Classifications

• • 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
  • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/10—Intaglio printing ; Gravure printing
• • 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
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/01—Dielectrics
  • H05K2201/0104—Properties and characteristics in general
  • H05K2201/0108—Transparent
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0242—Shape of an individual particle
  • H05K2201/0248—Needles or elongated particles; Elongated cluster of chemically bonded particles
• • 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
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0242—Shape of an individual particle
  • H05K2201/026—Nanotubes or nanowires
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
  • H05K3/1275—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing

Definitions

• Gravure coating is a known coating technology, see, for example, Gravure Process and Technology, Gravure Education Foundation and Gravure Association of American, Quebecor World Inc., 2003, which is hereby
• At least some embodiments provide a method comprising providing an ink comprising nanowires, the nanowires having a distribution of lengths, the distribution having a mean L m and standard deviation ⁇ ; providing a surface and a plurality of indentations in the surface, the plurality of indentations having a density of LPI (lines/inch); transferring the ink into the plurality of indentations; and transferring at least a portion of the ink from the indentations to a printing medium, where LPI is less than about 2.5 x 10 4 micron lines / inch divided by L m +3a.
• the nanowires may, for example, have aspect ratios of at least about 50, or at least about 100, or at least about 1000, or at least about 10,000.
• the surface may, for example, be the exterior (i.e., outward-facing) surface of a rotogravure cylinder.
• the ink may further comprise a polymer binder, such as, for example, a cellulosic polymer.
• a polymer binder such as, for example, a cellulosic polymer.
• some embodiments further provide methods where the printing medium is moving at a speed of U (feet/min) relative to the surface, the ink has a viscosity ⁇ (cps), and LPI is greater than about 473 - 67.6 ln( ⁇ ⁇ log 10 (U) ) lines per inch.
• Other embodiments provide conductive films produced according to such methods.
• Yet still other embodiments provide articles comprising such transparent conductive films such as, for example, electronic displays, touch screens, portable telephones, cellular telephones, computer displays, laptop computers, tablet computers, point-of-purchase kiosks, music players, televisions, electronic games, electronic book readers, transparent electrodes, solar cells, light emitting diodes, other electronic devices, medical imaging devices, medical imaging media, and the like.
• transparent conductive films such as, for example, electronic displays, touch screens, portable telephones, cellular telephones, computer displays, laptop computers, tablet computers, point-of-purchase kiosks, music players, televisions, electronic games, electronic book readers, transparent electrodes, solar cells, light emitting diodes, other electronic devices, medical imaging devices, medical imaging media, and the like.
• FIG. 1 shows an optical micrograph of the comparative coating sample Comp- 1.
• FIG. 2 shows an optical micrograph of the inventive coating sample Inv- 1.
• Transparent conductive films prepared through networking of silver nanowires have the potential to replace indium tin oxide as transparent conductors in many
• Transparent conductive films prepared from silver nanowires in organic binder can produce materials with electric resistivity as low as 10 ohm/sq with total light transmittance greater than about 85% when coated on a suitable support, such as, for example, polyethylene terephthalate (PET).
• PET polyethylene terephthalate
• such transparent conductive films can be prepared via conventional coating technologies including, for example, spray painting, dip- coating, spin-coating, knife coating, Mayer rod coating, roll coating, gravure coating, slot-die coating, slide coating, curtain coating, extrusion coating, and the like.
• gravure coating or printing can be an excellent technique to print conductive networks of metal nanowire meshes on a flexible substrate, since such printing methods apply only minor amounts of shear force to the coating solution during the coating process, even when printing transparent conductive films at very high speeds.
• Gravure printing of very thin layers of transparent and conductive coatings can also achieve excellent uniformity, both crossweb and downweb, since the engraved recesses, or cells, on the gravure cylinder precisely define the amount of coating solution to be delivered to the web.
• the ability to accurately control the cell transfer efficiency, or solution pickout efficiency, from the cells, as well as the ability to effectively merge solutions from individual cells can affect the capability for forming uniform conductive coatings with no visible cell patterns.
