KR20140059340A - Composition of metal ink - Google Patents
Composition of metal ink Download PDFInfo
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- KR20140059340A KR20140059340A KR1020120125317A KR20120125317A KR20140059340A KR 20140059340 A KR20140059340 A KR 20140059340A KR 1020120125317 A KR1020120125317 A KR 1020120125317A KR 20120125317 A KR20120125317 A KR 20120125317A KR 20140059340 A KR20140059340 A KR 20140059340A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
Abstract
The present invention relates to metal ink compositions characterized in that they comprise two or more particles which differ in the size of the particles constituting the metal ink. The mouth ratio of the particles is 1: 5 to 1:50, and the large particles have a core-shell structure. According to the present invention, there is an advantage that a high filling rate and a metal ink characteristic can be maintained by an economical method in a metal ink requiring expensive materials.
Description
The present invention relates to a metal ink composition comprising two or more different sized particles.
The importance of Transparent Conductive Electrodes (TCEs) is becoming increasingly important for applications such as touch panels, flat panel displays, and other optoelectronic devices. ITO is the most widely used transparent electrode in the field of organic solar cell, but because it is a sintered material, its process temperature is high and it is easily broken by external physical stimulation and is vulnerable to bending deformation. Also, when the substrate is coated on the polymer substrate, the film is broken when the substrate is bent. And, moreover, the price is increasing due to the scarcity of In, and there is a problem in supply.
Recently, conductive polymer, carbon nanotube, graphene, and metal nanowire and nanoparticles have been attracting attention as a flexible transparent electrode and a substitute for ITO as a solution to solve the problems of ITO.
However, carbon nanotubes or graphenes have low conductivity and difficult to improve the permeability. In addition, since the metal nanowires typified by Ag nanowires are expensive, the cost of manufacturing transparent electrodes is high due to only the Ag nanowire, and the roughness of the surface during the production of transparent electrodes is very difficult to perform lamination printing of the following materials for implementing devices such as TFTs . In addition, it has a limited process such as difficulty in ink jet printing and high temperature process, and the conductivity is decreased with stretching.
On the other hand, metal nanoparticles are produced in the form of conductive ink and used in the manufacture of electrodes by processes such as inkjet. Such metal nanoparticles may include particles of gold, silver, platinum, copper, nickel, iron, cobalt, zinc, chromium, manganese and the like.
Metal inks containing metal nanoparticles may consist of particles of the same or similar diameter, but on the other hand, they may have different sizes to increase the metal filling rate (hereinafter referred to as? It is advantageous and common to make a mixture of two or more particles. Also, the components of the metallic ink comprising two or more particles differing in diameter may be the same or may be of different components. In each case, the size and the composition of the particles constituting the metal ink are adjusted and manufactured and used in order to obtain the best output depending on the purpose and use of the ink.
In particular, a method of mixing two or more different sized particles made from one component to increase the filling rate of the metal ink is used when the characteristic of the specific metal ink by the one component is required. For example, silver (Ag) is preferred as a component of a metallic ink because it is advantageous in terms of electrical conductivity and oxidation resistance, and silver (Ag) is problematic because of its high price in terms of cost. Therefore, in the production of metal ink requiring the use of a specific component, it was attempted to develop a method of manufacturing a metal ink in a more economical manner, in particular, when it is an expensive material, while maintaining the characteristics of the metal ink.
Disclosure of Invention Technical Problem [8] The present invention provides a composition which increases the filling rate of metallic ink and effectively exhibits physical properties such as oxidation resistance and electrical conductivity. The present invention makes it possible to provide metal inks in an economical way, particularly when it is desired to use expensive materials as the material of metal inks.
The present invention provides a metal ink composition comprising particles of a core-shell structure and at least one particle differing in diameter from the particles.
Preferably, the particles of the core-shell structure comprise a shell layer formed from a precursor represented by the following formula on the surface of the metal particles of the core:
[Formula 1]
Wherein X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
Preferably, the core metal particles are copper, nickel, iron, cobalt, zinc, chromium or manganese particles.
Preferably, the core metal particles are made from a metal precursor having a structure represented by the following formula:
[Formula 2]
M is Cu, Ni, Fe, Co, Zn, Cr, or Mn, m is 1 to 5,
R is
(Wherein X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.)
Preferably, the core metal particles are made from metal hexanoate.
