WO2005101427A1 - Conducting metal nano particle and nano-metal ink containing it - Google Patents

Conducting metal nano particle and nano-metal ink containing it Download PDF

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Publication number
WO2005101427A1
WO2005101427A1 PCT/KR2004/002910 KR2004002910W WO2005101427A1 WO 2005101427 A1 WO2005101427 A1 WO 2005101427A1 KR 2004002910 W KR2004002910 W KR 2004002910W WO 2005101427 A1 WO2005101427 A1 WO 2005101427A1
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WO
WIPO (PCT)
Prior art keywords
metal
nano
metal particles
printed circuit
circuit board
Prior art date
Application number
PCT/KR2004/002910
Other languages
French (fr)
Inventor
Hyung-Sup Lim
Young-Chul Yoo
Sang-Jin Lee
Original Assignee
Sukgyung A.T Co., Ltd
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Filing date
Publication date
Application filed by Sukgyung A.T Co., Ltd filed Critical Sukgyung A.T Co., Ltd
Publication of WO2005101427A1 publication Critical patent/WO2005101427A1/en

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials

Definitions

  • the present invention relates to conductive metal nano particles and a nano-metal ink comprising the same, and more particularly, to conductive metal nano particles which may be prepared by directly printing a wiring on a resin film in a single process, thereby simplifying the production process and reducing the production cost, a nano-metal ink comprising the same, and a method for preparing a printed circuit board using the same.
  • FCCL flexible copper clad laminate
  • CCL copper foil laminated overall or a copper clad laminate
  • a desired circuit is prepared by applying an adhesive on a thermal resistant resin film such as polyimide, attaching a copper foil thereto and subjecting the laminate to a hot press process to prepare a flexible copper clad laminate or a copper clad laminate, or forming an intermediate layer comprising copper and an element other than copper, instead of the adhesive and attaching a copper foil to prepare a copper clad laminate which is a raw material of the printed circuit board, and remaining a wiring of a desired pattern on the copper clad laminate, and it is necessary to perform the lithography process including application of a photoresister, drying, exposure to light, washing, etching, removal of the photoresister and the like.
  • a thermal resistant resin film such as polyimide
  • the lithography process which is usually used in the semiconductor process requires expensive equipments including an apparatus for applying a photocurable photoresist, called as DFR (dry film register) , an apparatus for exposure, an apparatus for etching and etching solution, an apparatus for washing and washing solution, and apparatus for drying and the like as well as a photomask to manufacture a circuit and thus, is performed via complicated procedures at a high cost. Therefore, a dry type process introducing the deposition process into the printing process has been recently developed, in which copper ion and the like is deposited to form a wiring. However, this process also needs expensive equipments such as a vacuum system and a master pattern which is similar to- the photomask.
  • DFR dry film register
  • a wiring can be directly printed on a resin film without performing both the step to manufacture a copper clad laminate by bonding a copper foil to a resin film and the lithography process, whereby it is possible to provide a fine pattern, which cannot be obtained from the silkscreen method, in a single printing process.
  • the manufacture cost can be considerably reduced.
  • miniaturization of the wiring width with a micro line-width and pitch can be accomplished only by a printing technique, whereby it is possible to produce a highly integrated and highly effective printed circuit boards. Consequently, it is possible to realize thinness and lightness of portable electronic and electric equipments such as mobile phone, PDA, notebook computer.
  • the printed circuit board is prepared by scattering a wiring material directly to a part requiring the same, it is possible to effectively use the wiring material and also use noble metals having a low resistivity as a material for wiring, causing dramatically reduction in resistance.
  • conductive nano-metal particles comprising a) a metal and b) a hydrocarbon containing a carboxyl group.
  • reduced conductive nano-metal particles prepared by reduction of the above-described conductive nano-metal particles .
  • a method for preparing conductive nano-metal particles comprising mixing a) a solution of a metal salt and b) a solution of a hydrocarbonic acid having a carboxyl group or a salt thereof.
  • a nano-metal ink comprising the above-described conductive nano-metal particles or reduced conductive nano- metal particles.
  • a nano-metal paste comprising the above-described conductive nano-metal particles or reduced conductive nano- metal particles.
  • a method for preparing a printed circuit board comprising the step of printing a pattern on a resin film using the above-described nano-metal ink or paste.
  • a printed circuit board prepared by the above- described method for preparing a printed circuit board is provided.
  • Fig. 1 is a photograph of the wiring printed on Teflon using the nano-metal paste which has been prepared according to Example 2; and Fig. 2 is a photograph of the wiring printed on paper using the nano-metal paste which has been prepared according to Example 4.
  • the conductive nano-metal particles according to the present invention is characterized by comprising a) a metal and b) a hydrocarbon containing a carboxyl group.
  • the conductive nano-metal particles take the form of a metal having its surface surrounded by a hydrocarbon containing a carboxyl group.
  • the metal of a) used according to the present invention may include any metal conventionally known to have electric conductivity, concretely, silver (Ag) , copper (Cu) , nickel, platinum (Pt) , gold (Au) , or palladium (Pd) .
  • the hydrocarbon containing a carboxyl group of b) used according to the present invention may include both saturated hydrocarbons or unsaturated hydrocarbons, preferably having 6 to 20 carbon atoms, considering fluidity of the nano-metal particles and formation of the nano particle.
  • the conductive nano-metal particles has preferably an average particle size of 1 to 10 run, particularly an average particle size of 4.5 to 5.0 ran and a particle size distribution having D i0 value (a maximum diameter of 10% of the lower part in cumulative distribution) of 3.0 to 4.0 ran and D 9 o value (a maximum diameter of 90% of the lower part in cumulative distribution) of 6.0 to 7.0 nm.
