1. Fields of the Invention
The present invention relates to a method for manufacturing a conductive adhesive, especially to a method for manufacturing a conductive adhesive containing a one-dimensional (1D) conductive nanomaterial.
2. Descriptions of Related Art
One-dimensional (1D) nanostructures have low-dimensional physical and electronic transport properties and have been regarded as the most promising materials with features different from those of bulk materials due to its special structure in the last 10 years. One-dimensional (1D) nanostructures include nanowires, nanotubes, nanorods, nanopillars, nanofibrils, and quantum wires. 1D nanostructure is applied to nanoelectronic devices and functional components such as ultra-thin and full-color LED, printing equipment, field emission display (FED), low energy consumption nanowire LED, ammonia (NH3) sensors, hydrogen (H2) sensors, etc.
Nano-metal materials such as gold, tin, silver, platinum etc. have good electrical conductivity so that they are applied to interconnect materials. 1D metal nanomaterials are with unusual properties in the fields of optics, electricity, magnetism and chemistry. 1D metal nanomaterials have connected zero-dimensional metal nanomaterials in series so that 1D metal nanomaterials are with better electrical conductivity compared with zero-dimensional metal nanomaterials. Due to two kinds of dimensions of the nanomaterials, 1D metal nanomaterials still keep their unique nanoscale properties such as high activity, low sintering temperature, tunnelling effect etc. Thus 1D metal nanomaterials have broad applications such as Ultra Large Scale Integration (ULSIC) and optical conductive fiber. Metal nanowires that match with nanodots are used for connecting electronic parts so as to achieve high density arrangement in nanoscale electronics. Magnetic metal nanowires with good vertical magnetization are used as high density vertical magnetic recording materials. Quantum magnetic disks produced by template synthesis are used as nanoelectrode ensembles, applied to trace detection and gas sensors in the field of electrochemistry analysis.
Silver is the best conductive metal and is applied to coating material such as conductive silver paste with features of high electrical conductivity, stretchability, salt mist corrosion durability, and wide applicable temperature range. For further applications in electrical conductivity after nanolization, 1D silver nanowire is synthesized. 1D wire-like nanostructure has features of a good conductivity and lower temperature sintering. It is applied to electrodes, low temperature sintered conductive adhesives, superconductive thick film circuit, microwave absorbing materials, and electromagnetic wave absorbing materials and the amount of silver used is dramatically reduced.
As to the one dimensional conductive nanomaterials, carbon nanotube is the only commercial product available on the market now. For higher conductivity, metal materials such as silver or copper should be used. However, the mass production of silver or copper nanowires has not matured yet and the product is quite expensive. Thus there is a need to develop related techniques and metal materials are a new generation of materials.
1D silver nanostructures are mainly applied to electrical conductivity and biochemistry fields. For electrical conductivity, 1D silver nanostructures are prepared to form a transparent conductive film for electrode connection of semiconductors, solar cells and light emitting diode (LED) or are used in conductive coating for micro-electronic components and displays.
The applications of 1D silver nanostructures in biochemistry mainly includes biological microsensors and self-assembled DNA sensors. 1D conductive nanomaterial applied to transparent conductive films is mainly produced by precision etching. Catalyst is implanted by vapor deposition and then 1D silver nanostructures can grow into a network microstructure. Or 1D silver nanostructures are synthesis firstly by electrochemical etching template growth or wet chemical synthesis and then is arranged again. Yet the ways of arrangement are quite complicated. For example, the 1D silver nanostructures are produced by filtering, deposition and drying and then to form a film by micro-transfer printing technology. Or the film is produced by microscope probes or high temperature sintering. These ways are not proper for mass production and there are many restrictions on the substrate. The manufacturing cost is quite high. These are all opposite to the industrial mainstream-coating processes.
