WO2014126400A1 - Encre à nanoparticules métalliques conductrices et son procédé de préparation - Google Patents

Encre à nanoparticules métalliques conductrices et son procédé de préparation Download PDF

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WO2014126400A1
WO2014126400A1 PCT/KR2014/001193 KR2014001193W WO2014126400A1 WO 2014126400 A1 WO2014126400 A1 WO 2014126400A1 KR 2014001193 W KR2014001193 W KR 2014001193W WO 2014126400 A1 WO2014126400 A1 WO 2014126400A1
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metal nanoparticles
ink
nanoparticles
metal
solvent
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PCT/KR2014/001193
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English (en)
Korean (ko)
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최민영
송용설
양혜윤
임진선
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주식회사 아모그린텍
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Priority claimed from KR1020140016141A external-priority patent/KR101655365B1/ko
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Publication of WO2014126400A1 publication Critical patent/WO2014126400A1/fr

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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
    • 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
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment

Definitions

  • the present invention relates to conductive metal nanoparticle inks and methods of manufacturing the same, and in particular, the surface area of nanoparticles is reduced by transforming spherical nanoparticles into flakes using bead mill solution dispersion.
  • Conductive metal nanoparticle ink capable of forming a metal pattern having a low specific resistance and high dispersibility even at low temperature firing as the ink is prepared by mixing at least two kinds of nanoparticle powders having different particle sizes. It is about.
  • the pattern forming method using photolithography has an advantage of realizing a microcircuit, but has a disadvantage in that a process is complicated and expensive equipment is required.
  • the screen printing method using the silver paste has the advantage that the process is simple, but there is a disadvantage that it is difficult to implement a circuit having an ultra-fine pattern to continue to replace the screen.
  • the laser transfer method is a method in which expensive silver is coated on the entire surface of a circuit, and then a required circuit is drawn by a laser, which consumes silver, which is a wiring material.
  • a method of patterning circuit wiring by a non-contact printing method through inkjet is a technique of forming a wiring by directly discharging a predetermined amount of ink to an accurate position through an inkjet head.
  • the process is simple and has the advantage of shortening the manufacturing time, it requires a high dispersibility of nanoparticles.
  • Metal nanoparticles of uniform particle size used in such metal nano inks are mostly made by a chemical method that is dispersed and synthesized in a solution.
  • a nanoparticle ink having electrical conductivity uses a method of using fractional distillation after mechanical stirring by mixing an ink solvent and a dispersion solvent.
  • the conventional metal nanoink manufacturing method described above also has to consider the boiling point for the fractional distillation of the dispersion solvent and the ink solvent, so there is a limit to the solvent selection.
  • the conventional use of a large amount of the dispersion solvent is not only a wastewater treatment problem in the washing process, but also has a lot of washing process, there is a problem of losing a lot of metal powder in the washing process.
  • the conductive ink has a low resistance value after sintering at low temperature and low temperature heat treatment is a priority requirement.
  • conductive silver (Ag) nanoparticle ink is composed of silver nanoparticles and a minimum dispersant for dispersing them based on an ink solvent.
  • a dispersion method through stirring is used in combination with a minimal dispersant for dispersing silver nanoparticles in an ink solvent.
  • this conventional conductive ink manufacturing process has a disadvantage that the sintering temperature of the dispersant and the size of the silver nanoparticles affect the sintering temperature, and the burning point of the dispersant becomes the sintering temperature of the ink.
  • the metal nanoparticles may contain electrolytes, dispersants, and reducing agents in the colloidal solution. Melted Thus, the colloidal solution is centrifuged to remove the electrolyte, the reducing agent and the dispersant and to obtain metal nanoparticles. In this case, even if centrifugation is carried out, the resulting metal nanoparticles remain with the surface of the particles capped with, for example, a water-soluble polymer dispersant or a water-dispersible polymer dispersant of a polyacryl, polyurethane, or polysiloxane system.
  • the conductive nanoparticle ink using the silver nanoparticles capped with the dispersant may prepare 40 wt% ink using, for example, TGME (Triethylene Glycol Monomethyl Ether) as an ink solvent, but the glass substrate is used as the ink. After coating (printing) and sintering to form a conductive pattern or wiring, the resistivity of the conductive pattern is obtained as shown in FIG. 1 according to the sintering temperature.
  • TGME Triethylene Glycol Monomethyl Ether
  • the factors that can affect the specific resistance during such low temperature firing are the high boiling point (249 ° C.) of the TGME solvent and the high decomposition temperature (290.73 ° C.) of the dispersant.
  • the oil-based metal ink has the advantages of smaller nanoparticle size, easier manufacturing of high concentration, and continuous ejection from the head, compared to the water-based metal ink, but the crack of the wiring of the printed image is severe and the line width is not uniform. Because of this, surface treatment is essential and has a disadvantage of high firing temperature.