  • the particles When the particles fall in the foregoing ranges, they can be injected through a nozzle of an ink jet without clogging the nozzle and be appropriately fixed onto a substrate for printing.
  • the conductive nano-metal particles comprise preferably 50 to 99 wt% of a metal and 1 to 50 wt% of a hydrocarbon, more preferably 80 to 97 wt% of a metal and 3 to 20 wt% of a hydrocarbon.
  • the particles When the contents of the metal and the hydrocarbon are in the foregoing ranges, the particles are excellent in terms of formation of conductive circuit wiring, dispersion stability and conformity of equipment in an ink jet.
  • the conductive nano-metal particles can be used as an ink for forming wiring of a printed circuit board.
  • the conductive nano-metal particles can be prepared by a method for preparing conductive nano-metal particles comprising the step of mixing a) a metal salt or a solution of a metal salt and b) a solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof.
  • the conductive nano-metal particles are prepared by the step of mixing a) a solution of a metal salt and b) a solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof.
  • the metal salt of a) include water-soluble salts such as silver nitrate (AgN0 3 ) , silver acetate (AgCH 3 C00) , copper nitrate (Cu(N0 3 ) 2 ), copper acetate (Cu (CH 3 COO) 2 ) , copper chloride (CuCl 2 ) , nickel nitrate, nickel acetate, nickel sulfate, chloroplatinic acid (H 2 PtCle) , chloroauric acid (HAuCl 4 ) , palladium chloride (PdCl 2 ) and the like, acetalacetonates such as nickel acetylacetonate, copper acetylacetonate and the like which are soluble in an organic solvent, and alkoxides such as nickel ethoxide, copper ethoxide and the like which are hydrolysable.
  • water-soluble salts such as silver nitrate (AgN0 3 ) , silver acetate
  • the metal salt is not particularly limited as long as it contains cation of an electrically conductive metal.
  • the hydrocarbonic acid or the salt thereof include both acid and salt forms of a hydrocarbon containing a carboxyl group (COCf function) which may be saturated or unsaturated.
  • Its preferred example include those having 6 to 20 carbon atoms, conceretely sodium citrate, sodium glutamate, sodium iso- stearate, sodium myristate, sodium palmitate, sodium stearate, sodium oleate, sodium iso-stearate, potassium citrate, potassium glutamate, potassium laurate, potassium myristate, potassium palmitate, potassium stearate, potassium oleate, potassium iso-stearate and the like, which may be reacted with the salt containing cation of the conductive metal to form the salt of the conductive metal with the saturated hydrcarbonic acid or unsaturated hydrocarbonic acid.
  • they also may include the materials known to the art..
  • the solvent used in the solution of the metal salt and the solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof is not particularly limited as long as it can dissolve the metal salt or hydrocarbonic acid or salt and may include both water-based solvents and oil-based solvents.
  • the concentrations of the solution of the metal salt and the solution of hydrocarbonic acid containing a carboxyl group or a salt thereof are not particularly limited.
  • the solutions may be mixed in an appropriate ratio as needed. Particularly, considering the yield, they are preferably mixed in an molar ratio of 1 to 5 : 5 to 1, more preferably in an molar ratio of 1 : 1.
  • the conductive nano-metal particles according to the present invention may be subjected to washing and drying steps for removal of impurities, as needed. For the washing and drying, the conventional washing and drying processes are applicable . Also, the conductive nano-metal particles according to the present invention may be converted to reduced conductive nano-metal particles via a reduction step.
  • the reduction step a part of the hydrocarbon bonded to metal ion is removed by forming carbon dioxide and water, whereby the metal content in the reduced conductive nano-metal particles becomes higher than that in the conductive nano-metal particles.
  • the metal content in the reduced conductive nano-metal particles is 95 wt% or more, in terms of printing of wiring.
  • the reduction though not particularly limited, is performed by heating the conductive nano-metal particles in an oxygen atmosphere or an inert atmosphere considering easiness of reduction reaction and yield.
  • a reducing agent may be added prior to heating. Concrete examples of the reducing agent include triethyl a ine .
  • the heating is performed at 70 to 300 °C for 2 to 24 hours.
  • the present invention provides a nano-metal ink comprising conductive nano-metal particles or reduced conductive nano-metal particles prepared as described above.
  • the nano-metal ink comprises i ) conductive nano-metal particles or reduced conductive nano-metal particles and ii ) a solvent and may further comprise a dispersing agent, a thickening agent or an additive, as needed.
  • the solvent may any solvent which is conventionally used in inks, preferably a solvent suitable for ink-jet printers.
  • the content of the conductive nano-metal particles or reduced conductive nano-metal particles of i) in the nano-metal ink according to the present invention is not particularly limited as long as it can produce conductive wiring through printing.
  • the nano-metal ink according to the present invention comprises i ) 10 to 90 wt% of conductive nano-metal particles or reduced conductive nano-metal particles and ii ) 90 to 10 wt% of a solvent and may further comprise 0.01 to 10 wt% of a dispersing agent, a thickening agent or an additive, as needed.
  • the nano ink using the conductive nano-metal particles according to the present invention has a viscosity of 2000 to 20000 cps, preferably 8000 to 9000 cps, while the nano ink using the reduced conductive nano-metal particles according to the present invention has a viscosity of 10 to 500 cps, preferably 10 to 100 cps.
  • the nano-metal ink may be prepared in the form of paste by selecting a proper solvent and including 0.01 to 10 parts by weight of a thickening agent relative to 100 parts by weight of the sum of the nano-metal particles and the solvent.
  • the solvent is terpineol and the thickening agent is ethyl cellulose.
  • the nano-metal paste is particularly suitable for screen printing. In this case, the nano-metal paste has preferably a viscosity of 30000 to 300000 cps, more preferably a viscosity of 80000 to 150000 cps.
