EP4291614A1 - Composition d'encre conductrice à base d'un composite nanotube de carbone-argent - Google Patents

Composition d'encre conductrice à base d'un composite nanotube de carbone-argent

Info

Publication number
EP4291614A1
EP4291614A1 EP22753556.4A EP22753556A EP4291614A1 EP 4291614 A1 EP4291614 A1 EP 4291614A1 EP 22753556 A EP22753556 A EP 22753556A EP 4291614 A1 EP4291614 A1 EP 4291614A1
Authority
EP
European Patent Office
Prior art keywords
silver
cnt
ink composition
cnts
ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22753556.4A
Other languages
German (de)
English (en)
Inventor
Yongan Yan
Stefan Maat
Troy Robinson
Satyabrata Raychaudhuri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yazaki Corp
Original Assignee
Yazaki Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yazaki Corp filed Critical Yazaki Corp
Publication of EP4291614A1 publication Critical patent/EP4291614A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • IMS In-mold structural electronics
  • thermoformable prints are prepared using silver-based conductive inks with various organic binders (Reference #1-5). However, the presence of an electrically insulating polymeric organic binder significantly reduces the electrical conductivity of the printed inks.
  • Figure 1 depicts prints with the ink of the present invention.
  • the sintered silver particles (nanoparticles and flakes) are cross-linked with metallized carbon nanotube (CNT) strands.
  • CNT metallized carbon nanotube
  • Figure 2 shows a schematic process to prepare a dispersion of CNT that are metallized with silver (Ag) nanoparticles (NP).
  • Figure 3 illustrates a general procedure for preparing and printing of the present ink composition.
  • Figure 4 shows a schematic drawing of plates for (left) stencil printing and (right) screen printing, to form a rectangular printed shape.
  • Figure 7 shows micrographic images of prints without (left) or with (right) incorporation of 0.1 wt% Ag-CNT.
  • the left shows large cracks and the right shows that the cracks were eliminated by incorporation of Ag-CNT.
  • Figure 8 shows SEM images of a silver print prepared from ink containing non- metallized CNT. Image at right is a close-up of boxed area in image at left.
  • FIG 9 shows schematic drawings of Ag nanoparticles attached to CNT surface via either van der Waals pi-pi interaction (left, comparative) or by covalent bonding to CNT carbon framework (right, the present invention).
  • Figure 10 is a block diagram showing the printing and thermoforming process.
  • Figure 12 is a graph showing line resistance vs. thermoform elongation for printed lines prepared using different types of silver-based inks.
  • the present invention provides a silver-based ink composition with CNTs as an additive; further, the CNTs are metallized with silver (Ag) nanoparticles (NP).
  • the ink composition produces conductive prints with good thermoform elongation and high electrical conductivity.
  • the present ink composition comprises: (a) silver (Ag)-metallized CNTs comprising CNTs having covalently bound silver nanoparticles (Ag-CNT), (b) silver particles, and (c) a solvent.
  • the composition comprises 15 to 90 percent by weight (wt%) of silver, 0.001 to 5 wt% CNT, and 10 to 85 wt% of solvent.
  • the wt% of silver in the composition includes silver nanoparticles bound to CNTs, and unbound silver particles.
  • the wt% of CNT in the composition includes CNTs only, and does not include silver nanoparticles bound to the CNT.
  • the composition comprises 0.01 to 0.5 wt% of CNT.
  • the composition comprises 45 to 85 wt% or 45 to 75 wt% of silver. In one embodiment, the composition comprises 15 to 55 wt% or 25 to 55 wt% of solvent. In a preferred embodiment, the composition comprises 65 - 85 wt% of silver. In a preferred embodiment, the composition comprises 15 - 35 wt% of solvent.
  • the weight ratio of CNT to silver is about 1:0.1 to 1:100, preferably 1:1 to 1:50, or 1:1 to 1:10.
  • the silver nanoparticles are covalently bound to the carbon nanotubes forming the Ag-metallized CNT.
  • Prints with an ink composition having bare CNTs without covalently bound silver nanoparticles do not provide sufficient thermoform elongation, and do not reduce the tendency for printed dried ink to crack.
  • bare CNTs and silver particles do not mix well in an ink composition, and the bare CNTs and silver particles remain separated in the ink composition.
  • the Ag metallization of CNTs makes them more compatible with silver particles, and improves the mixing of Ag- metallized CNTs and Ag particles in an ink composition.
  • the weight % of Ag NP in the silver particles Ag is in the range of 0-100%, preferably in the range of 20-80% or 25-80%, and more preferably in the range of 30-50 or 40-60%.