Preferably, the shell layer of the particles of the core-shell structure is formed from the same material as the particles differing in diameter from the particles.
Preferably, the diameter ratio of the particles differing in diameter from the particles of the core-shell structure is from 1: 5 to 1:50.
Preferably, the particles of the core-shell structure have a diameter of 100 to 150 nm.
Preferably, the ratio of the particles differing in diameter to the particles of the core-shell structure is from 10: 1 to 2000: 1 by weight.
The metal ink composition according to the present invention can increase the filling rate of the metal ink by keeping the size of the component particles different, and can maintain excellent oxidation resistance and electrical conductivity properties. In addition, even when an expensive material is required as the material of the metal ink, there is an advantage that it can be provided by an economical method.
Further, the present invention is advantageous in that the particles of relatively large size in the metal ink composition can be prepared in a uniform shape, which enables the particle size to be controlled by an easy method.
FIG. 1A shows a manufacturing process of silver nanoparticles in the embodiment, and FIG. 1B is a SEM photograph of the particles produced therefrom.
FIG. 2A shows a process for producing particles of a Cu @ Ag core-shell structure in an embodiment, and FIG. 2B is an SEM photograph of particles produced therefrom.
Fig. 3 schematically shows the structure of an ink composition and a coating film formed therefrom in the examples.
4 is an SEM photograph of the coating film produced in the example.
5 is an SEM photograph of the coating film prepared in the comparative example.
The present invention relates to a metal ink composition having improved fill factor from a difference in particle diameter of particles constituting a metal ink composition, and a method for producing the same. The metal ink composition of the present invention comprises particles of the core-shell structure and one or more particles differing in diameter from the particles. The particles of the core-shell structure are relatively large particles of the ink composition components. In one embodiment, the core component in the core-shell structure is made from a metal that is oxidatively strong but relatively inexpensive, while the shell layer on the surface uses a metal that is highly conductive. Whereby the particles have improved oxidation stability at a low cost and excellent conductivity. In addition, the use of particles of the core-shell structure to provide relatively large particles as the ink composition component of the present invention is more effective than a method of manufacturing large-diameter particles using one material.
In one embodiment, the particles of the core-shell structure form a shell layer from the precursor represented by the following formula on the surface of the metal particles of the core:
[Formula 1]
Wherein X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
As the metal constituting the core particles, copper, nickel, iron, cobalt, zinc, chromium, and manganese having low oxidation stability may be used. In order to prepare the metal particles of the core therefrom, a metal precursor having a structure represented by the following formula can be used:
[Formula 2]
M is Cu, Ni, Fe, Co, Zn, Cr, or Mn, m is 1 to 5,
R is
(Wherein X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.)
It is a substance with the property of being highly soluble in a non-polar solvent. Therefore, it is easy to prepare a reaction liquid for producing core metal particles.
In one embodiment of the present invention, a reaction liquid is prepared by dissolving metal hexanoate in a solvent and a capping agent. The capping agent participates in the reduction reaction of the metal hexanoate and surrounds the formed nanoparticles to stabilize the particles. Therefore, in the process of preparing nanoparticles from metal hexanoate, the particle size can be easily controlled according to the kind of the capping agent used. In addition, uniform nanoparticles can be obtained. As a capping agent, an amine is used as an embodiment. The amine preferably contains an alkyl group having 4 to 18 carbon atoms. In the present invention, as a capping agent, butylamine, octylamine, dodecylamine, oleylamine and the like may be preferably used.
To produce metal particles of the core from metal hexanoate, the metal hexanoate of the organic phase is reduced to a reducing agent of the aqueous phase as shown in FIG. 2A, for example. The metal hexanoate is transported by the distribution equilibrium between the organic phase and the water phase and is reduced by the reducing agent present in the aqueous phase. According to the above process, aggregation phenomenon of particles formed from a rapid reaction can be prevented. It can also prevent the oxidation of metals that may occur during the reaction. As a metal particle of the core thus formed, a shell layer is formed by introducing and reducing the precursor represented by the formula 1 as shown in FIG. 2A as an embodiment.