  • the present invention provides a method for preparing a printed circuit board comprising the step of printing a pattern on a resin film with the nano-metal ink.
  • the method for preparing the printed circuit board comprises the steps of: a) printing a metal wiring on a resin film using the nano-metal ink; b) drying the printed circuit board having the metal wiring printed thereon from the step a) ; and c) calcining the dried printed circuit board from the step b) .
  • the metal contained in the nano-metal ink may be copper, silver, gold, platinum, nickel or a mixture thereof which has a low resistivity among conductive metals.
  • the printing using the ink may be performed by any of the printing means known to the art, concretely including ink jet, screen and the like, with the screen being preferred.
  • the ink jet includes any type of printing methods known to the art to involve injecting an ink to print a pattern.
  • a wiring diagram is completed according to the digital printing method and the nano-metal ink is injected on a resin film according to the pattern of the completed wiring diagram to print the pattern of the desired metal wiring.
  • the resin film used in the step a) includes resin films commonly used in PCB or FPCB, preferably thermal resistant resin film including PTFE or polyimide.
  • a protective film may be deposited on the resin film prior to the printing of the metal wiring in the step a) .
  • the protective film which can be used in the present invention include conventional films comprising PTFE or polyimide and may be laminated into a double-layered structure to enhance protection function.
  • an intermediate layer may be laminated on the resin film prior to the printing of the metal wiring in the step a) .
  • the intermediate layer may be constructed by double printing, in which a mixture of an element which is different from the element of the metal wiring, that is a pure metal, is printed on the resin film by the same method for the pure metal wiring and the actual metal wiring is printed on the wiring of the intermediate layer.
  • the wiring is a copper layer while the intermediate layer is an alloy layer formed of copper and nickel.
  • the drying in the step b) may be performed, as needed.
  • the ink may be dried immediately after printing and thus, a outwardly distinguishable drying process may not be carried out.
  • the calcination in the step c) is performed to remove the dispersing agent, thickening agent or additive remaining in the ink dried in the drying step and to induce bonding between the nano-metal particles or reduction and bonding of the nano-metal salt to metal.
  • the calcination is preferably performed at a high temperature for a long period of time, particularly at 150 to 350 ° C for 10 to 30 minutes.
  • the printed circuit board which can be prepared according to the above-described method includes flexible printed circuit boards as well as general printed circuit boards.
  • the printed circuit board according to the present invention may be constructed to have the wiring thin and fine and thus is advantageous in miniaturization and high integration, particularly application to flexible printed circuit boards.
  • the present invention provides a printed circuit board prepared by the method for forming a wiring as described above and thus, includes printed circuit boards or flexible printed circuit boards which is applicable to various fields including portable, electronic/electric equipments for portable, industrial, official and household uses . Now, preferred examples are presented to help understanding of the present invention. However, it should be understood that the following examples are only for illustrative purposes and the scope of the present invention is not limited thereto.
  • Example 1 16.98 g of silver nitrate was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (AgN0 3 ) . Next, sodium citrate was weighed and dissolved in ultra pure water to prepare 0.1 mol/L solution. The silver nitrate solution and the sodium citrate solution were mixed in an apparatus equipped with a stirrer to give silver citrate. The silver citrate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80 ° C for 12 hours.
  • Example 2 16.98 g of silver nitrate was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (AgN0 3 ) . Next, sodium myristate was weighed and dissolved in ultra pure water to prepare 0.1 mol/L solution. The silver nitrate solution and the sodium myristate solution were mixed in an apparatus equipped with a stirrer to give silver myristate. The silver myristate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80 °C for 12 hours to give silver myristate as white fine particles.
  • the mixture was heated at a mild temperature to produce a silver paste.
  • the produced silver paste had a silver content of 50 to 60 wt%, a viscosity of 80,000 to 150,000 cP.
  • screen printing was performed and the substrate kept in an electric muffle furnace set at 220 °C for about 10 minutes to give a Ag metal wiring, which has a resistivity of 5.6 x 10 " ⁇ ⁇ cm.
  • Example 3 5 wt% of chloroauric acid was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (AgN0 3 ) . Next, sodium stearate was weighed and dissolved in ultra pure water to prepare 0.1 mol/L solution. The chloroauric acid solution and the sodium stearate solution were mixed in an apparatus equipped with a stirrer to give silver stearate. The silver stearate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80 ° C for 12 hours to give gold myristate as white fine particles.
  • the produced substance was put into an aliphatic hydrocarbon having a low dielectric constant, such as n- hexane, n-decanol or PGMEA solution, stirred and settled to give red Au sol.
  • a thickening agent and an additive were added to prepare an ink having a viscosity of 10 to 100 cps .
  • a wiring was printed using the prepared ink on an ink jet recording apparatus the print was kept in an electric muffle furnace set at 220 °C for about 10 minutes to give a Au metal wiring, which has a resistivity of 3.6 x 10 S ⁇ cm.
  • Example 4 16.98 g of copper nitrate was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (CuN0 3 ) . Next, sodium myristate was weighed and dissolved in ultra pure water to prepare 0.2 mol/L solution. The copper nitrate solution and the sodium citrate solution were mixed in an apparatus equipped with a stirrer to give copper citrate. The copper myristate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80 ° C for 12 hours to give copper myristate as white fine particles.
  • the copper myristate thus obtained was put into a 4- neck flask and thermally treated in N2 atmosphere at 250 ° C for 4 hours.
  • 292 g of copper myristate was put into a 3-neck flask along with 810 g of triethyl amine and a desk top circulator was set to at 5 ° C and kept at this temperature. Then, the temperature was raised to 80 ° C using a heating mantle and kept at this temperature for 2 hours. After 2 -hours, the reaction solution was directly added to 1L of methanol and settled. The supernatant was removed and the residual was washed 5 to 7 times with methanol and dried to give copper powder which contains myristate in an amount of less than 5 wt%.