  • Korean Patent Publication No. 2008-102098 in order to solve this problem, by selecting an ink additive soluble in a lipophilic solvent and optimizing the composition of the metal ink to increase the adhesive strength with the substrate when forming the wiring by inkjet printing to prevent cracking
  • an ink additive soluble in a lipophilic solvent in order to solve this problem, by selecting an ink additive soluble in a lipophilic solvent and optimizing the composition of the metal ink to increase the adhesive strength with the substrate when forming the wiring by inkjet printing to prevent cracking
  • a non-aqueous metal ink composition which hardens well at low temperature
  • distributed metal nanoparticle to the non-aqueous organic solvent with an additive is proposed.
  • non-aqueous metal ink composition metal nanoparticles synthesized in a non-aqueous solution are used for compatibility with a solvent by using a non-aqueous organic solvent.
  • a conventional inkjet metal ink composition has a complicated process procedure and generation of waste water, and as the baking is performed at 250 ° C., low temperature sintering at 150 ° C. or less has a problem.
  • Korean Patent Publication No. 2006-17686 discloses metal nanoparticles; Cosolvents; A dispersant for maintaining the metal nanoparticles in a stable dispersed state in the ink; And a conductive ink composition for an inkjet printer including a humectant for preventing clogging at the nozzle portion of the inkjet printer on the surface of the substrate, and ink pattern printing on the substrate surface and heat treating the ink composition printed on the substrate surface. It is proposed that the heat treatment temperature is 100 to 600 °C.
  • the method of forming the metal pattern only illustrates that the metal pattern is formed by performing heat treatment at a temperature of 300 to 500 ° C. through the embodiment, but does not suggest that the metal pattern is implemented by heat treatment at a low temperature of less than 150 ° C. I can't.
  • the present invention has been made in view of the above-described problems of the prior art, the object of which is to change the nanoparticles by transforming the sphere-shaped nanoparticles into flakes (flakes) using a bead mill solution dispersion method
  • the present invention provides a conductive metal nanoparticle ink for contact printing and a method of manufacturing the same, which can form a metal pattern having a low specific resistance even at low temperature firing by maximizing the surface area of the particles.
  • Another object of the present invention is to improve the dispersion characteristics as the ink is prepared by mixing two kinds of metal nanoparticles having different sizes, and to reduce the specific resistance of the sintering temperature and the metal pattern, and to reduce the material cost.
  • the present invention provides a metal nanoparticle ink and a method of manufacturing the same.
  • Still another object of the present invention is to provide a conductive metal nanoparticle ink capable of producing an environmentally friendly conductive metal nanoparticle ink by simplifying a manufacturing process by dispersing the metal nanoparticles directly with an ink solvent and dispersing the same by a bead mill solution dispersion method. It is to provide a manufacturing method thereof.
  • the present invention to achieve the above object, the metal nanoparticles made of flake shape; And an ink solvent in which the metal nanoparticles are dispersed.
  • the ink may include 10 to 90% by weight of the metal nanoparticles and 10 to 90% by weight of the ink solvent.
  • the surface area of the nanoparticles can be maximized to form a metal pattern having a low specific resistance even at low temperature firing.
  • the metal nanoparticles may be formed by mixing at least two metal nanoparticles having different sizes, thereby improving dispersing characteristics, lowering sintering temperature and specific resistance of the metal pattern, and reducing material costs.
  • the metal nanoparticles When the metal nanoparticles are prepared through electrolysis, the metal nanoparticles may further include a dispersant surrounding the metal nanoparticles.
  • the metal nanoparticles are any one selected from the group consisting of Ag, Pt, Au, Mg, Al, Zn, Fe, Cu, Ni, and Pd or It may be composed of two or more alloys, and the metal nanoparticles are any one selected from the group consisting of In, Ti, Cr, Ta, Tw and Co, which can be obtained by a chemical method or a mechanical method in addition to the electrolysis method. It may consist of one or two or more alloys.
  • the metal nanoparticles used in the conductive metal nanoparticle ink are preferably silver (Ag) nanoparticles in consideration of the material cost and the electrical conductivity and the degree of oxidation.
  • the present invention comprises the steps of preparing at least two spherical metal nanoparticles of different sizes; And a bead milling step of bead milling at least two spherical metal nanoparticles having different sizes, together with an ink solvent, to uniformly disperse the metal nanoparticles in the ink solvent and simultaneously to shape the shape of the metal nanoparticles into a flake shape. It provides a method for producing a conductive metal nanoparticle ink comprising a.
  • the present invention is a separation step of removing the electrolyte and dispersant from the colloidal solution containing the spherical metal nanoparticles obtained through electrolysis and separating the metal nanoparticles by size; A ball milling step of milling at least two metal nanoparticles having different sizes from the separated metal nanoparticles by ball milling; And a bead milling step of injecting the pulverized spherical metal nanoparticles together with the ink solvent to uniformly disperse the metal nanoparticles in the ink solvent and simultaneously shaping the shape of the metal nanoparticles into a flake shape. It provides a method for producing a conductive metal nanoparticle ink, characterized in that.
  • the conductive metal nanoparticle ink according to the present invention the metal nanoparticles made of a flake shape; And an ink solvent in which the metal nanoparticles are dispersed, and the ink includes 10 to 90% by weight of the metal nanoparticles and 10 to 90% by weight of the ink solvent.
