KR20150136924A - Composition for conductive layer and conductive layer prepared by using the same and transparent conductors comprising the conductive layer - Google Patents
Composition for conductive layer and conductive layer prepared by using the same and transparent conductors comprising the conductive layer Download PDFInfo
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- KR20150136924A KR20150136924A KR1020140064653A KR20140064653A KR20150136924A KR 20150136924 A KR20150136924 A KR 20150136924A KR 1020140064653 A KR1020140064653 A KR 1020140064653A KR 20140064653 A KR20140064653 A KR 20140064653A KR 20150136924 A KR20150136924 A KR 20150136924A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- Spectroscopy & Molecular Physics (AREA)
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- Dispersion Chemistry (AREA)
- Non-Insulated Conductors (AREA)
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Abstract
Description
More particularly, the present invention relates to a composition for forming a conductive layer having excellent transparency, conductivity, durability, and developability, a conductive layer prepared using the same, and a transparent conductor having the conductive layer. .
Generally, a transparent conductive thin film means a thin conductive film coated on an insulating surface or a substrate having a high light transmittance, and the conductive thin film is required to have high light transmittance and high surface conductivity. When the conductivity is poor, it is difficult to drive smoothly, and when the transmittance is lowered, the display performance is lowered. However, if the thickness of the conductive thin film is increased in order to improve the conductivity of the conductive thin film, the transmittance decreases and the light transmittance decreases because of increasing the surface reflectance and absorption rate of the conductive thin film. Therefore, it is recognized that it is very difficult to improve both the conductivity and the transmittance have.
At present, vacuum deposited metal oxide such as indium tin oxide (ITO) is widely used as a transparent conductive thin film. However, since the metal oxide film has a weak mechanical strength and is not flexible, There is a limit to the application to a flexible display. In addition, since a high deposition temperature or an annealing process at a high temperature is required in order to achieve high conductivity levels, deformation of organic functional films employed in a substrate or a device may be caused. In addition, A disadvantage has been pointed out that special equipment is required.
To improve this, a transparent electroconductive film coated with a composition containing an electroconductive oxide and an electroconductive polymer is proposed (JP-A-2008-095015). However, it has a disadvantage that it is difficult to obtain sufficient electric conductivity, and in particular, it is difficult to satisfy both electric conductivity and light transmittance.
In addition, a method of preventing light scattering by using a metal nanowire and a secondary conductive medium (CNT (carbon nanotube), conductive polymer, ITO, etc.) in combination is proposed (JP-A No. 2010-525526). However, since the secondary conductive medium (coloring material) such as CNT, conductive polymer, or ITO is used in combination, the transparency may be deteriorated.
It is an object of the present invention to provide a composition for forming a conductive layer that is excellent in transparency, conductivity, durability, and can significantly improve developability.
1. A composition for forming a conductive layer, comprising a metal nanowire and a protein resin, wherein the protein resin is casein, collagen or a mixture thereof.
2. The composition for forming a conductive layer according to 1 above, wherein the metal nanowire is silver nanowire.
3. The composition for forming a conductive layer according to 1 above, wherein the protein resin is contained in an amount of 30 to 95% by weight based on 100% by weight of the composition for forming a conductive layer based on solid content after drying.
4. The composition for forming a conductive layer according to 1 above, wherein the composition for forming a conductive layer further comprises a crosslinking agent.
5. The composition for forming a conductive layer according to 4 above, wherein the crosslinking agent is at least one selected from the group consisting of alkoxy metal, melamine, boric acid, water-soluble aldehyde, water-soluble ketone and water-soluble alkyl halide.
6. A conductive layer formed of the composition for forming a conductive layer according to any one of items 1 to 5 above.
7. The conductive layer of claim 6, wherein the conductive layer further comprises an electrically conductive polymeric layer thereon.
8. A transparent conductor comprising a support and an upper conductive layer on at least one side of the support.
The composition for forming a conductive layer, which comprises a metal nanowire and a protein resin according to the present invention, wherein the protein resin is casein, collagen or a mixture thereof, may be a cellulose resin, a polyvinylpyrrolidone and a polyvinyl alcohol resin The metal nanowires of the composition for forming a conductive layer are uniformly distributed by effectively coordinating the metal nanowires with the non-covalent electron pairs of the amide group and the hydroxyl group, as compared with the case where the metal nanowires are used.