  • a solvent such as terpineol and a thickening agent such as ethyl cellulose were added to the resulting powder.
  • the mixture was heated at a mild temperature to produce a copper paste.
  • the produced silver paste had a copper content of 50 to 60 wt%, a viscosity of 80,000 to 150,000 cP.
  • screen printing was performed and the substrate kept in an electric muffle furnace set at 350 ° C under an inert gas (N2) or oxygen (02) atmosphere for about 10 minutes to give a Cu metal wiring, which has a resistivity of 9.3 x 10 " 6 ⁇ cm.

Abstract

The present invention relates to conductive metal nano particles and an nano-metal ink comprising the same, and more particularly, conductive metal nano particles comprising a metal and a hydrocarbon containing a carboxyl group, a production method thereof, a nano-metal ink comprising the conductive nano particles and a method for preparing printed circuit board using the nano-metal ink. According to the present invention, it is possible to laminate both the production of copper clad laminate (CCL) to bond a copper foil to a film and lithography process and simplify the production process by directly printing a wiring on a resin film in a single process and considerably reduce the manufacture cost and produce highly integrated and highly effective printed circuit board through miniaturization of line width in the printed circuit board. According to the present invention, in formation of a wiring on a flexible printed circuit board (FPCB) used in electronic appliances and electrical equipment such as mobile phones, PDA, notebook computers and the like or a wiring of a general appliance, the printed circuit board (PCB) or flexible printed circuit board (FPCB), metal nano-particles for forming the wiring is prepared, the metal nano-particles are converted into ink, which is then printed. The printed circuit board(PCB) or flexible printed circuit board IBPCB) prepared by a novel method is applied to electric and electronic appliances for industrial, official or house hold.

Description

CONDUCTING ,METAL NANO PARTICLE AMD NANO-METAL INK CONTAINING IT
Technical Field The present invention relates to conductive metal nano particles and a nano-metal ink comprising the same, and more particularly, to conductive metal nano particles which may be prepared by directly printing a wiring on a resin film in a single process, thereby simplifying the production process and reducing the production cost, a nano-metal ink comprising the same, and a method for preparing a printed circuit board using the same.
Background Art Conventionally, flexible printed circuit boards (FPCB) used in various electronic appliances such as mobile phones, PDAs, notebook computers and the like and printed circuit boards (PCB) used in electric and electronic equipment for general industrial uses, office uses and household uses have been produced through a series of complicated processes, in which a flexible copper clad laminate (FCCL) having a copper foil laminated overall or a copper clad laminate (CCL) is partially etched by the lithography process, remaining a desired wiring. Thus, according to the prior art, a desired circuit is prepared by applying an adhesive on a thermal resistant resin film such as polyimide, attaching a copper foil thereto and subjecting the laminate to a hot press process to prepare a flexible copper clad laminate or a copper clad laminate, or forming an intermediate layer comprising copper and an element other than copper, instead of the adhesive and attaching a copper foil to prepare a copper clad laminate which is a raw material of the printed circuit board, and remaining a wiring of a desired pattern on the copper clad laminate, and it is necessary to perform the lithography process including application of a photoresister, drying, exposure to light, washing, etching, removal of the photoresister and the like. However, the lithography process which is usually used in the semiconductor process requires expensive equipments including an apparatus for applying a photocurable photoresist, called as DFR (dry film register) , an apparatus for exposure, an apparatus for etching and etching solution, an apparatus for washing and washing solution, and apparatus for drying and the like as well as a photomask to manufacture a circuit and thus, is performed via complicated procedures at a high cost. Therefore, a dry type process introducing the deposition process into the printing process has been recently developed, in which copper ion and the like is deposited to form a wiring. However, this process also needs expensive equipments such as a vacuum system and a master pattern which is similar to- the photomask. Therefore, though some sub-processes may be omitted, it is still a process which should be performed a series of complicated procedures using expensive equipments at the high manufacture cost. Further, the tendency of thinness and lightness of electric and electronic appliances urges the manufacturers of printed circuit boards which are used in such appliances also to realize high density and high integration of their products. For this, miniaturization is needed to narrow line-width and pitch between lines of a printed circuit board. However, the silkscreen type printing technique which has been applied to the conventional printed circuit board fails to satisfy the request for such miniaturization. In addition, though the miniaturization of a printed circuit board for thinness and lightness of the above-described appliances requires reduction in line-width. However, when the line- width is narrowed, line resistance is increased. In order to lower the line resistance, noble metals such as gold, silver and platinum having low resistivity is to be used. This has a problem in substantial application of noble metal lines since it consumes a large amount of expensive noble metals. Therefore, it is required to conduct research for a method for preparing a printed circuit board which can considerably reduce the manufacture cost through simplification of the process. In order to solve the problems involved in the prior art as described above, it is an object of the present invention to provide conductive metal nano particles which can produce highly integrated micro printed circuit board having a micro line-width and pitch only by simple printing apparatus and printing process and directly print a wiring on a resin film in a single process, thereby simplify the process and significantly reducing the unit cost of production, a method for preparing the same and an ink and an paste comprising the conductive metal nano particle. It is another object of the present invention to provide a method for preparing a printed circuit board which can prepare a highly integrated micro printed circuit board that is so capable of highly effectively using a material for the wiring that a noble metal having a low resistivity may be used as a material of the wiring and has a micro line-width and pitch and a printed circuit board prepared therefrom. Thus, according to the present invention, a wiring can be directly printed on a resin film without performing both the step to manufacture a copper clad laminate by bonding a copper foil to a resin film and the lithography process, whereby it is possible to provide a fine pattern, which cannot be obtained from the silkscreen method, in a single printing process. Also, since the expensive equipments such as exposure and etching apparatuses are not used, the manufacture cost can be considerably reduced. Further, in the printed circuit board, miniaturization of the wiring width with a micro line-width and pitch can be accomplished only by a printing technique, whereby it is possible to produce a highly integrated and highly effective printed circuit boards. Consequently, it is possible to realize thinness and lightness of portable electronic and electric equipments such as mobile phone, PDA, notebook computer. In addition, since the printed circuit board is prepared by scattering a wiring material directly to a part requiring the same, it is possible to effectively use the wiring material and also use noble metals having a low resistivity as a material for wiring, causing dramatically reduction in resistance. Thus, it is advantageously miniaturize more the wiring width and wiring peach miniaturization
Disclosure of Invention According to the present invention, there are provided conductive nano-metal particles comprising a) a metal and b) a hydrocarbon containing a carboxyl group. Also, according to the present invention, there are provided reduced conductive nano-metal particles prepared by reduction of the above-described conductive nano-metal particles . Also, according to the present invention, there is provided a method for preparing conductive nano-metal particles comprising mixing a) a solution of a metal salt and b) a solution of a hydrocarbonic acid having a carboxyl group or a salt thereof. Also, according to the present invention, there is provided a nano-metal ink comprising the above-described conductive nano-metal particles or reduced conductive nano- metal particles. Also, according to the present invention, there is provided a nano-metal paste comprising the above-described conductive nano-metal particles or reduced conductive nano- metal particles. Also, according to the present invention, there is provided a method for preparing a printed circuit board comprising the step of printing a pattern on a resin film using the above-described nano-metal ink or paste. Also, according to the present invention, there is provided a printed circuit board prepared by the above- described method for preparing a printed circuit board.