  • the conductive metal nanoparticle ink contains less than 10% by weight of the metal nanoparticles
  • the content of the conductive nanoparticles is so small that the resistance of the circuit pattern is reduced. This increasing problem may occur, and the viscosity is too high when containing more than 70% by weight of the metal nanoparticles inkjet printing is impossible.
  • Ink having a concentration of 70 to 90 wt% has high viscosity and is not jetted, and may be applied as a conductive paste for screen printing.
  • the ink is preferably prepared by adding an auxiliary solvent to the ink solvent, so that the bead mill process is performed, and then, dispersion is performed in the ink solvent, followed by fractional distillation in a subsequent process.
  • a low concentration ink having a low content of metal nanoparticles may be obtained by diluting a high concentration ink.
  • the content of the metal nanoparticles in the ink is 10 to 50% by weight, it shows excellent jetting property even when a head of 30 pl (pico liter) nozzle size is used for inkjet printing, and the content of the metal nanoparticles is 10 In the case of 40 wt% to 40 wt%, excellent jetting property is shown in the head of the 5 pl nozzle size.
  • the metal nanoparticles may be prepared through electrolysis, or may be obtained by a chemical method or a mechanical method in addition to the electrolysis method, and those prepared through electrolysis are preferable in view of the size or uniformity of the nanoparticles.
  • the metal nanoparticles used in the ink of the present invention are manufactured by electrolysis, the metal nanoparticles having a spherical shape are separated from the colloidal solution by centrifugation and then pulverized through a ball milling and a bead milling process. As the molding is performed, the spherical metal nanoparticles are deformed into a flake shape.
  • Ink prepared using flake-shaped metal nanoparticles according to the present invention is compared to the conventional ink prepared using spherical metal nanoparticles, when the pattern is formed into ink and then subjected to a sintering process
  • the ink of the present invention has a larger contact area than the conventional ink, thereby lowering the resistivity of the metal pattern.
  • the ink of the present invention using flake-shaped metal nanoparticles has a large surface area because the metal nanoparticles are flattened at the time of pattern formation, and thus the contact between the particles is greater than the metal pattern made of spherical metal nanoparticles.
  • the area is increased. Accordingly, even after sintering, the stacking density of the metal nanoparticles is increased to lower the specific resistance, and the adhesion to the substrate is also improved.
  • the metal nanoparticles When the metal nanoparticles are prepared through electrolysis, they are present in a colloidal state in an electrolyte in a form surrounded by a dispersant. In this case, when the metal nanoparticles solidify the colloidal solution in which the metal nanoparticles are dispersed, the conductive nanoparticle ink is prepared according to the centrifugation process, and printed by contact method to form a circuit wiring. Since most of the dispersant that adversely affects can be removed, electrical conductivity can be expected to be improved.
  • the dispersant surrounding the metal nanoparticles contained in the conductive nanoparticle ink is preferably included in the range of 0.5 to 10% by weight, and less than 0.5% by weight may cause a problem in the dispersion of the ink.
  • the high concentration ink having a high content of the metal nanoparticles also increases the content of the dispersant. In this case, the dispersant is undesirable due to the aggregation of the dispersant and the increase in the specific resistance when it exceeds 10% by weight.
  • the present invention using nanoparticles having a flake shape shows better resistivity properties than conventional inks using spherical nanoparticles.
  • the surface capping metal nanoparticles can be easily dispersed in a solvent to be easily prepared in a dispersible ink, It shows dispersion stability that does not aggregate for a long time even after being prepared with ink.
  • Solvents that can be used for ink preparation include terpineol, ethyl alcohol, methyl alcohol, isopropyl alcohol, 2-methoxy ethanol, Alcohols such as propyl alcohol, pentyl alcohol, hexyl alcohol, butyl alcohol, octyl alcohol, ethylene glycol, diethylene glycol (diethylene glycol), triethylene glycol, poly-ethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, tri glycol monomethyl ether (TGME: Triethylene Glycol Monomethyl Ether), Glycols such as Propylene Glycol Methyl Ether Acetate, Glycerine, Acetone, Formamide (f ormamide, methyl ethyl ketone, methane, ethane, ethane, propane, butane, pentane, hexane, heptane, octane ), Most solvents such as nonane, decane,
  • the conductive nanoparticle ink may have different dispersion states, specific resistance, and jetting properties even through the same process depending on the ink solvent and the dispersant.
  • the size selection is performed to remove the electrolyte and the dispersant from the colloidal solution containing the spherical metal nanoparticles obtained through electrolysis and to select the metal nanoparticles by size. step; A ball milling step of milling at least two metal nanoparticles having different sizes from the separated metal nanoparticles by ball milling; And a bead milling step of injecting the pulverized spherical metal nanoparticles together with the ink solvent to uniformly disperse the metal nanoparticles in the ink solvent and simultaneously shaping the shape of the metal nanoparticles into a flake shape. It provides a method for producing a conductive metal nanoparticle ink, characterized in that.