The precursor has a high solubility for the nonpolar solvent and provides a distribution equilibrium between the nonpolar solvent and the polar solvent. This is a means to prevent aggregation, which has been a problem when compared to other precursor materials that have been used to form shell layers on metal particle surfaces. That is, with respect to the precursor, it is possible to control the rate of the redox reaction so as not to cause aggregation by controlling the distribution equilibrium between the non-polar and polar solvents. Accordingly, the precursor of the present invention, which is administered to the surface of the metal particles, is adsorbed only on the surface of the particles without being agglomerated to form a shell layer. Accordingly, the present invention can provide a core-shell structure in which a uniform shell layer is formed on the surface. The particles of the core-shell structure thus produced have a diameter of 100 to 150 nm.
Next, as the component of particles having different diameters included in the ink composition together with the particles of the core-shell structure, those produced from the same material as the shell layer of the core-shell structure may be used. In the core-shell structure, the shell layer improves the oxidation stability of the core and is often a noble metal component having excellent conductivity. However, it is economically disadvantageous to manufacture all the particles of the ink composition with only these noble metals. Therefore, it is possible to increase the filling ratio of the ink composition by simultaneously providing the large-sized particles by forming only the shell layer of the core-shell structure and by making only the remaining small particles of the ink composition from the noble metal component, That is, properties such as oxidation stability or excellent conductivity can be maintained.
In addition, as shown in FIG. 3, when a film is prepared from an ink composition, the shell layer is melted by thermoplasticity or the like to form a coating film, It is advantageous because fusion with small particles of the same component is performed. As a result of the fusion of the same components, a film having excellent film properties can be produced while preventing oxidation of the core component.
In the present invention, the particle size ratio between the particles differing in particle diameter from the particles of the core-shell structure is preferably 5: 1 to 50: 1. When the difference in particle size is smaller than the above range, the effect of improving the filling rate by mixing is not sufficiently exhibited. On the other hand, when the particle size difference is larger than the above range, particles having different sizes are not mixed well, And the effect due to mixing is not exhibited. More preferably, the intergranular particle size ratio is from 6: 1 to 10: 1.
One or more particles that differ in diameter from the particles of the core-shell structure means that the small particles can be provided as one or more species that differ in particle size. That is, when the particle size of the core-shell structure is determined, for example, as small particles, the difference in particle diameter with respect to the particle size may be 1:10 and 1:50. Small particles having a diameter ratio difference of 1: 5 to 1: 50 can effectively fill voids created from the alignment of the particles of the core-shell structure in the composition, thereby improving the filling rate.
The ratio of the large particles to the small particles contained in the composition of the present invention is preferably 10: 1 to 2000: 1 by weight. If the larger particles, that is, the particles of the core-shell structure, are contained in an amount less than the above-mentioned range, the effect of the mixing is lowered because the remaining small particles are crowded together, while the particles of the core- If it is included, small particles filling between the large particles are not enough, and the effect of improving the filling rate is decreased.
To prepare the small particles contained in the composition of the present invention, a manufacturing process as shown in FIG. 1A is followed, but not limited thereto. The reducing agent in the water layer is added to the precursor solution of the organic layer so that the precursor is reduced by the reducing agent present in the water layer when the precursor is moved to the water layer by the equilibrium distribution of the organic layer and the water layer of the precursor. According to this method, the reduction reaction occurs slowly due to the distribution equilibrium, so that the aggregation of the generated metal particles can be prevented. It is also easy to control the reaction rate.
Hereinafter, the present invention will be described in detail with reference to examples. However, it should be understood that the present invention is not limited to this because it is intended to facilitate understanding of the invention.
Example
1. Preparation of Ag nanoparticles
In a 250 ml flask, 0.6 g of Ag-Oleate was dissolved in 3.6 g of hexane (Hexane). Subsequently, oleylamine having 18 carbon atoms was added to the solution at 4 times the molar concentration of the Ag-Oleate to prepare an organic phase solution. Subsequently, 3.6 g of water was added to another 250 ml flask, and trisodium citrate as a reducing agent was added at a molar concentration of 1/4 of the Agolate to prepare a solution of the aqueous phase. Subsequently, the aqueous solution was dropped into the organic phase solution at a rate of 100 ml per hour, stirred for 30 minutes, and then left for 60 minutes to obtain 0.5 g of a precipitate.
The precipitate was washed twice with ethanol and dried to synthesize Ag nanoparticles.
Transmission electron microcopy (TEM) was taken to confirm the size of the particles. It was confirmed that particles having an average diameter of 10 nm were produced as shown in Fig. 1B.