Brief Description of Drawings Further objects and advantages of the invention can be more fully understood from the following detailed description taken in conjunction with the accompanying drawings in which: Fig. 1 is a photograph of the wiring printed on Teflon using the nano-metal paste which has been prepared according to Example 2; and Fig. 2 is a photograph of the wiring printed on paper using the nano-metal paste which has been prepared according to Example 4.
Best Mode for Carrying Out the Invention Now, the present invention is described in detail. The conductive nano-metal particles according to the present invention is characterized by comprising a) a metal and b) a hydrocarbon containing a carboxyl group. Preferably, the conductive nano-metal particles take the form of a metal having its surface surrounded by a hydrocarbon containing a carboxyl group. The metal of a) used according to the present invention may include any metal conventionally known to have electric conductivity, concretely, silver (Ag) , copper (Cu) , nickel, platinum (Pt) , gold (Au) , or palladium (Pd) . The hydrocarbon containing a carboxyl group of b) used according to the present invention may include both saturated hydrocarbons or unsaturated hydrocarbons, preferably having 6 to 20 carbon atoms, considering fluidity of the nano-metal particles and formation of the nano particle. The conductive nano-metal particles has preferably an average particle size of 1 to 10 run, particularly an average particle size of 4.5 to 5.0 ran and a particle size distribution having Di0 value (a maximum diameter of 10% of the lower part in cumulative distribution) of 3.0 to 4.0 ran and D9o value (a maximum diameter of 90% of the lower part in cumulative distribution) of 6.0 to 7.0 nm. When the particles fall in the foregoing ranges, they can be injected through a nozzle of an ink jet without clogging the nozzle and be appropriately fixed onto a substrate for printing. Also, the conductive nano-metal particles comprise preferably 50 to 99 wt% of a metal and 1 to 50 wt% of a hydrocarbon, more preferably 80 to 97 wt% of a metal and 3 to 20 wt% of a hydrocarbon. When the contents of the metal and the hydrocarbon are in the foregoing ranges, the particles are excellent in terms of formation of conductive circuit wiring, dispersion stability and conformity of equipment in an ink jet. The conductive nano-metal particles can be used as an ink for forming wiring of a printed circuit board. The conductive nano-metal particles can be prepared by a method for preparing conductive nano-metal particles comprising the step of mixing a) a metal salt or a solution of a metal salt and b) a solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof. Preferably, the conductive nano-metal particles are prepared by the step of mixing a) a solution of a metal salt and b) a solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof. Concrete examples of the metal salt of a) include water-soluble salts such as silver nitrate (AgN03) , silver acetate (AgCH3C00) , copper nitrate (Cu(N03)2), copper acetate (Cu (CH3COO) 2) , copper chloride (CuCl2) , nickel nitrate, nickel acetate, nickel sulfate, chloroplatinic acid (H2PtCle) , chloroauric acid (HAuCl4) , palladium chloride (PdCl2) and the like, acetalacetonates such as nickel acetylacetonate, copper acetylacetonate and the like which are soluble in an organic solvent, and alkoxides such as nickel ethoxide, copper ethoxide and the like which are hydrolysable. However, in preparation of the conductive nano metal salt particles, the metal salt is not particularly limited as long as it contains cation of an electrically conductive metal. Also, in the solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof, the hydrocarbonic acid or the salt thereof include both acid and salt forms of a hydrocarbon containing a carboxyl group (COCf function) which may be saturated or unsaturated. Its preferred example include those having 6 to 20 carbon atoms, conceretely sodium citrate, sodium glutamate, sodium iso- stearate, sodium myristate, sodium palmitate, sodium stearate, sodium oleate, sodium iso-stearate, potassium citrate, potassium glutamate, potassium laurate, potassium myristate, potassium palmitate, potassium stearate, potassium oleate, potassium iso-stearate and the like, which may be reacted with the salt containing cation of the conductive metal to form the salt of the conductive metal with the saturated hydrcarbonic acid or unsaturated hydrocarbonic acid. In addition to the above-listed materials, they also may include the materials known to the art.. Also, the solvent used in the solution of the metal salt and the solution of a hydrocarbonic acid containing a carboxyl group or a salt thereof is not particularly limited as long as it can dissolve the metal salt or hydrocarbonic acid or salt and may include both water-based solvents and oil-based solvents. The concentrations of the solution of the metal salt and the solution of hydrocarbonic acid containing a carboxyl group or a salt thereof are not particularly limited.