  • the weight % of Ag FP in the silver particles is in the range of 0-100%, preferably in the range of 20-80% or 20-75%, and more preferably in the range of 40-60% or 50-70%.
  • the silver particles Ag comprise 5-60 wt% of silver nanoparticles (Ag NP) and 40-95 wt% of silver flake particles (Ag FP).
  • the silver particles Ag comprise 40-60 wt% of silver nanoparticles (Ag NP) and 40-60 wt% of silver flake particles (Ag FP).
  • a greater proportion of Ag FP increases stretchability, but decreases conductivity, whereas a greater proportion of Ag NP increases conductivity, but decreases stretchability.
  • This ink composition having an approximately even mixture of Ag NP and Ag FP, provides a good combination of conductivity and stretchability in the resulting printed articles.
  • the solvent is preferably an organic solvent, such as alcohols, esters, alcohol esters, glycols, glycol ethers, and ketones.
  • organic solvents include isopropanol (IP A), 2-ethoxyethanol, methyl n-amyl ketone, diisobutyl ketone, 2-butoxy ethanol, 1 -(2-methoxypropoxy)-2-propanol (MPP), di(propylene glycol) methyl ether, 2-(2-ethoxyethoxy)ethanol, n-methyl-2-pyrrolidone, ethylacetate, diethylene glycol monobutyl ether, diethylene glycol, diethylene glycol n-butyl ether acetate, 2,2,4- trimethyl-l,3-pentanediol monoisobutyrate (TMPD-MIB, or Texanol), diethylene glycol dibutyl ether (DGDE), methyl 5-(dimethylamino)-2
  • the solvent has a boiling temperature above 150°C, or between 150°C and 300°C.
  • solvents may include MPP, a glycol ether, TMPD-MIB, or any combination thereof.
  • the solvent is a mixture of two or more solvents, and the mixture has a boiling temperature above 100°C, or between 100°C and 350°C, or preferably between 130°C and 280°C.
  • the present ink formulation preferably does not contain a polymeric organic binder or a resin binder such as a polyester, acrylic polymer, acrylic block copolymer, acrylic polymer having tertiary alkyl amide functionality, polysiloxane polymer, polystyrene copolymer, polyvinyl polymer, divinylbenzene copolymer, polyetheramide, polyvinyl acetal, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, methylene polyvinyl ethers, cellulose acetates, styrene acrylonitrile, amorphous polyolefin, thermoplastic urethane, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl acetate terpolymer, functional ethylene vinyl acetate, ethylene acrylate copolymer, ethylene acrylate terpolymer, ethylene butadiene
  • the present ink composition does not contain a surfactant, such as sodium dodecylbenzene sulfonate, which is often used to disperse and stabilize CNTs in a liquid mixture.
  • a surfactant such as sodium dodecylbenzene sulfonate
  • CNTs in the present ink composition are stable and remain dispersed in the mixture without settling for at least 6 months.
  • the present ink composition can be sintered or cured at 100-150°C for 30 minutes to one hour, and does not need a high sintering temperature (e.g., 250°C or above), which is not compatible with most types of plastic substrates such as polycarbonate (PC) or polyethylene terephthalate (PET).
  • a high sintering temperature e.g. 250°C or above
  • plastic substrates such as polycarbonate (PC) or polyethylene terephthalate (PET).
  • Figure 1 illustrates prints with the present ink composition.
  • the sintered silver particles nanoparticles and flakes
  • the metallized CNT nanofibers are cross-linked with metallized CNT nanofibers.
  • the present invention is also directed to a process for preparing Ag-metallized CNT.
  • the process comprises the steps of: (a) mixing a CNT dispersion comprising CNTs having covalently bonded carboxyl groups in a first solvent with ammonium hydroxide, ammonia, or an alkyl amine, and a silver salt to cause a chemical reaction resulting in a diamine silver (Ag(NH 3 ) 2 +1 ) complex, and (b) reacting the mixture of (a) with formic acid, resulting in CNTs having silver (Ag°) nanoparticles covalently bound on their surfaces, to form CNTs covalently bound with silver nanoparticles.
  • Figure 3 illustrates the general procedure for preparing the present ink composition, and for preparing printed components using the present ink composition.
  • the starting CNTs having carboxyl (COOH) groups can be prepared, for example, by reacting CNTs with a HN0 3 solution to form a dispersion comprising CNTs with carboxyl groups ( Figure 3, step 1).