After being mixed with resin, nano silver can be coated directly and cured at low temperature. Refer to two related techniques, Chinese Patent. App. No. 10154638, silver nanowires are prepared by wet chemical synthesis. After purification and drying, the silver nanowires are mixed with epoxy resin or phenolic resin to be coated and a film is formed. As to Chinese Patent. App. No. 10050523, a conductive adhesive is formed by silver nanowires and acrylic resin. Then the conductive adhesive is coated. Although the above two patents report good conductivity of the conductive adhesive and the conductive film, the incompatibility between aqueous solution containing silver nanowires and solvent-based resin has not been discussed. Aggregation occurs while mixing nanomaterials with different surface properties and poor-dispersed conductive medium is unable to connect and form an electric circuit. Thus the dispersion is a main bottleneck in the technology of enhancing conductivity of nanomaterials, especially the silver nanowires with good conductivity. The present invention provides a method for manufacturing a conductive adhesive containing one-dimensional conductive nanomaterials. The conductive adhesives obtained according to the present invention have good conductivity. Moreover, the amount of conductive material used is dramatically reduced and the manufacturing processes are simplified.
Therefore it is a primary object of the present invention to provide a method for manufacturing a conductive adhesive containing a one-dimensional (1D) conductive nanomaterial. A conductive adhesive is produced by mixing the 1D conductive nanomaterial with water-based or solvent-based colloid. The conductive adhesive has good industrial applications, not influenced by industrial adaptability and environmental adaptability. The conductive adhesive also has better conductivity.
It is another object of the present invention to provide a method for manufacturing a conductive adhesive containing a 1D conductive nanomaterial. The conductive adhesive obtained by the present invention has better conductivity. Moreover, the cost is reduced effectively because that less amount of 1D conductive nanomaterial is used.
In order to achieve above objects, a method for manufacturing a conductive adhesive containing a 1D conductive nanomaterial according to the present invention includes following steps. Add and disperse one conductive nanomaterial into ethanol to form a nanosacle dispersing solution. The conductive nanomaterial is in the form of nanowires, nanotubes, nanorods, or conductive material with 1D nanostructure. Then add a modification solution into the nanosacle dispersing solution to form a mixed solution. Stir and heat the mixed solution. Add a resin solution into the mixed solution and mix the mixed solution and the resin solution evenly to produce a conductive adhesive. Next modify rheological properties of the conductive adhesive obtained.
Another method for manufacturing a conductive adhesive containing a 1D conductive nanomaterial according to the present invention includes following steps. Add and disperse one conductive nanomaterial into ethanol to form a nanosacle dispersing solution. The conductive nanomaterial is in the form of nanowires, nanotubes, nanorods, or conductive material with 1D nanostructure. Then add a resin solution into the nanosacle dispersing solution, stir the nanosacle dispersing solution and the resin solution to mix evenly and get a colloidal mixture. Heat and concentrate the colloidal mixture so as to get a conductive adhesive.
The structure and the technical means adopted by the present invention to achieve the above and other objects can be best understood by referring to the following detailed description of the preferred embodiments and the accompanying drawings, wherein:
Refer to
Then take the step S12, add a resin solution into a nanoscale dispersing solution, stir and mix the mixture evenly to form a colloidal mixture. The resin solution is formed by mixing water based resin with an aqueous solution. Lastly, run the step S14, heat and concentrate the colloidal mixture to get a conductive adhesive. The following embodiments are conductive adhesives formed by mixing a conductive nanomaterial with a resin solution containing water-based resin.
In accordance with above steps, a conductive adhesive is produced. In this embodiment, the conductive nanomaterial is silver and the conductive nanomaterial is in the form of nanowire. The water based resin of the resin solution is PVA (polyvinyl alcohol). Back to
Then take the step S12, add a resin solution into nanoscale dispersing solution and stir the mixture evenly to form a colloidal mixture. The resin solution is prepared by heating and dissolving 10 g water-based PVA resin in 90 g aqueous solution. The mixture of the nanoscale dispersing solution and the resin solution is stirred evenly by a stirrer so as to form a colloidal mixture. The stirring time is 30 minutes.
Next run the step S14, heat and concentrate the colloidal mixture to get a conductive adhesive. The heating temperature is controlled at 80 degree Celsius. Continue stirring the mixture during heating processes until the viscosity has reached 1800 cp and then stop heating.