  • the metal nanoparticle colloidal solution may be a metal nanoparticle colloidal solution obtained by direct current or alternating current electrolysis.
  • the separation or removal of the electrolyte and the dispersant from the metal nanoparticle colloidal solution may use a centrifugal separation method. Since the obtained metal nanoparticles cannot be completely removed when the electrolyte and the dispersant are separated or removed by centrifugation, the surface of the particles is capped with a polyacrylic, polyurethane, or polysiloxane-based water-soluble polymer dispersant or water-dispersible polymer dispersant. And remain.
  • the dispersant is, for example, Disperbyk TM -111, Byk TM -154, Disperbyk TM -180, Disperbyk TM -182, Disperbyk TM -190, Disperbyk TM -190, Disperbyk TM -192, Disperbyk TM -193, Disperbyk TM -2012, Disperbyk TM -2015, Disperbyk TM -2090, Disperbyk TM -2091; Tevo TM 715w, Tego TM 735w, Tego TM 740w TM, Tego TM 745w TM, Tego TM 750w, Tego TM 755w, Tego TM 775w from Evonik; Solbrise TM 20000, Solsperse TM 43000, Solsperse TM 44000 from Lubrizol; Ciba's EFKA TM 4585; Dow's Orotan TM 731A, Orotan TM 1124; T
  • Removal of the electrolyte and the dispersant from the metal nanoparticle colloidal solution using a centrifugal separation method, by separating the precipitated metal nanoparticles by size by the centrifugation method by size can be easily prepared mixed metal nanoparticles. .
  • the centrifugation is preferably carried out at 8000 rpm for 4 hours, in which case a yield of 95% or more is obtained.
  • the viscosity of the ink obtained according to the invention ranges from 10 to 72585 cP and increases in proportion to the content of the metal nanoparticles, ie concentration.
  • the viscosity shows a range of 5477 to 72585 cP.
  • the ink is not jettable and can be used for screen printing.
  • the metal nanoparticles precipitated by the centrifugation are stacked in order from the largest to the smallest, and thus the metal nanoparticles obtained for each layer by size are obtained in a state of being agglomerated together.
  • At least two metal nanoparticles having different sizes from the separated metal nanoparticles are first milled by ball milling and separated into small sizes, thereby effectively milling in the subsequent bead milling process. Pretreatment is carried out.
  • a co-solvent is added as needed, and after the dispersing step, the co-solvent is further removed by fractional distillation.
  • the auxiliary solvent preferably has a boiling point lower than that of the ink solvent so that the auxiliary solvent can be removed by fractional distillation.
  • the auxiliary solvent may be added for supplementation of the prescribed amount when the mixed amount of the metal nanoparticles and the ink solvent to be added to the bead mill is less than the sample prescribed amount to be added to the bead mill.
  • the auxiliary solvent is a small content of the ink solvent mixed with the metal nanoparticles in the case of high concentration ink is added for smooth transfer when supplying the mixture to the bead mill using a feed pump, or after the metal nanoparticles bead mill equipment after bead milling It can be added as a washing solvent to wash what is attached to it.
  • the auxiliary solvent is preferably added above the prescribed amount replenishment to supplement the sample when the mixed amount of the metal nanoparticles and the ink solvent is less than the sample amount to be added to the bead mill.
  • the auxiliary solvent may be at least one selected from the group consisting of ethanol, methanol, propanol, isopropanol, acetone, toluene and hexane.
  • the conductive metal nanoparticle ink obtained according to the manufacturing method may include 10 to 90% by weight of the metal nanoparticles and 10 to 90% by weight of the ink solvent.
  • 10 to 80% by weight ink may be prepared using the 90% by weight ink.
  • the ratio of the mixing amount of the metal nanoparticles and the ink solvent and bead added to the bead mill is set to 3: 7.
  • Beads used for bead milling preferably have a size of 100 to 200um, and when the size of the beads is less than 100um, it takes a long time to form the spherical metal nanoparticles into a flake shape, the work efficiency is reduced, If it exceeds 200um there is a problem that the uniform dispersion of the metal nanoparticles are not made.
  • the amount of beads put into the bead mill is 400 g is the ideal bead amount when the sample standard of the bead mill equipment is 1L, and even if too large, the dispersibility is low, the specific resistance is also low when the dispersibility is poor.
  • the bead milling process is preferably performed at 500 to 6000 rpm for 1 to 10 hours. That is, the rotor rotation speed of the bead mill is preferably 500 ⁇ 6000rpm, if the rpm is too fast can not give sufficient energy for the crushing metal nanoparticles, there is a problem that the dispersion force is rather falling. If the rotor rotational speed of the bead mill is out of the range of 500 ⁇ 6000rpm also increases the size of the nanoparticles, the dispersion is lowered and the specific resistance is increased.
  • the metal nanoparticle ink when manufacturing the metal nanoparticle ink, at least two metal nanoparticles having different sizes from the metal nanoparticles obtained in the size selection step are pulverized by ball milling, and the at least two spherical particles having different pulverized sizes are pulverized.