However, in terms of preparation process and yield, they are each preferably 0.01 mol/L to 1.0 mol/L, more preferably 0.1 mol/L to 0.2 mol/L. Also, the solutions may be mixed in an appropriate ratio as needed. Particularly, considering the yield, they are preferably mixed in an molar ratio of 1 to 5 : 5 to 1, more preferably in an molar ratio of 1 : 1. Also, the conductive nano-metal particles according to the present invention may be subjected to washing and drying steps for removal of impurities, as needed. For the washing and drying, the conventional washing and drying processes are applicable . Also, the conductive nano-metal particles according to the present invention may be converted to reduced conductive nano-metal particles via a reduction step. Through the reduction step, a part of the hydrocarbon bonded to metal ion is removed by forming carbon dioxide and water, whereby the metal content in the reduced conductive nano-metal particles becomes higher than that in the conductive nano-metal particles. Preferably, the metal content in the reduced conductive nano-metal particles is 95 wt% or more, in terms of printing of wiring. The reduction, though not particularly limited, is performed by heating the conductive nano-metal particles in an oxygen atmosphere or an inert atmosphere considering easiness of reduction reaction and yield. As needed, a reducing agent may be added prior to heating. Concrete examples of the reducing agent include triethyl a ine . Preferably, the heating is performed at 70 to 300 °C for 2 to 24 hours. Also, the present invention provides a nano-metal ink comprising conductive nano-metal particles or reduced conductive nano-metal particles prepared as described above. The nano-metal ink comprises i ) conductive nano-metal particles or reduced conductive nano-metal particles and ii ) a solvent and may further comprise a dispersing agent, a thickening agent or an additive, as needed. The solvent may any solvent which is conventionally used in inks, preferably a solvent suitable for ink-jet printers. Also, the content of the conductive nano-metal particles or reduced conductive nano-metal particles of i) in the nano-metal ink according to the present invention is not particularly limited as long as it can produce conductive wiring through printing. Preferably, the nano-metal ink according to the present invention comprises i ) 10 to 90 wt% of conductive nano-metal particles or reduced conductive nano-metal particles and ii ) 90 to 10 wt% of a solvent and may further comprise 0.01 to 10 wt% of a dispersing agent, a thickening agent or an additive, as needed. Also, the nano ink using the conductive nano-metal particles according to the present invention has a viscosity of 2000 to 20000 cps, preferably 8000 to 9000 cps, while the nano ink using the reduced conductive nano-metal particles according to the present invention has a viscosity of 10 to 500 cps, preferably 10 to 100 cps. When the viscosity of the nano ink falls in the foregoing range, the produced wiring is excellent in terms of conductivity, yield and conformity of equipment in printers . Also, the nano-metal ink may be prepared in the form of paste by selecting a proper solvent and including 0.01 to 10 parts by weight of a thickening agent relative to 100 parts by weight of the sum of the nano-metal particles and the solvent. Preferably, the solvent is terpineol and the thickening agent is ethyl cellulose. The nano-metal paste is particularly suitable for screen printing. In this case, the nano-metal paste has preferably a viscosity of 30000 to 300000 cps, more preferably a viscosity of 80000 to 150000 cps. With the viscosity of the paste falling in the foregoing range, the ink is excellent in printability and formation of wiring. Also, the present invention provides a method for preparing a printed circuit board comprising the step of printing a pattern on a resin film with the nano-metal ink. Concretely, the method for preparing the printed circuit board comprises the steps of: a) printing a metal wiring on a resin film using the nano-metal ink; b) drying the printed circuit board having the metal wiring printed thereon from the step a) ; and c) calcining the dried printed circuit board from the step b) . The metal contained in the nano-metal ink may be copper, silver, gold, platinum, nickel or a mixture thereof which has a low resistivity among conductive metals. Also, the printing using the ink may be performed by any of the printing means known to the art, concretely including ink jet, screen and the like, with the screen being preferred. The ink jet includes any type of printing methods known to the art to involve injecting an ink to print a pattern. Thus, a wiring diagram is completed according to the digital printing method and the nano-metal ink is injected on a resin film according to the pattern of the completed wiring diagram to print the pattern of the desired metal wiring. The resin film used in the step a) includes resin films commonly used in PCB or FPCB, preferably thermal resistant resin film including PTFE or polyimide. Also, in an embodiment of the method for forming a wiring on a printed circuit board according to the present invention, in order to prevent reaction or diffusion between the nano-metal ink and the resin film and improve the bonding between the wiring and the resin, a protective film may be deposited on the resin film prior to the printing of the metal wiring in the step a) . The protective film which can be used in the present invention include conventional films comprising PTFE or polyimide and may be laminated into a double-layered structure to enhance protection function. In addition to the lamination of the protective films, an intermediate layer may be laminated on the resin film prior to the printing of the metal wiring in the step a) . The intermediate layer may be constructed by double printing, in which a mixture of an element which is different from the element of the metal wiring, that is a pure metal, is printed on the resin film by the same method for the pure metal wiring and the actual metal wiring is printed on the wiring of the intermediate layer. For example, in an embodiment, the wiring is a copper layer while the intermediate layer is an alloy layer formed of copper and nickel. The drying in the step b) may be performed, as needed. According to the type of the dispersing agent used in the nano-metal ink and viscosity of the ink, the ink may be dried immediately after printing and thus, a outwardly distinguishable drying process may not be carried out. The calcination in the step c) is performed to remove the dispersing agent, thickening agent or additive remaining in the ink dried in the drying step and to induce bonding between the nano-metal particles or reduction and bonding of the nano-metal salt to metal. In order to prevent deterioration in the resin film and diffusion, the calcination is preferably performed at a high temperature for a long period of time, particularly at 150 to 350°C for 10 to 30 minutes. The printed circuit board which can be prepared according to the above-described method includes flexible printed circuit boards as well as general printed circuit boards. Specially, the printed circuit board according to the present invention may be constructed to have the wiring thin and fine and thus is advantageous in miniaturization and high integration, particularly application to flexible printed circuit boards. Also, the present invention provides a printed circuit board prepared by the method for forming a wiring as described above and thus, includes printed circuit boards or flexible printed circuit boards which is applicable to various fields including portable, electronic/electric equipments for portable, industrial, official and household uses . Now, preferred examples are presented to help understanding of the present invention. However, it should be understood that the following examples are only for illustrative purposes and the scope of the present invention is not limited thereto.