Refer to
The difference between this embodiment and the embodiment one is in that the amount of conductive nanomaterial used is 50 g and a conductive adhesive is obtained according to the steps in the embodiment one. Refer to
The difference between this embodiment and the embodiment one is in that the amount of the conductive nanomaterial used is 400 g and a conductive adhesive is obtained according to the steps in the embodiment one. Refer to
The conductive adhesive in the above three embodiments is formed by a conductive nanomaterial and resin solution containing water-based resin. Refer to
Refer to
Next take the step S24, stir and heat the mixed solution. Refer to the step S26, add a resin solution and a curing agent to the mixed solution. Stir and mix the mixed solution, the resin solution and the curing agent evenly to form a conductive adhesive. The resin solution is prepared by mixing a resin with an aqueous solution while the resin can be water-based resin or solvent-based resin. Finally, take the step S28, modify the rheological properties of the conductive adhesive. The rheological properties are modified by adding a thixotropic agent or a thickening agent into the conductive adhesive. The followings are embodiment of conductive adhesives formed by conductive nanomaterials and resin solution containing oleoresin.
This embodiment produces a conductive adhesive according to the above steps. In this embodiment, the conductive nanomaterial is silver, the conductive nanomaterial is in the form of nanowires. The oleoresin and the curing agent in the resin solution are respectively epoxy and BDMA (benzyl dimethyl amine). Back to
Then run the step S22, add a modification solution into the nanoscale dispersing solution to form a mixed solution. The modification solution is formed by mixing 0.05 g silane surface modifying agent a surface modifying agent, or a mixture of a surface modifying agent with 10 g acetone. Next take the step S24, stir and heat the mixed solution. After stirring and mixed solution evenly, heat for removing ethanol and acetone from the mixed solution.
Take the step S26, add a resin solution into the mixed solution and stir the resin solution and the mixed solution evenly to form a colloidal mixture. The resin solution is prepared by 10 g solvent epoxy resin mixed with BDMA. The mixture of the mixed solution and the resin solution is stirred evenly by a stirrer so as to form a colloidal mixture. The stirring time is 30 minutes. The last step is S28, modify the rheological properties of the conductive adhesive. In this embodiment, 0.05 g diluted thixotropic agent is added for modifying the rheological properties.
Refer to
The difference between this embodiment and the above one is in that no modification solution is added in this embodiment while other steps and conditions are the same. When the nanoscale dispersing solution and the resin solution are mixed and stirred, the conductive nanomaterial and the resin solution can not be mixed well and are separated from each other. There is no strong aggregation of the conductive nanomaterial observed. Although there is still an adhesive obtained, the four point probe is unable to measure the surface electrical resistivity of the adhesive. This means that the adhesive obtained without addition of the surface modifying agent has poor electrical conductivity.
Compared with the embodiment four, the oleoresin and the surface modifying agent are directly mixed for 60 minutes and then add nanoscale dispersing solution into the mixture in this embodiment. Stir and heat the mixture to get a conductive adhesive. Refer to
The difference between this embodiment and the embodiment four is in that the amount of the conductive nanomaterial is 150 g and the modification solution is formed by mixing 0.075 g silane surface modifying agent with 10 g acetone while other conditions are the same. There is no obvious aggregation observed in a conductive film formed by a conductive adhesive in this embodiment being coated on a substrate. Use a four point probe to measure surface electrical resistivity of the conductive film of this embodiment and the surface electrical resistivity is 2.2×100 Ω/square.
The difference between this embodiment and the embodiment four is in that the amount of the conductive nanomaterial is 200 g and the modification solution is formed by mixing 0.1 g silane surface modifying agent with 10 g acetone while other conditions are the same. There is no obvious aggregation observed in a conductive film formed by a conductive adhesive in this embodiment being coated on a substrate. Use a four point probe to measure surface electrical resistivity of the conductive film of this embodiment and the surface electrical resistivity is 4.5×10−1 Ω/square. Refer to
Compared with the embodiment one, the difference between this embodiment and the embodiment one is in the form of the conductive nanomaterial used. This embodiment uses 100 g silver nanoparticles dispersed in ethanol while other conditions are the same. There is no obvious aggregation observed in the conductive adhesive of this embodiment. The conductive adhesive of this embodiment is coated on a substrate to form a conductive film. Then use a four point probe to measure surface electrical resistivity of the conductive film and the surface electrical resistivity is 5.0×107 Ω/square.