  • the metal nanoparticles of the phase are added to the bead mill together with the ink solvent to uniformly disperse the metal nanoparticles in the ink solvent and simultaneously shape the metal nanoparticles into a flake shape to prepare an ink.
  • the ink is prepared by bead milling one type of metal nanoparticles having the same size, the specific resistance of the metal pattern obtained using the same is low, but since the precipitation of the metal nanoparticles occurs, the dispersibility is poor. After storage it becomes impossible to use.
  • At least two kinds of metal nanoparticles having different sizes are preferably mixed.
  • the at least two kinds of metal nanoparticles having different sizes are 20 nm and 100 nm, and the mixing ratio X of the metal nanoparticles of 20 nm and the metal nanoparticles of 100 nm is 8: 2 ⁇ X ⁇ 0: It is preferable to set it to 10 range.
  • the mixing ratio (X) of the metal nanoparticles of 20 nm and the metal nanoparticles of 100 nm is larger than 8: 2 by weight ratio, the wire resistance, sheet resistance and specific resistance are greatly increased, and the metal nanoparticles of 20 nm at the mixing ratio (X) are increased.
  • the content of the particles is 0% by weight, precipitation of the nanoparticles occurs and there is a problem in that dispersibility is poor.
  • the surface area of the nanoparticles is maximized so that a low specific resistance is obtained even at low temperature firing.
  • a conductive pattern can be formed.
  • the dispersing characteristics may be improved, the sintering temperature and the specific resistance of the metal pattern may be reduced, and the material cost may be reduced.
  • the conductive metal nanoparticle ink having low specific resistance can be prepared.
  • the present invention simplifies the manufacturing process by using only the ink solvent without using a dispersion solvent, and eliminates the problem of wastewater treatment and the loss of many metal nanoparticle powders that occur in the washing process according to the conventional use of a large amount of the dispersion solvent. can do.
  • the fineness of the conductive nanoparticle ink is increased by increasing the degree of dispersion of the metal nanoparticles by using bead milling. Dispersion can be expected.
  • the present invention is not limited to the selection of an organic or aqueous solvent by the strong dispersing force of the bead mill.
  • the present invention can be expected to have a high recovery rate because the continuous operation is possible when dispersing the metal nanoparticles using bead milling (bead milling).
  • the present invention is not limited to the kind of the solution to be initially synthesized, and by solidifying and synthesizing the conductive nanoink, the colloidal solution in which the metal nanoparticles are dispersed can be included, thereby facilitating solvent exchange.
  • the present invention can use the colloidal solution in which the metal nanoparticles are initially dispersed, as it is, and the composition is simple and the manufacturing process is simple, so that the conductive metal nanoparticle ink can be manufactured at low cost.
  • the present invention can be mass-produced at low cost by a roll-to-roll method such as gravure, gravure offset, screen printing, coating, etc., and can realize a low resistivity metal pattern even at low temperature sintering.
  • 1 is a graph showing the specific resistance according to the sintering temperature for a conventional ink obtained using spherical Ag nanoparticles
  • FIG. 2 is a process flow diagram illustrating a method of manufacturing a conductive metal nanoparticle ink according to a preferred embodiment of the present invention
  • 3A and 3B are SEM photographs showing 20 nm and 100 nm spherical Ag nanoparticles used in the present invention, respectively.
  • Figure 4 is a SEM photograph showing the flake-shaped Ag nanoparticles obtained after performing the bead milling process according to the present invention
  • 5 is a cross-sectional SEM photograph when forming a metal pattern with an ink prepared by bead milling a mixed powder mixed with 20 nm and 100 nm Ag nanoparticles at a ratio of 5: 5 according to the present invention with an ink solvent,
  • FIG. 6 is a cross-sectional SEM photograph when forming a metal pattern with an ink prepared by bead milling together with an ink solvent using only 100 nm Ag nanoparticles according to the present invention
  • FIG. 7 is a graph showing the particle size according to the mixing ratio of 20nm and 100nm Ag nanoparticles when ball milling and bead milling mixed Ag nanoparticles according to the present invention.
  • FIG. 10 is a graph showing the sheet resistance characteristics of the ink obtained by using the flake-shaped Ag nanoparticles according to the present invention according to the sintering time.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a conductive metal nanoparticle ink according to a preferred embodiment of the present invention.
  • the method for producing a conductive metal nanoparticle ink comprises the steps of preparing a colloidal solution containing spherical metal nanoparticles by electrolysis (S21); A size selection step (S21) of removing the electrolyte, the reducing agent and the dispersant from the colloidal solution containing the obtained spherical metal nanoparticles by centrifugation, and selecting and classifying the centrifuged metal nanoparticles by size; A ball milling step (S24) of grinding the at least two metal nanoparticles having different sizes from the metal nanoparticles selected by the size by ball milling; Bead milling step of putting the pulverized spherical metal nanoparticles together with the ink solvent to bead mill (bead mill) to uniformly disperse the metal nanoparticles in the ink solvent and to shape the shape of the metal nanoparticles into flake shape ( S25); Removing the auxiliary solvent by fractional distillation
  • colloidal solutions containing the metal nanoparticles can be obtained using, for example, direct current (DC) or alternating current (AC) electrolysis methods. That is, the metal nanocrystal obtained by using the direct current electrolysis method proposed in the Patent No. 1001631 proposed by the present applicant, the alternating current electrolysis method proposed in the Patent Publication No. 2011-31121, or by using another well-known electrolysis method Colloidal solutions containing particles can be used.