[Example] Example 1 16.98 g of silver nitrate was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (AgN03) . Next, sodium citrate was weighed and dissolved in ultra pure water to prepare 0.1 mol/L solution. The silver nitrate solution and the sodium citrate solution were mixed in an apparatus equipped with a stirrer to give silver citrate. The silver citrate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80°C for 12 hours. 10 g of the silver citrate thus obtained was taken into 20 g of diacetone alcohol having 0.2 wt% of EC (ethyl cellulose (300 cps) ) , based on the total weight, dissolved therein and the mixture was mixed for about 5 minutes in a mixing apparatus capable of simultaneously rotating and revolving to prepare an ink having a viscosity 8,000 to 9,000 cps . The prepared ink was mounted on an ink jet recording apparatus and printed on a glass substrate. As a result, a circuit wiring was formed. after printing, the printed substrate was passed through a heating furnace at 150 °C to give a metal wiring having excellent conductivity.
Example 2 16.98 g of silver nitrate was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (AgN03) . Next, sodium myristate was weighed and dissolved in ultra pure water to prepare 0.1 mol/L solution. The silver nitrate solution and the sodium myristate solution were mixed in an apparatus equipped with a stirrer to give silver myristate. The silver myristate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80 °C for 12 hours to give silver myristate as white fine particles. 120 g of the silver myristate thus obtained and 289.7 g of triethyl amine were put into a 3-neck flask and a desk top circulator was set to at 5°C and kept at this temperature. Then, the temperature was raised to 80 °C using a heating mantle and kept at this temperature for 2 hours. After 2 hours, the reaction solution was directly added to 1L of methanol and settled. The supernatant was removed and the residual was washed 5 to 7 times with methanol and dried to give silver powder which contains myristate in an amount of less than 5 wt%. A solvent such as terpineol and a thickening agent such as ethyl cellulose were added to the resulting powder. The mixture was heated at a mild temperature to produce a silver paste. The produced silver paste had a silver content of 50 to 60 wt%, a viscosity of 80,000 to 150,000 cP. Using the produced paste, screen printing was performed and the substrate kept in an electric muffle furnace set at 220 °C for about 10 minutes to give a Ag metal wiring, which has a resistivity of 5.6 x 10" δΩ cm.
Example 3 5 wt% of chloroauric acid was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (AgN03) . Next, sodium stearate was weighed and dissolved in ultra pure water to prepare 0.1 mol/L solution. The chloroauric acid solution and the sodium stearate solution were mixed in an apparatus equipped with a stirrer to give silver stearate. The silver stearate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80°C for 12 hours to give gold myristate as white fine particles. 100 g of the gold stearate thus obtained was put into a 3-neck flask and an inert gas (N2 gas or Ar gas) was introduced thereto in an amount of 0.1 N m2/hr. Heat was applied to the whole of the flask so that the temperature inside the flask was 280°C. As the temperature went up, the gold stearate was reduced and C and H were converted into CO, C02, H20 and the like via carbonization with the inert gas which were then forced out of the flask to finally give a dark-red substance. The produced substance was put into an aliphatic hydrocarbon having a low dielectric constant, such as n- hexane, n-decanol or PGMEA solution, stirred and settled to give red Au sol. To the produced sol, a thickening agent and an additive were added to prepare an ink having a viscosity of 10 to 100 cps . A wiring was printed using the prepared ink on an ink jet recording apparatus the print was kept in an electric muffle furnace set at 220 °C for about 10 minutes to give a Au metal wiring, which has a resistivity of 3.6 x 10 SΩ cm. Example 4 16.98 g of copper nitrate was weighed and dissolved in ultra pure water so that the total volume was equal to 1 L to prepare 0.1 mol/L solution of silver nitrate (CuN03) . Next, sodium myristate was weighed and dissolved in ultra pure water to prepare 0.2 mol/L solution. The copper nitrate solution and the sodium citrate solution were mixed in an apparatus equipped with a stirrer to give copper citrate. The copper myristate was washed with ultra pure water until Na ion was not detected and after completion of washing, dried in a drier at 80 °C for 12 hours to give copper myristate as white fine particles. The copper myristate thus obtained was put into a 4- neck flask and thermally treated in N2 atmosphere at 250 °C for 4 hours. 292 g of copper myristate was put into a 3-neck flask along with 810 g of triethyl amine and a desk top circulator was set to at 5°C and kept at this temperature. Then, the temperature was raised to 80°C using a heating mantle and kept at this temperature for 2 hours. After 2 -hours, the reaction solution was directly added to 1L of methanol and settled. The supernatant was removed and the residual was washed 5 to 7 times with methanol and dried to give copper powder which contains myristate in an amount of less than 5 wt%. A solvent such as terpineol and a thickening agent such as ethyl cellulose were added to the resulting powder. The mixture was heated at a mild temperature to produce a copper paste. The produced silver paste had a copper content of 50 to 60 wt%, a viscosity of 80,000 to 150,000 cP. Using the produced paste, screen printing was performed and the substrate kept in an electric muffle furnace set at 350 °C under an inert gas (N2) or oxygen (02) atmosphere for about 10 minutes to give a Cu metal wiring, which has a resistivity of 9.3 x 10" 6Ω cm.