The difference between this embodiment and the embodiment one is in the form of the conductive nanomaterial used. This embodiment uses 200 g silver nanoparticles dispersed in ethanol while other conditions are the same. There is no obvious aggregation observed in the conductive adhesive of this embodiment. The conductive adhesive of this embodiment is coated on a substrate to form a conductive film. Then use a four point probe to measure surface electrical resistivity of the conductive film and the surface electrical resistivity is 4.4×100 Ω/square.
The difference between this embodiment and the embodiment one is in the form of the conductive nanomaterial used. This embodiment uses 800 g silver nanoparticles dispersed in ethanol while other conditions are the same. There is no obvious aggregation observed in the conductive adhesive of this embodiment. The conductive adhesive of this embodiment is coated on a substrate to form a conductive film. Then use a four point probe to measure surface electrical resistivity of the conductive film and the surface electrical resistivity is 3.3×10−1 Ω/square. Refer to
Use the steps in the embodiment four while the difference between this embodiment and the embodiment four is in the form of the conductive nanomaterial used. This embodiment uses 200 g silver nanoparticles dispersed in ethanol while other conditions are the same. There is no obvious aggregation observed in the conductive adhesive of this embodiment. The conductive adhesive of this embodiment is coated on a substrate to form a conductive film. Then use a four point probe to measure surface electrical resistivity of the conductive film and the surface electrical resistivity is 1×1013 Ω/square.
Use the steps in the embodiment four while the difference between this embodiment and the embodiment four is in the form of the conductive nanomaterial used. This embodiment uses 400 g silver nanoparticles dispersed in ethanol while other conditions are the same. There is no obvious aggregation observed in the conductive adhesive of this embodiment. The conductive adhesive of this embodiment is coated on a substrate to form a conductive film. Then use a four point probe to measure surface electrical resistivity of the conductive film and the surface electrical resistivity is 5×102 Ω/square.
Use the steps in the embodiment four while the difference between this embodiment and the embodiment four is in the form of the conductive nanomaterial used. This embodiment uses 800 g silver nanoparticles dispersed in ethanol while other conditions are the same. There is no obvious aggregation observed in the conductive adhesive of this embodiment. The conductive adhesive of this embodiment is coated on a substrate to form a conductive film. Then use a four point probe to measure surface electrical resistivity of the conductive film and the surface electrical resistivity is 3.8×10−1 Ω/square. Refer to
In summary, the present invention provides a method for manufacturing a conductive adhesive containing a conductive nanomaterial in which a 1D conductive nanomaterial is mixed with water-based or solvent-based resin solution. 1D conductive nanomaterials have high aspect ratio and excellent conductivity. Thus they also have good physical properties and electron transport properties. Therefore the amount of conductive nanomaterial used is dramatically reduced. Moreover, the conductive adhesive manufactured by the present invention is observed and analyzed by an electron microscope. The results show that the conductive adhesive has been modified and the conductive nanomaterial is dispersed in colloidal evenly. The present invention provides a technique that mixes 1D conductive nanomaterials with colloids having different properties. The technique has high industrial applicability.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details, and representative devices shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Number | Name | Date | Kind |
---|---|---|---|
6741019 | Filas et al. | May 2004 | B1 |
7632425 | Simone et al. | Dec 2009 | B1 |
7645497 | Spath et al. | Jan 2010 | B2 |
7955528 | Chung et al. | Jun 2011 | B2 |
8043800 | Naoi | Oct 2011 | B2 |
8094247 | Allemand et al. | Jan 2012 | B2 |
8174667 | Allemand et al. | May 2012 | B2 |
8540899 | Miller | Sep 2013 | B2 |
20080143906 | Allemand et al. | Jun 2008 | A1 |
20110070404 | Naoi | Mar 2011 | A1 |
20110096388 | Agrawal et al. | Apr 2011 | A1 |
20110297642 | Allemand et al. | Dec 2011 | A1 |
20120031460 | Hosoya et al. | Feb 2012 | A1 |
20120094090 | Yamazaki et al. | Apr 2012 | A1 |
20120107598 | Zou et al. | May 2012 | A1 |
Number | Date | Country |
---|---|---|
WO 2010003138 | Jan 2010 | WO |
Number | Date | Country | |
---|---|---|---|
20120001130 A1 | Jan 2012 | US |