  • DC direct current
  • AC alternating current
  • the present invention preferably contains metal nanoparticles having a uniform shape and a narrow particle distribution (uniform particles) of a desired size (20 to 100 nm), which is characterized by dispersing agent in a specific frequency band of an AC power source. It can be obtained by adjusting the concentration of the reducing agent in accordance with the intensity of the current of the alternating current power applied. Therefore, the colloidal solution containing the metal nanoparticles obtained by using the electrolysis method includes an electrolyte, a reducing agent and a dispersant introduced into the reaction vessel for the electrolysis process.
  • the metal nanoparticle colloidal solution having a particle size in the range of 20 to 100 nm is centrifuged in order to remove the electrolyte, the reducing agent and the dispersant which are unnecessary for ink preparation.
  • the metal nanoparticle colloidal solution having a particle size in the range of 20 to 100 nm is centrifuged in order to remove the electrolyte, the reducing agent and the dispersant which are unnecessary for ink preparation.
  • alternating electrolysis is performed using a pair of silver (Ag) electrodes for a predetermined time, for example, in a centrifuge, since the dissolved electrolyte water contains a large number of silver nanoparticles in an excess dispersant, Centrifugation at 8000 RPM for 4 hours to remove the electrolyte, reducing agent and dispersant contained in the colloidal solution to obtain silver nanoparticles.
  • the metal nanoparticles obtained are left in a state where the particle surface is capped with, for example, a water-soluble polymer dispersant or a water-dispersible polymer dispersant of a polyacryl, polyurethane, or polysiloxane system.
  • the metal nanoparticles classified by size after centrifugation are mixed with at least two kinds of metal nanoparticles having different sizes, for example, 20 nm and 100 nm, according to a preset mixing ratio, followed by first milling by ball milling. (S24).
  • the mixing ratio (X) of the metal nanoparticles of 20 nm and the metal nanoparticles of 100 nm is preferably set in a weight ratio of 8: 2 ⁇ X ⁇ 0:10, preferably in a range of 8: 2 to 3: 7.
  • the mixing ratio (X) of the metal nanoparticles of 20 nm and the metal nanoparticles of 100 nm is larger than 8: 2 by weight ratio, the wire resistance, sheet resistance and specific resistance are greatly increased, and the metal nanoparticles of 20 nm at the mixing ratio (X) are increased.
  • the content of the particles is 0% by weight, precipitation of the nanoparticles occurs and there is a problem in that dispersibility is poor.
  • the first milling using the ball milling is milling to disperse the agglomerated nanoparticles during centrifugation, and is a pretreatment step for increasing the efficiency of the subsequent bead milling, for example, 100 rpm for 15 hours.
  • the pulverized spherical metal nanoparticles are added to a bead mill together with an ink solvent to prepare the ink, thereby uniformly dispersing the metal nanoparticles in the ink solvent and simultaneously forming the shape of the metal nanoparticles into a flake shape.
  • Bead milling is performed to mold (S25).
  • the process of making a bead mill sample to be added to the bead mill at the time of bead milling is as follows.
  • the sample prescribed amount of the bead mill equipment is 1L
  • the amount of the metal nanoparticles to be added determines the amount of the auxiliary solvent to be added together with the ink solvent by the concentration of the ink to be prepared finally.
  • the auxiliary solvent is a high concentration ink, that is, the content of the ink solvent mixed with the metal nanoparticles is small.
  • the ink solvent is added for smooth transfer in the feed pump.
  • the metal nanoparticles may be added as washing solvents to clean the adherence to the bead mill equipment.
  • the mixed amount of the metal nanoparticles and the ink solvent is less than 1 L of the sample prescribed amount to be added to the bead mill, for example, when the amount of the metal nanoparticles is not sufficient as 270 g and the ink solvent TGME 320 g, Ethanol used as a solvent may cover the insufficient portion (410g).
  • the additional amount of the auxiliary solvent is correspondingly determined.
  • a sample prepared by diluting with ethanol to a viscosity of 100 cP or less is prepared.
  • the bead mill is prepared by injecting a bead mill sample prepared above, that is, primary milled spherical metal nanoparticles and an ink solvent (with an auxiliary solvent, if necessary) into a bead mill.
  • the metal nanoparticles are uniformly dispersed in the ink solvent and spherical.
  • the shape of the metal nanoparticles of the phase is deformed into a flake shape.
  • beads used for bead milling are 100-200um in size, and when the beads are small in size of less than 100um, it takes a long time to form spherical metal nanoparticles into flake shape. The efficiency is lowered, and if it exceeds 200um it is not possible to uniformly disperse the metal nanoparticles.