Furthermore, when a conductive layer is formed by coordinating with a non-covalent electron pair of a nitrogen or an oxygen of a protein resin, which is casein, collagen or a mixture thereof, and the metal nanowire is formed, corrosion of the metal due to acid, oxygen, moisture and the like is suppressed, Can be suppressed.
In addition, the composition for forming a conductive layer according to the present invention can improve transparency by including a nano-sized metal wire, and can easily develop hydrolysis of amide by a basic aqueous solution by including a protein resin, have.
The present invention relates to a metal nanowire and a protein resin, wherein the protein resin is selected from the group consisting of casein, collagen or a mixture thereof, which exhibits excellent transparency, conductivity and durability, And a transparent conductor comprising the conductive layer and the conductive layer.
Hereinafter, the present invention will be described in detail.
< Conductive layer Composition for forming >
The composition for forming a conductive layer of the present invention comprises metal nanowires and a protein resin, wherein the protein resin is casein, collagen or a mixture thereof.
The metal used for the metal nanowire according to the present invention is not particularly limited and examples thereof include gold, platinum, silver, palladium, rhodium, lithium, ruthenium, osmium, iron, cobalt, copper and tin. They may be used alone or in combination of two or more. It is preferable to use a metal other than silver and silver in consideration of conductivity and stability, and it is more preferable to use silver alone.
In order to form a long electrically conductive path, the metal nanowire may have an average length of 3 to 500 mu m, preferably 3 to 300 mu m. The average diameter is preferably small considering transparency, and is preferably large considering the electrical conductivity. For example, the average diameter may be 10 to 300 nm, preferably 30 to 200 nm.
The metal nanowires can be manufactured by a method commonly used in the art such as a liquid phase method and a vapor phase method. For example, silver nanowires can be used as Adv. Mater., 2002, 14, 833-837; Chem.Mater., 2002, 14, 4736-4745; The gold nanowires are disclosed in Japanese Patent Laid-Open Nos. 2006-233252; Copper nanowires are disclosed in Japanese Patent Application Laid-Open No. 2002-266007; Cobalt nanowires can be produced by using, for example, Japanese Patent Application Laid-Open No. 2004-149871.
The content of the metal nanowires according to the present invention is not particularly limited and may be, for example, 5 to 70% by weight based on 100% by weight of the conductive layer forming composition based on solid content after drying. When the content of the metal nanowires is less than 5% by weight, the effect of improving the conductivity is insufficient. When the content is more than 70% by weight, transparency may be deteriorated.
The protein resin, which is casein, collagen, or a mixture thereof, according to the present invention contains an amide group and a hydroxy group, and thus can have transparency, conductivity, durability and developability superior to conventional ones.
Specifically, the protein resin according to the present invention has the above-mentioned specific functional groups, thereby effectively aligning the metal nanowires with the non-covalent electron pairs in comparison with the conventional cellulose resin, polyvinyl pyrrolidone and polyvinyl alcohol resin, It is possible to uniformly distribute the metal nanowires of the composition and to maintain excellent transparency and conductivity.
Further, when a conductive layer is formed by coordination bonding of a metal nano wire and a non-covalent electron pair of a nitrogen or oxygen of a protein resin which is a casein, collagen or a mixture thereof, corrosion of the metal due to acid, oxygen, moisture, etc. is suppressed to enhance durability It can contribute to suppressing the deterioration of conductivity.
In addition, the protein resin of the present invention can exhibit excellent developability due to easy hydrolysis reaction of amide by a basic aqueous solution.
The protein resin according to the present invention can be any of casein and collagen. More specifically, for example, casein may be a protein resin obtained from milk, and collagen may be a protein resin obtained from animal tissue.
The content of the protein resin according to the present invention is not particularly limited and may be, for example, 30 to 95% by weight based on 100% by weight of the conductive layer forming composition based on solid content after drying. If the content of the protein resin is less than 30% by weight, the transparency improving effect and the durability improving effect are insufficient. If the content is more than 95% by weight, the conductivity may be lowered.
The composition for forming a conductive layer according to the present invention may further comprise a solvent for dissolving / dispersing the above-mentioned components.
Such a solvent is not limited to a specific substance, and examples thereof include water and isopropanol, methanol, ethanol, diethylene glycol monobutyl ether, acetonitrile, tetrahydrofuran, N-methylmorpholine, dimethylsulfoxide , Dimethylformaldehyde, and the like. These solvents may be used alone or in admixture of two or more, preferably water, and the other water-soluble solvent may be further used if necessary.