• the density of gravure cells, or lines per inch (LPI) of the gravure pattern on a given gravure cylinder needs to be chosen to match the coating solution rheology in order to provide sufficient solution pickout efficiency, as well as coating consistency and uniformity. For low viscosity solutions, fine cylinders with higher LPI are preferred, whereas for higher viscosity solutions, coarser cylinders are preferred.
• Applicants have recognized that for coating of dispersion solutions containing one-dimensional metal nanowires, knowledge of the metal nanowire length distribution can be taken into account in selecting the appropriate gravure cylinder pattern and cell size.
• the gravure cell opening size approaches the average wire length size plus the standard deviation of the length distribution, the gravure cells can behave like an effective filter that allows only small amounts of short wires to be incorporated into the grooves.
• the resulting coating though similar in wet lay down, would show little or no conductivity due to the diminished fraction of longer wires.
• use of gravure cylinders with larger cell opening sizes can allow nanowires to enter gravure cells without such severe skewing of the wire size distributions in the cells.
• the coating solution rheology should also be considered.
• the preferred gravure cylinder cell density for printing one-dimensional nanoparticle solutions expressed in lines per inch (LPI) is provided by the combined inequalities of the equations:
• a and B are constants specific to the polymer binder and solvent composition.
• — ⁇ is the coating solution viscosity in centipoises.
• U gravure coating web speed, in feet per minute.
• L m and ⁇ are the average length and standard deviation, respectively, of the one-dimensional nano-particles employed in the coating solution, in microns ( ⁇ ).
• Cellulosic polymers are polysaccharides or derivatives of polysaccharides, that may have degrees of polymerization of, for example, 100, 1000, 10,000, or more. These include derivatives of cellulose, such as, for example, esters and ethers of cellulose.
• Cellulosic esters include cellulose acetates, such as, for example, cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate (CAB), and the like.
• Cellulosic ethers include, for example, methylcellulose, ethylcellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and the like. These and other such cellulosic polymers will be understood by those skilled in the art.
• a method comprising:
• LPI is less than about 2.5 x 10 4 micron lines / inch divided by L m +3a.
• D The method according to embodiment C, wherein the polymer binder comprises at least one cellulosic polymer.
• the printing medium is moving at a speed of U (feet/min) relative to the surface, the ink has a viscosity ⁇ (cps), and LPI is greater than about 473 - 67.6 ln( ⁇ ⁇ logioOJ) ) lines per inch.
• Silver nanowire dispersion solutions comprising the following ingredients were prepared:
• MEK Methyl ethyl ketone
• ethyl lactate isopropanol
• Samples Inv-1 through Inv-6 exhibited excellent coating quality and good conductivity. Sample Comp-1 was non- conductive, while Samples Comp-2 and Comp-3 exhibited poor coating quality. Accordingly, Samples Inv-1 through Inv-6 satisfied the conditions of both Eqn. (la) and Eqn. (lb).
• Sample Comp-1 is depicted in Figure 1. As shown in Table 1, coating quality was only fair and this film was not conductive. This is believed to be due to poor inclusion of nanowires from the dispersion solution. Note that Sample Comp-1 did not satisfy the conditions of either Eqn. (la) or Eqn. (lb).
• Samples Comp-2 and Comp-3 were coated with coarse cylinders to attempt to improve inclusion of nanowires into the cells. However, their coating viscosities appeared to be too low for efficient solution pick up and transfer, resulting in poor print quality. Note that Samples Comp-2 and Comp-3 did not satisfy the conditions of Eqn. (la).
• Silver nanowire dispersion solutions comprising the following ingredients were prepared:
• Silver nanowires (51 nm + 5.4 average diameter, 23.5 + ⁇ . ⁇ average length, based on measurement of at least 100 wires)

Landscapes

• Dispersion Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Conductive Materials (AREA)
• Non-Insulated Conductors (AREA)
• Manufacturing Of Electric Cables (AREA)
• Printing Methods (AREA)
• Parts Printed On Printed Circuit Boards (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

Priority Applications (4)

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Publications (1)

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Citations (3)

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• 2011
  • 2011-11-11 US US13/294,355 patent/US8763525B2/en not_active Expired - Fee Related
  • 2011-11-12 JP JP2013544490A patent/JP5856625B2/ja not_active Expired - Fee Related
  • 2011-11-12 EP EP11802185.6A patent/EP2653016A1/en not_active Withdrawn
  • 2011-11-12 WO PCT/US2011/060492 patent/WO2012082281A1/en not_active Ceased
  • 2011-11-12 KR KR1020137015440A patent/KR20140010000A/ko not_active Withdrawn
  • 2011-11-12 CN CN201180060685.3A patent/CN103262664B/zh not_active Expired - Fee Related
  • 2011-12-02 TW TW100144465A patent/TW201231297A/zh unknown

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Non-Patent Citations (3)

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