  • the ratio of the mixing amount of the metal nanoparticles and the ink solvent and bead added to the bead mill is set to 3: 7.
  • the sample prescribed amount of the bead mill is 1L
  • the amount of beads to be put into the bead mill is 400 g is the most ideal bead amount, even if too large, the dispersibility is low, if the dispersibility is low, the resistivity is also low.
  • the rotor rotation speed of the bead mill is too fast exceeding 6000rpm, sufficient energy necessary for crushing cannot be given to the metal nanoparticles, so the dispersing force is lowered. If the rotor rotation speed of the bead mill is outside the range of 500 ⁇ 6000rpm, the size of nanoparticles In addition, the dispersion becomes low and the resistivity increases accordingly.
  • the most preferable bead mill condition is 4000 RPM, 1 to 2 hours, in which case the specific resistance is lowest while ensuring dispersibility (size of nanoparticles).
  • the auxiliary solvent is removed by fractional distillation when ethanol or the like is added as a co-solvent to meet the sample prescribed amount of the bead mill equipment or to prepare a high viscosity ink (S26).
  • the auxiliary solvent is required to have a boiling point lower than the boiling point of the ink solvent so that it can be removed by fractional distillation.
  • the auxiliary solvent one selected from the group consisting of ethanol, methanol, propanol, isopropanol and acetone can be used. have.
  • a fractional distillation process is performed only when ethanol is added in addition to the ink solvent.
  • 400 g of metal nanoparticles and 600 g of ink solvent (TGME) are used to prepare an ink having a metal nanoparticle content of 40 wt%.
  • the ink can be prepared without a fractional distillation process.
  • additional auxiliary solvent is added for smooth transfer in the feed pump when feeding the mixture from the hopper to the stirrer or bead mill using the feed pump.
  • a silver colloidal solution in which silver nanoparticles were dispersed using the alternating current electrolysis method proposed in Korean Patent Application Publication No. 2011-31121 was prepared.
  • electrolytes, dispersants and reducing agents are dissolved in the silver colloidal solution.
  • centrifugation is performed at 8000 RPM for 4 hours. The particles were obtained.
  • bead milling was performed to prepare the ink of Samples 1 to 9.
  • the mixing ratio between the 20 nm silver (Ag) nanoparticles and the 100 nm silver (Ag) nanoparticles is all based on weight ratio.
  • the bead mill conditions were rotor rpm: 2000 and 4000, pump rpm: 250 ml / min, bead size: 100-200 um.
  • the size (diameter) of the nanoparticles was measured by DLS (Dynamic Light Scattering) method.
  • FIG. 3A and 3B are SEM photographs showing 20 nm silver nanoparticles and 100 nm silver nanoparticles each having a spherical shape
  • FIG. 4 is an SEM photograph showing flake-shaped Ag nanoparticles obtained after the bead milling process according to the present invention. Is shown.
  • the flake-shaped Ag nanoparticles obtained by bead milling spherical silver nanoparticles each have a plate-like structure, and thus have a large surface area. As a result, the contact area between the particles is large. It can be seen that the increase.
  • FIG. 5 is a cross-sectional SEM photograph when a metal pattern is formed from the ink of Sample 6 prepared by bead milling a mixed powder of 20 nm and 100 nm spherical Ag nanoparticles in a ratio of 5: 5 according to the present invention with an ink solvent;
  • FIG. 6 is a cross-sectional SEM photograph when forming a metal pattern with ink of Sample 9 prepared by bead milling with an ink solvent using only 100 nm spherical Ag nanoparticles according to the present invention.
  • the wire resistance, sheet resistance, and specific resistance show a tendency that the higher the mixing ratio (X) of the 20nm Ag nanoparticles is from 10: 0 to 0:10, the smaller the lower.
  • the mixing ratio of 20nm Ag nanoparticles is 3: 7, it shows the lowest wire resistance, sheet resistance and specific resistance.
  • the ball mill was progressed for 15 hours ( ⁇ ), followed by bead milling 2000 rpm, 30 minutes ( ⁇ ) and bead milling 4000 rpm, 1 hour ( ⁇ ) After proceeding, the obtained particle size was measured and described in Table 2 below, and is graphically represented in FIG. 7.
  • the particle size increased as the mixing ratio of the 100 nm spherical Ag nanoparticles increased, and as the bead milling rpm was increased and the treatment time was long.
  • the specific resistance decreased as the mixing ratio of the 100 nm spherical Ag nanoparticles increased, and decreased as the bead milling rpm and the treatment time increased.
  • the mixing ratio of 20 nm and 100 nm spherical Ag nanoparticles was set to 6: 4 (sample 5), and bead milling was performed at 4000 rpm for 4 hours, and then the sintering temperature was obtained using the 20 wt% ink.
  • the specific resistance according to the sintering temperature was measured in the range of 130 ° C. to 200 ° C. and shown in FIG. 9.