  • the acidic water is then removed from the dispersion and the CNTs having carboxyl groups are ready for storage or use.
  • This procedure generates COOH functional groups on the CNT surface, dissolves inorganic impurities such as iron catalyst residue, and allows the CNTs to be dispersed and remain suspended in a variety of solvents, including most organic solvents, and water if there are sufficient COOH groups.
  • CNTs having carboxyl groups are first dispersed in a proper solvent, for example, an alcohol such as isopropyl alcohol (IP A), ethyl alcohol, or MPP, a glycol ether such as 2-butoxyethanol or diethylene glycol, TMPD-MIB, or any combination thereof (Figure 3, step 2), to which an ammonium salt (such as ammonium hydroxide), ammonia, or an alkylamine (such as hexylamine) and a silver salt (Ag +1 , such as silver acetate or silver nitrate) are added (Figure 3, step 3).
  • a proper solvent for example, an alcohol such as isopropyl alcohol (IP A), ethyl alcohol, or MPP, a glycol ether such as 2-butoxyethanol or diethylene glycol, TMPD-MIB, or any combination thereof
  • an ammonium salt such as ammonium hydroxide
  • ammonia such as ammonium hydroxide
  • ammonia such as hexy
  • ammonium hydroxide NH4OH
  • ammonia NH 3
  • an alkylamine an alkylamine
  • some ammonia attaches to the carboxyl groups in the CNT, and some dissolves in the solvent.
  • a silver salt added to the dispersion can completely dissolve by forming silver ions (Ag +1 ) coordinated to ammonia, i.e. Ag(NH 3 ) 2 +1 on the CNT surface and in the dispersion, for example:
  • the molar ratio for Ag +1 ion: NH4OH: formic acid is about 1: 0.2-20: 0.1-5, and preferably about 1:4:1.
  • some silver particles are covalently bonded to the CNT surface while some may remain in the dispersion in the form of nanoparticles.
  • the present invention is also directed to a process for preparing the present ink composition.
  • the process comprises the steps of: (a) mixing a first CNT dispersion comprising CNTs having carboxyl groups in a first solvent with ammonium hydroxide, ammonia, or an alkyl amine, and a silver salt, and reacting for a period of time; (b) reacting the mixture of (a) with formic acid to form CNTs having silver nanoparticles covalently bound on the surface to obtain a second CNT dispersion comprising CNTs covalently bound with silver nanoparticles; and (c) mixing a solution comprising silver particles with the second CNT dispersion to form the ink composition.
  • the dispersion comprising CNTs covalently bound with silver particles is processed via three-roll milling or through a high-shear, high-pressure process, or both, in order to reduce the size of CNT aggregates in the dispersion.
  • the dispersion is processed via three- roll milling using a 5 - 20 pm gap.
  • the dispersion is high-shear, high- pressure processed by passing it through an orifice or channel 80 - 250 pm in diameter for one or more passes.
  • a solution comprising silver particles is mixed with the Ag NP metallized CNT dispersion (Figure 3, step 4).
  • the silver particles can be silver nanoparticles, silver flake particles, or a mixture thereof.
  • the silver particles are first dispersed in an organic solvent such as an alcohol such as isopropyl alcohol (IP A), ethyl alcohol, or MPP, a glycol ether such as 2-butoxyethanol or diethylene glycol, TMPD-MIB, or any combination thereof, before mixing with the Ag NP metallized CNT dispersion.
  • IP A isopropyl alcohol
  • MPP ethyl alcohol
  • a glycol ether such as 2-butoxyethanol or diethylene glycol, TMPD-MIB, or any combination thereof
  • the mixing of Ag NP metallized CNT with silver particles is accomplished by using planetary mixing, 3-roll milling, or by a high pressure, high shear process.
  • an adjustment to the solvent amount in the composition is optionally applied, to achieve the most appropriate viscosity of the ink for the printing process to be used (Figure 3, step 5).
  • This adjustment may entail either addition of solvent (to reduce viscosity) or removal of solvent through evaporation (to increase viscosity).
  • the present ink composition can be used to print various electrically conducting components such as lines, shapes, patterns, and circuits on flat substrates by using stencil printing, screen printing, or inkjet printing ( Figure 3, step 6).
  • the printed components on the substrates can be formed into a 3D shape by thermoforming or mechanical-forming processes, while maintaining their electrical conductance without cracking.
  • Printed components made with the present ink composition have high thermoform elongation and electrical conductivity, and are superior to printed components produced from inks containing polymeric organic binders.
  • the printed components typically have a thickness >3 pm, preferably >10 pm, and more preferably >15 pm.