2. Preparation of particles of Cu @ Ag core-shell structure
(1) Production of copper nanoparticles
1.1 g of copper 2-ethylhexanoate (Cu (II) 2-ethylhexanoate), 0.7 g of butylamine and 30 mL of xylene were dissolved in a 100-mL round bottom flask. The solution was heated to 60 ° C and a solution of 0.2 g of hydrazine (reagent of 80% purity) dissolved as a reducing agent in a mixed solution of 12 ml of ethanol and 18 ml of water was rapidly injected at once. After the addition, copper (Cu) nanoparticles were formed by allowing the reaction solution to stand at 60 ° C for 4 hours.
(2) Formation of a shell layer
The solution containing the copper nanoparticles was cooled to room temperature. Then, 0.6 g of acetaldehyde (using a reagent of 85% purity) was added to quench the reduction reaction of the reducing agent. Next, a solution containing copper nanoparticles was placed in a constant temperature bath set at 25 캜. A solution prepared by dissolving 150 parts by weight of silver 2-methylhexanoate and 0.1 part by weight of triethylamine relative to the nanoparticles in 30 mL of xylene was slowly dropped at a rate of 10 ml / min Respectively. Then, it was allowed to stand at room temperature for 1 hour to form a shell layer.
SEM (Scanning Electron Microscope) was taken to confirm the size of the particles. It was confirmed that particles having an average diameter of 100 nm were produced as shown in FIG. 2B.
3. Preparation of Metal Ink Composition
As shown in FIG. 3, 0.05 g of the prepared Ag nanoparticles and 0.5 g of the Cu @ Ag core-shell structure were mixed. It was then prepared with 25 wt% of anhydrous octane inks. Next, the glass substrate was spin-coated at a speed of 2000 rpm for 30 seconds. The coating film was formed by heat treatment at 300 캜 for 15 minutes in an inert atmosphere (H 2 (5%) + Ar (95%)).
Comparative Example
An ink of 25 weight% of anhydrous octane was prepared on Cu @ Ag nanoparticles synthesized in the examples, and then spin-coated on a glass substrate at a speed of 2000 rpm for 30 seconds. Treated at 300 캜 for 15 minutes in an inert atmosphere (H 2 (5%) + Ar (95%)).
Evaluation example
In order to observe the coating film properties of the coating films obtained in Examples and Comparative Examples, the surface was photographed by Scanning Electron Microscope (SEM).
4, in the case of the coating film prepared in the example, the shape of particles on the surface is hardly visible. That is, it can be confirmed that a smooth coating film is formed.
On the other hand, in FIG. 5, the shape of particles on the surface is rarely observed. That is, when the ink composition is prepared using only a single particle, the space between the particles is not filled, and the coating film formed therefrom has a somewhat uneven surface.
Claims (9)
Wherein the particles of the core-shell structure comprise a shell layer formed from a precursor represented by the following formula on the surface of the metal particles of the core:
[Formula 1]
Wherein X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or halogen, and n is an integer of 0 to 23.
Wherein the core metal particles are copper, nickel, iron, cobalt, zinc, chromium or manganese particles.
Wherein the core metal particles are formed from a precursor represented by the following formula:
[Formula 2]
M is Cu, Ni, Fe, Co, Zn, Cr, or Mn, m is 1 to 5,
R is
(Wherein X is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a halogen, and n is an integer of 0 to 23.)
Wherein said core metal particles are made from metal hexanoate.
Wherein the shell layer of the particles of the core-shell structure is formed from the same material as the particles differing in diameter from the particles.
Wherein the diameter ratio of particles differing in diameter from the particles of the core-shell structure is from 5: 1 to 50: 1.
Wherein the particles of the core-shell structure have a diameter of 100 to 150 nm.
Wherein the ratio of particles differing in diameter to the particles of the core-shell structure is in a weight ratio of 10: 1 to 2000: 1.
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| KR1020120125317A KR20140059340A (en) | 2012-11-07 | 2012-11-07 | Composition of metal ink |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3636051A4 (en) * | 2017-06-05 | 2020-12-30 | Nano-Dimension Technologies, Ltd. | Flocculates of metallic, geometrically discrete nanoparticles compositions and methods of forming the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3636051A4 (en) * | 2017-06-05 | 2020-12-30 | Nano-Dimension Technologies, Ltd. | Flocculates of metallic, geometrically discrete nanoparticles compositions and methods of forming the same |
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