protective coating comprises from 0.05 to 5.0 wt% of an acrylic monomer or oligomer relative to the total composition weight; And 0.005 to 0.05 wt% of silver nanowires.

According to another preferred embodiment of the present invention, the coating composition according to the present invention further comprises at least one selected from the group consisting of ethyl acetate, ethylene glycol monoethylene ether and mixtures thereof.

According to another preferred embodiment of the present invention, a conductive film comprising silver nanowires comprises a substrate; A silver nanowire layer formed on the substrate; and a protective layer overcoated on the silver nanowire layer, wherein the protective layer comprises 0.05 to 5.0 wt% of an acrylic monomer or oligomer, based on the total weight of the protective layer composition; And 0.005 to 0.05 wt% of silver nanowires.

The composition according to the present invention protects the silver nanowire surface while at the same time imparting resistance to the alkali in the etching process and allowing selective removal by acid. This makes it possible to form a pattern with an acidic series etching solution after ultraviolet curing. Also, the film coated by the composition according to the present invention allows the silver nanowire surface to be protected while maintaining the required electrical conductivity in the transparent electrode.

Figure 1 shows an optical image of the surface change after UV curing of the composition according to the invention, wherein (a) shows a silver nanowire monolayer image and (b) is coated on a composition comprising an acrylic monomer The image of the layer that was cured by ultraviolet ray is shown.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the embodiments shown in the accompanying drawings, but the present invention is not limited thereto. In the following description, components having the same reference numerals in different drawings have similar functions, so that they will not be described repeatedly unless necessary for an understanding of the invention, and the known components will be briefly described or omitted. However, It should not be understood as being excluded from the embodiment of Fig.

The coating composition for coating the silver nanowire layer according to the present invention comprises 0.05 to 5.0 wt% of an acrylic monomer or oligomer, And 0.005 to 0.05 wt% of silver nanowires. The composition further comprises at least one selected from the group consisting of ethyl acetate, ethylene glycol monoethylene ether, and mixtures thereof. Further, the conductive film according to the present invention comprises a substrate; A silver nanowire layer formed on the substrate; and a protective layer overcoated on the silver nanowire layer, wherein the protective layer comprises 0.05 to 5.0 wt% of an acrylic monomer or oligomer, based on the total weight of the protective layer composition; And 0.005 to 0.05 wt% of silver nanowires.

This is explained in detail below.

Silver nanowires can be made into a wire using the isotropic growth induction due to the difference in reactivity of the nanoparticle surface, which determines the electrical conductivity of the transparent electrode and is composed of various crystal planes. Silver has the highest electrical conductivity among metals, and silver nanowires can have resistance values of, for example, 80 to 120 Ω. Silver nanowire compositions can be made by dispersing a polyester resin, such as, for example, silver nanowires and acrylic polyester resins, in a solvent such as distilled water. In addition, alcohol may be added to reduce the surface energy for the substrate. Alcohols reduce the surface tension between the substrate and the coating layer. The substrate can be, but is not limited to, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) or polyimide (PI). The silver nano-coated layer coated on such a substrate may have, for example, a light transmittance of 91.0 to 93% and a sheet resistance of 150 to 30 Ω / sqm. The composition according to the present invention may be overcoated on the silver nanoparticle layer. The coating composition for the protective coating according to the present invention may be overcoated with various substrates or silver nano-coated layers and is not limited by the substrate or silver nano-coated layer.

The coating composition according to the invention may for example comprise from 0.005 to 0.05 wt.% Silver nanowires per weight of the total composition; 0.05 to 5.0 wt% of an acrylic monomer or oligomer; And one selected from the group consisting of ethyl acetate, ethylene glycol monoethyl ether, and mixtures thereof to make the whole 100 wt%. And may further comprise one or more additives selected from the group consisting of cellulose acetate butyrate, photo-initiator and fluoro surfactant. The amount of the additive may be, for example, 0.05 to 5.0 wt%, 0.005 to 1.0 wt%, and 0.001 to 0.01 wt%, respectively, based on the total weight of the composition, but is not limited thereto.

The acrylic monomer or oligomer is, for example, selected from the group consisting of pentaerythritol tetraacrylate (PETTA), trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), ditrimethylolpropane tetraacrylate (DiTMPTTA) But are not limited to, dipentaerythritol pentaacrylate (DiPEPA) or dipentaerythritol hexaacrylate (DPHA).

Ethyl acetate, ethylene glycol monoethyl ether and mixtures thereof may consist solely of, for example, ethyl acetate or ethylene glycol monoethyl ether or may be composed of a mixture of ethyl acetate: ethylene glycol monoethyl ether = 10: 5 to 15 in a weight ratio .

Photo-initiators may be, for example, 2,2-dimethoxy 2-phenyl-acetophenone, but are not limited to, various types of light for ultraviolet curing An initiator may be added to the composition according to the invention.

The acrylic monomer or oligomer has a function of crosslinking when irradiated with ultraviolet rays to protect the surface of the silver nanowire layer and to impart resistance to alkali in the etching process. Also, it can be selectively removed by an acid so that a pattern can be formed.