The content of the solvent is not particularly limited within a range where the solvent can function, but it may be contained in an amount of 70 to 98% by weight, preferably 80 to 98% by weight based on the total weight of the composition. When the content of the solvent is in the range of 80 to 98% by weight based on the total weight of the composition, the solid content and viscosity can be maintained at an appropriate level, thereby increasing the coating property.
If necessary, the composition for forming a conductive layer according to the present invention may further comprise a crosslinking agent.
The cross-linking agent is a component for improving the cohesive strength. The type of the cross-linking agent is not particularly limited, and examples thereof include melamine derivatives, alkoxy metal compounds, boric acid based compounds, water soluble aldehyde based compounds, water soluble ketone based compounds, water soluble alkyl halide based compounds, They may be used alone or in combination of two or more.
Examples of the melamine derivatives include hexamethylol melamine, hexamethoxymethyl melamine, hexabutoxymethyl melamine and the like. Examples of the alkoxy metal-based ones include aluminum triisopropoxide, and the water-soluble Examples of the aldehyde-based ones include glyoxal. Among them, a water-soluble aldehyde-based crosslinking agent is preferable considering the stability of the aqueous solution, the dispersibility of the metal nanowires, and the lowering of the conductivity with time.
The content of the cross-linking agent is not particularly limited within a range capable of performing the function, but may be 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin.
The composition for forming a conductive layer of the present invention may contain additives such as plasticizers, antioxidants, corrosion inhibitors, defoamers, fillers, surfactants, colorants (fuels and pigments), and the like which are commonly used in the art within the scope of the present invention. And the like.
< Conductive layer And transparent Conductor >
The present invention also provides a transparent conductor comprising a conductive layer formed on at least one surface of a transparent support with the composition for forming a conductive layer.
The transparent support is not particularly limited, and may be made of a rigid or flexible material conventionally used for a transparent support. For example, glass, polyethersulphone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET) polyethyelene terepthalate, polyphenylene sulfide (PPS), polyallylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate acetate propionate, CAP) can be used.
The transparent support preferably has excellent surface smoothness. For example, the surface smoothness may have an arithmetic average roughness Ra of 5 nm or less and a maximum height average roughness Rz of 50 nm or less. Preferably, Ra may be 2 nm or less and Rz may be 30 nm or less, and more preferably Ra may be 1 nm or less and Rz may be 20 nm or less.
The surface smoothness can be improved by laminating a primer layer such as a thermosetting resin, an ultraviolet ray hardening resin, an electron beam hardening resin, a radiation setting resin, etc. on the surface of the transparent support, or by machining such as polishing, , A corona, a surface treatment with plasma, or the like. In general, the surface smoothness can be measured by an atomic force microscope (AFM) according to the surface preparation standard (JIS B 0601-2001).
The transparent support according to the present invention may have an appropriate thickness, for example, from 50 to 500 mu m, and preferably from 100 to 200 mu m.
The conductive layer can be formed by a liquid phase film forming method in which the composition for forming a conductive layer is coated on at least one surface of a transparent support and dried. The coating method is not particularly limited and a method well known in the art can be used. For example, spin coating, spray coating, roll-to-roll, bar coating, dip coating, casting, die coating, blade coating, gravure coating, Can be used. Further, a direct pattern forming method using an inkjet printing method gravure printing method, a screen printing method, or the like can be used.
If necessary, an electrically conductive polymer layer may be additionally formed on the conductive layer in the present invention. The electrically conductive polymer is not particularly limited and includes, for example, polypyrrole; Polyaniline; Polyacetylene type such as trans polyacetylene and cis-polyacetylene; Polythiophene, polyisothionaphthalene, polythienylene vinylene, poly 3-alkylthiophene, poly 3,4-ethylenedioxythiophene (poly 3, 4-ethylenedioxythiophene); Polyphenylene type materials such as poly p-phenylene, polyphenylene sulfide and polyphenylene vinylene; For example, polytoludine, polyazine, polyacene, polyfuran, polyazulene, and the like. Among them, polyethylenedioxythiophene or polyaniline-based ones are preferable in consideration of electrical conductivity and transparency.
The transparent conductor of the present invention can be used as an electrode of an electronic product. Examples of electronic appliances to which the electrode according to the present invention can be applied include touch panels, flat panel displays, electronic papers, flexible displays, antistatic panels for flexible displays, solar panels, and the like, but are not limited thereto.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
Example
(One) Conductive layer Preparation of composition for forming
A composition for forming a conductive layer having the composition and content shown in Table 1 below was prepared.