Claims

What Is Claimed Is:
1. Conductive nano-metal particles comprising a) a metal and b) a hydrocarbon containing a carboxyl group.
2. The conductive nano-metal particles according to claim 1, in which the nano-metal particles are used as an ink for forming a wiring on a printed circuit.
3. The conductive nano-metal particles according to claim 1, in which the nano-metal particles have an average particle size of 1 to 10 nm .
4. The conductive nano-metal particles according to claim 1, in which the metal is contained in an amount of 50 to 99 wt % and the hydrocarbon is contained in an amount of 1 to 50 wt %.
5. A method for preparing conductive nano-metal particles comprising the step of mixing comprising mixing a) a solution of a metal salt and b) a solution of a hydrocarbonic acid having a carboxyl group or a salt thereof.
6. The method according to claim 5, which comprises the steps of: i ) mixing a) a solution of a metal salt, and b) a solution of a hydrocarbon containing a carboxyl' group or a salt thereof; and ii ) washing and drying the conductive nano-metal particles prepared in the step i) .
7. The method according to claim 6, in which the metal salt of the step i)-a) is at least one selected from the group consisting of silver nitrate (AgN03) , silver acetate (AgCH3C00) , copper nitrate (Cu(N03)2), copper acetate (Cu (CH3C00) 2) , copper chloride (CuCl2) , nickel nitrate, nickel acetate, nickel sulfate, chloroplatinic acid (H2PtCl6) , chloroauric acid (HAuCl4) , palladium chloride (PdCl2) , nickel acetylacetonate, copper acetylacetonate, nickel ethoxide and copper ethoxide.
8. The method according to claim 6, in which the hydrocarbonic acid containing a carboxyl group or salt thereof of the step i)-b) is at least one selected from the group consisting of citric acid, glutamic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, iso- stearic acid, sodium citrate, sodium glutamate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, sodium oleate, sodium iso-stearate, potassium citrate, potassium glutamate, potassium laurate, potassium myristate, potassium palmitate, potassium stearate, potassium oleate and potassium iso-stearate, which have 6 to 20 carbon atoms.
9. The method according to claim 6, in which the solution of the metal salt of the step i)-a) and the solution of hydrocarbonic acid containing a carboxyl group or a salt thereof of the step of i)-b) are each used in a concentration of 0.01 mol/L to 1.0 mol/L.
10. A method for preparing reduced conductive nano- metal particles comprising the step of reducing the conductive nano-metal particles from claim 5 or 6.
11. The method according to claim 10, in which the reduction is performed by heating the conductive nano-metal particles in an oxygen atmosphere or an inert atmosphere.
12. The method according to claim 11, in which the heating is performed after mixing the conductive nano-metal particles with an reducing agent.
13. Reduced conductive nano-metal particles prepared according to any one of claims 10 to 12.
14. The reduced conductive nano-metal particles according to claim 13, the content of the metal in the reduced conductive nano-metal particles is at least 95 wt% .
15. A nano-metal ink comprising the conductive nano- metal particles or reduced conductive nano-metal particles according to claim 1 or 13.
16. The nano-metal ink according to claim 15, which comprises : i ) 10 to 90 wt% of the conductive nano-metal particles or reduced conductive nano-metal particles; and ii ) 10 to 90 wt% of a solvent.
17. The nano-metal ink according to claim 15, in which the nano-metal ink comprises the conductive nano-metal particles and has a viscosity of 5000 to 10000 cps.
18. The nano-metal ink according to claim 15, in which the nano-metal ink comprises the reduced conductive nano- metal particles and has a viscosity of 10 to 500 cps.
19. The nano-metal ink according to claim 1, in which the nano-metal ink further comprises a dispersing agent, a thickening agent or an additive.
20. A nano-metal paste comprising: i ) 10 to 90 parts by weight of conductive nano-metal particles or reduced conductive nano-metal particles; ii ) 10 to 90 parts by weight of a solvent; and iii) 0.01 to 10 parts by weight of a thickening agent.
21. The nano-metal paste according to claim 20, in which the nano-metal paste has a viscosity of 80000 to 150000 cps .
22. A method for preparing a printed circuit board comprising the step of printing a pattern on a resin film using the nano-metal ink according to claim 15 or the paste according to claim 20.
23. The method according to claim 22, in which the printed circuit board is a flexible printed circuit board (FPCB) .
24. The method according to claim 22, which comprises the steps of: a) printing a metal wiring on a resin film using the nano-metal ink; b) drying the printed circuit board having the metal wiring printed thereon from the step a) ; and c) calcining the dried printed circuit board from the step b) . The metal contained in the nano-metal ink may be copper, silver, gold, platinum, nickel or a mixture thereof which has a low resistivity among conductive metals.
25. The method according to claim 22, in which the resin film used in the step a) is a thermal resistant resin film including PTFE or polyimide.
26. The method according to claim 24, in which the calcinations in the step c) is performed at 150 to 350°C for 10 to 30 minutes.
27. The method according to claim 22, in which the resin film used in the step a) is a resin film having a protective film thereon and the metal wiring is printed on the protective film using the nano-metal ink.
28. The method according to claim 22, in which the resin film used in the step a) is a resin film having an intermediate layer bonded thereto and the metal wiring is printed on the intermediate layer using the nano-metal ink.
29. The method according to claim 28, in which the intermediate layer is formed of an alloy of copper and nickel.
30. A printed circuit board prepared by the method according to any one of claims 22 to 29.
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