The acrylic monomer or oligomer may be from 0.05 to 5.0 wt%, preferably from 0.8 to 1.5 wt%, of the total coating composition.

The composition according to the present invention overcoats the silver nanowire layer to protect the silver nanowire against the external environment. The protective coating layer is top coated onto the silver nanowire layer and silver nanowires are present in the top coating layer. In order for the top coating layer to have a film structure having a certain level of electrical conductivity, a silver nanowire is added to a solution of a UV monomer to form a composition. Generally, when a sufficient amount of ink has to be applied so that the protective coating layer has sufficient hardness and the amount of application is increased, the surface resistance value is increased, and thereby the nanowire layer can be electrically insulated. The silver nanowires added to the composition according to the present invention have a bridge function between silver nanowires, thereby preventing electrical insulation.

The composition according to the present invention overcoats the silver nanowire layer so that electrical insulation is prevented, and the haze is reduced while maintaining the surface gloss.

The coating compositions according to the invention are described below.

Example

An ink composition composed of an acrylic polyester resin binder, distilled water, alcohol and silver nanowire is coated in a film thickness of 2 to 20 μm on a polyethylene terephthalate (PET) substrate using a slot die coating method or a microgravure coating method Thereby forming a silver nanowire layer. The composition according to the present invention was overcoated on the silver nanowire layer by the same or similar method. The coating thickness was similar to the thickness of the silver nanowire layer and was cured by ultraviolet radiation. The UV monomer solution was prepared by adding 0.005 to 0.05 w% of silver nanowires to acrylic monomer and used as a solvent in a weight ratio of 50:50 of a mixture of acetylacetate and ethylene glycol monoethyl ether. Staromer products were used as acrylic monomers. Solut 2100, Irgacure 184, ICT FS-8100, FS-8000 and NI-M100 of EASTMAN were used as additives. FS-8100, FS-8000 and NI-M100 correspond to fluorine surfactants and Irgacure corresponds to photoinitiators.

Example 1 Example 2 Example 3 Example 4 Remarks Acryl Monomer (PETTA) One 1.5 2 5 Each component is in weight%, and the sheet resistance unit is Ω / sqm Photoinitiator 0.1 0.15 0.2 0.5 menstruum Banlance Balance Balance Balance Surfactants 0.1 0.1 0.1 0.1 Sheet resistance 80 80 170 850

Cellulose acetate butyrate was added to improve surface properties such as hardness and gloss retention, and the test results were as follows.

Example 5 Example 6 Example 7 Example 8 UV monomer 1.5 1.5 1.5 1.5 Photoinitiator 0.15 0.15 0.15 0.15 EA 48 48 48 48 EGEE Balance value Balance value Balance value Balance value Surfactants 0.1 0.1 0.1 0.1 CAB - 0.05 0.1 0.15 result Permeability 91.80 91.75 91.75 91.75 Hayes 0.95 0.85 0.85 0.85 Sheet resistance 80 80 80 80 Remarks EGEE represents ethylene glycol mono-ethyl ether, CAB represents cellulose acetate butyrate, and the balance value represents the amount that makes the entirety 100 wt%. The components are expressed in weight%, the sheet resistance unit is Ω / sqm, the haze is%, EA is ethyl acetate, .

The change of properties according to the fluorine surfactant was measured.

Example 9 Example 10 Example 11 Example 12 UV monomer 1.5 1.5 1.5 1.5 Photoinitiator 0.15 0.15 0.15 0.15 EA 50 50 50 50 EGEE Balance value Balance value Balance value Balance value Surfactants 0.01 0.025 0.05 0.1 CAB 1.5 1.5 1.5 1.5 result Permeability 91.80 91.77 91.74 91.72 Hayes 0.95 0.95 0.98 1.0 Sheet resistance 80 80 80 80 Remarks EGEE represents ethylene glycol mono-ethyl ether, CAB represents cellulose acetate butyrate, and the balance represents the amount that makes the whole 100 wt%. it means.

From the above test results, it can be seen that the haze is reduced by the addition of cellulose acetate butyrate (using Solus 2100). However, when used in amounts greater than the amount of UV monomer, side effects of the blue system were found to occur.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention . The invention is not limited by these variations and modifications, but is limited only by the claims appended hereto.

Figure 1 (a): Silver nanowire single layer < RTI ID = 0.0 >
1 (B): After coating, the ultraviolet cured conductive film layer

Claims

0.05 to 5.0 wt% of an acrylic monomer or oligomer based on the total composition weight; And 0.005 to 0.05 wt.% Of silver nanowires.

The coating composition of claim 1, further comprising at least one selected from the group consisting of ethyl acetate, ethylene glycol monoethylene ether, and mixtures thereof.

materials;
A silver nanowire layer formed on the substrate; and
Wherein the silver comprises a protective layer overcoated on the nanowire layer,
The protective layer may comprise 0.05 to 5.0 wt% of an acrylic monomer or oligomer based on the total weight of the protective layer composition; And silver nanowires comprising between 0.005 and 0.05 wt% silver nanowires.