(Parts by weight)
(A)
(B)
(C)
(D)
B-1: α-casein from bovine milk (Aldrich)
B-2: β-casein from bovine milk (Aldrich)
B-3: Collagen from calf skin (Aldrich)
B-4: Polyacrylic resin
B-5: Polyvinyl alcohol resin
B-6: Polyvinylpyrrolidone resin
C-1: Hexamethylol melamine
C-2: Aluminum triisopropoxide
C-3: Glyoxal
D: Water
(2) Transparent Conductor Produce
After the composition for forming a conductive layer was prepared, a composition for forming a conductive layer was spin-coated on a polyethylene terephthalate film having a thickness of 100 占 퐉, followed by heating at 120 占 폚 for 30 minutes to obtain a silver nanowire of 0.005g / So as to prepare a transparent conductor.
Experimental Example
A composition for forming a conductive layer in Examples and Comparative Examples was laminated by spin coating a composition for forming a conductive layer on a polyethylene terephthalate film having a thickness of 100 占 퐉 and then heated at 120 占 폚 for 30 minutes so that the metal nanowire was 0.005 g / So as to prepare a transparent conductor.
(1) Evaluation of transparency
The transparency of the prepared transparent conductor was measured by a transmittance at a wavelength of 500 nm using a UV-3100PC machine manufactured by Shimadzu Corporation.
<Evaluation Criteria>
?: Transmittance of 90% or more.
Χ: Less than 90% transmittance.
(2) Conductivity evaluation
The surface resistance of the conductive layer was measured by a four-terminal method using Loresta GP TCP-T250 (manufactured by Mitsubishi Chemical Corporation), and the conductivity was calculated from the obtained surface resistance value and film thickness by the following formula .
[Equation 1]
Conductivity (S / cm) = 1 / {film thickness (cm) x surface resistance (? /?)}
<Evaluation Criteria>
○: Conductivity 100 (S / cm) or more.
?: Conductivity 50 (S / cm) or more and less than 100 (S / cm).
X: Conductivity less than 50 (S / cm).
(3) Durability evaluation
The conductive layer on which the surface resistance was measured in the above conductivity evaluation was continuously heated in a constant temperature drier at 125 캜 for 240 hours. After heating, the mixture was allowed to cool to room temperature, and the surface resistance value after heating was measured by the above-mentioned method to calculate the conductivity. The durability was calculated from the retention of conductivity before and after the heat resistance test.
<Evaluation Criteria>
○: Conductivity retention rate is 90% or more.
?: Conductivity retention ratio of 70% or more and less than 90%.
Χ: Conductivity retention less than 70%.
(4) Developability evaluation
The prepared transparent conductor was immersed in a 1 M KOH aqueous solution, left for 1 hour, taken out, washed with pure water, and the remaining amount of the conductive layer remaining on the polyethylene terephthalate film was confirmed by a microscope to evaluate developability.
As can be seen from Table 2, the metal nanowire and the protein resin of the present invention are excellent in transparency, conductivity and durability in the case of a composition for forming a conductive layer, which is casein, collagen or a mixture thereof. However, it was confirmed that the developability was remarkably improved.
However, the transparency and durability of Example 8 containing the protein resin of the present invention in a small amount were somewhat lowered, and in Example 9 containing the protein resin of the present invention in an excess amount, the conductivity was somewhat lowered.
However, in the comparative examples, it was confirmed that the overall durability and developability were remarkably lowered.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140064653A KR20150136924A (en) | 2014-05-28 | 2014-05-28 | Composition for conductive layer and conductive layer prepared by using the same and transparent conductors comprising the conductive layer |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020140064653A KR20150136924A (en) | 2014-05-28 | 2014-05-28 | Composition for conductive layer and conductive layer prepared by using the same and transparent conductors comprising the conductive layer |
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| Publication Number | Publication Date |
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| KR20150136924A true KR20150136924A (en) | 2015-12-08 |
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| KR1020140064653A KR20150136924A (en) | 2014-05-28 | 2014-05-28 | Composition for conductive layer and conductive layer prepared by using the same and transparent conductors comprising the conductive layer |
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| KR (1) | KR20150136924A (en) |
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- 2014-05-28 KR KR1020140064653A patent/KR20150136924A/en not_active Application Discontinuation
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