  • the ink of the present invention was shown to be excellent in the resistivity characteristics at the sintering temperature of 130 °C to 150 °C. Therefore, plastic substrates such as polyethylenenaphthalate (PEN), polyethersulfone (PES), cyclic olefin copolymer (COC), polyimide (COC) and polyimide (PI) having a use temperature of 150 ° C or higher Edo coating process, gravure, gravure offset or screen printing, such as contact printing method to form a pattern and then sintered to form a conductive pattern.
  • PEN polyethylenenaphthalate
  • PES polyethersulfone
  • COC cyclic olefin copolymer
  • COC polyimide
  • PI polyimide
  • the present invention can be applied to various low-temperature firing applications such as an electromagnetic interference (EMI) film, a touch screen panel (TSP), a radio frequency identification (RFID) tag or an antenna or paper.
  • EMI electromagnetic interference
  • TSP touch screen panel
  • RFID radio frequency identification
  • the mixing ratio of 20 nm and 100 nm spherical Ag nanoparticles was set to 6: 4 (sample 5), and bead milling at 4000 rpm for 4 hours, followed by spin coating using the obtained 20 wt% ink.
  • the sintering temperature was changed to 130 °C ( ⁇ ), 150 °C ( ⁇ ), 170 °C ( ⁇ ) respectively, and the sintering time (4 minutes, 15 minutes, 30 minutes, 45 minutes, 60
  • the sheet resistance according to the minute is measured and shown in Table 4 and FIG. 10.
  • the sheet resistance properties of the ink prepared according to the present invention were found to be applicable to applications requiring low-temperature firing and a short time firing process.
  • the sheet resistance is about 2 times lower than the line resistance.
  • the viscosity of the ink can be applied to a variety of contact printing methods, such as gravure for the touch screen panel (TSP) manufacturing, gravure offset process, coating process for EMI film production.
  • TSP touch screen panel
  • the conductive metal nanoparticle ink is manufactured by using silver nanoparticles as the metal nanoparticles, but it is of course possible to use other kinds of metal nanoparticles such as Cu which can be used for ink production.
  • the present invention maximizes the surface area of nanoparticles by transforming spherical nanoparticles into plate flakes using bead mill solution dispersion, and at least two nanoparticle powders having different particle sizes.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

La présente invention concerne une encre à nanoparticules métalliques conductrices et son procédé de préparation. La surface de nanoparticules est maximisée par transformation de nanoparticules sphériques en flocons lamellaires à l'aide d'un procédé de dispersion de solution en broyeur à billes ; et un modèle métallique présentant une faible résistivité et une haute dispersibilité peut être formé même lors de la mise en œuvre d'un frittage à basse température selon une préparation d'une encre, par mélange d'au moins deux poudres de nanoparticules présentant différentes tailles de particule. L'encre à nanoparticules métalliques conductrices de la présente invention comprend des nanoparticules métalliques en forme de flocon et un solvant d'encre dans lequel les nanoparticules métalliques sont dispersées ; et les nanoparticules métalliques sont de préférence formées par mélange d'au moins deux types de nanoparticules métalliques présentant différentes tailles de particule. L'encre peut être préparée par : pulvérisation d'au moins deux types de nanoparticules métalliques sphériques, présentant différentes tailles de particule, par broyage à boulets ; et broyage à billes des nanoparticules métalliques sphériques pulvérisées avec un solvant d'encre, ce qui disperse ainsi de manière homogène les nanoparticules métalliques dans le solvant d'encre et donne simultanément aux nanoparticules métalliques une forme de flocon.
PCT/KR2014/001193 2013-02-14 2014-02-13 Encre à nanoparticules métalliques conductrices et son procédé de préparation WO2014126400A1 (fr)

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KR1020140016141A KR101655365B1 (ko) 2013-02-14 2014-02-12 전도성 금속 나노입자 잉크 및 그의 제조방법

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100099970A (ko) * 2009-03-04 2010-09-15 엘에스전선 주식회사 나노미터 두께의 금속 마이크로판을 함유하는 전도성 페이스트용 조성물
KR20110019421A (ko) * 2008-06-12 2011-02-25 나노마스 테크놀러지스, 인코포레이티드 전도성 잉크 및 페이스트
JP2011044509A (ja) * 2009-08-20 2011-03-03 Mitsubishi Materials Corp 導電性インク組成物及び該組成物を用いて形成された太陽電池モジュール
KR20120138703A (ko) * 2011-06-14 2012-12-26 주식회사 아모그린텍 전도성 금속 나노입자 잉크 및 그의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110019421A (ko) * 2008-06-12 2011-02-25 나노마스 테크놀러지스, 인코포레이티드 전도성 잉크 및 페이스트
KR20100099970A (ko) * 2009-03-04 2010-09-15 엘에스전선 주식회사 나노미터 두께의 금속 마이크로판을 함유하는 전도성 페이스트용 조성물
JP2011044509A (ja) * 2009-08-20 2011-03-03 Mitsubishi Materials Corp 導電性インク組成物及び該組成物を用いて形成された太陽電池モジュール
KR20120138703A (ko) * 2011-06-14 2012-12-26 주식회사 아모그린텍 전도성 금속 나노입자 잉크 및 그의 제조방법

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