  • the printed components have electrical conductivity relative to that of bulk silver of > 5%, preferably > 10% or > 15%.
  • the printed components exhibit a thermoform elongation of > 5%, preferably > 10% or > 15%.
  • Printed components may be produced with the present ink compositions via, for example, stencil printing, screen printing, gravure printing, flexographic printing, offset printing, and inkjet printing, among others.
  • Stencil printing and screen printing are common and similar techniques that transfer inks onto a substrate through a stencil plate having apertures matching the design of the desired component.
  • the apertures in stencil printing are completely open, while in screen printing the apertures are filled with a wire mesh ( Figure 4).
  • stencil printing produces relatively thicker prints while screen printing produces thinner prints but with relatively high resolution.
  • the maximum length of CNT strands should be less than about 50% of the circumference of the wire of the screen mesh, preferably less than about 1/3 of the circumference of the screen mesh wire. Also, the maximum length of CNT strands should be less than about 50% of the width of the mesh opening between wires. For example, for a size 200 mesh screen having wire diameter of 38 pm and mesh opening of 89 pm, the maximum length of a CNT strand would be about 40 pm. For example, the length of CNT strands should be between about 1 pm and 40 pm, or between about 1 pm and 30 pm.
  • Nitric acid solution ( ⁇ 3N) was prepared by adding 180 g of 70% nitric acid to 408 g of deionized water and stirring for at least 5 min.
  • the nitric acid solution was mixed with 20 g of as-received SWCNT.
  • the mixture was simultaneously sonicated and mechanically stirred at 50°C for 4 h and then the dispersion was stirred overnight. This process served both to generate COOH groups on the SWCNT and to dissolve inorganic impurities.
  • the mixture was then vacuum-filtered to remove most of the acidic water.
  • the CNT wet cake was dispersed in 800 g deionized water, sonicated and stirred for at least 30 min and then vacuum-filtered to remove water. These procedures were repeated 5 times to remove acid and dissolved inorganic impurities.
  • a SEM image of the Ag-metallized CNT is shown in Figure 5.
  • Example 3 Ink containing Ag (NP+FP) and Ag-metallized CNT (Ag-CNT)
  • the prepared ink (150 g) contained silver particles composed of 50 wt% Ag FP and 50 wt% Ag NP, (i.e., a 1 : 1 ratio of NP:FP) and Ag-CNT.
  • the weight ratio of CNT to Ag (NP + FP) was 0.2 wt%, and solvent content in the ink was about 30 wt%.
  • An ink composition was prepared according to Example 3 except the silver particles consisted entirely of silver flakes (Ag FP), and the amount of CNT (as Ag-CNT) was 0.067 wt% relative to the amount of Ag FP. The amount of Ag as nanoparticles bonded to CNT was 0.4 wt% relative to the amount of Ag FP.
  • a SEM image of a stencil print prepared from this ink and cured at 130°C is shown in Figure 6a. The image illustrates that the silver nanoparticles bonded to the CNT surfaces also effectively bonded the CNT to the flake surfaces, and the CNT cross-linked the silver flake particles together without using organic binder.
  • a silver ink containing 60 wt% Ag NP and 40 wt% solvent was stencil printed as 16 pm thick lines on a polycarbonate substrate and cured at 130°C for 30 min.
  • the prints showed long and wide (100 x 20 pm) cracks (Figure 7, left panel).
  • Ag-CNT Ag- metallized CNT
  • Example 5 The 0.1 wt% Ag-metallized CNT in Example 5 was replaced with 0.15 wt% dispersed CNT without Ag metallization.
  • the print prepared from this ink had a thickness of 16 pm and cracks were continually present in the prints ( Figure 8). This result indicates that the non- metallized CNT do not provide the necessary strong surface interaction between CNT and silver particles that was demonstrated by the Ag-metallized CNT in Example 5.
  • Example 7 Inks containing CNTs with non-covalently bonded silver nanoparticles (comparative example)
  • This ink was prepared by a similar method as described in Example 1 of US 9,418,769. About 100 ml of ethanol and 1.18 ml of benzyl mercaptan were mixed; then, 8 ml of the resultant solution and 1000 ml of ethanol containing 3.4 g of AgNCh were added at a molar ratio of benzyl mercaptan to Ag of 1:25 to prepare Ag nanoparticles functionalized with benzyl mercaptan. About 50 mg ultrasonically dispersed SWCNT in ethanol were mixed with 150 ml of the above solution of Ag nanoparticles functionalized with benzyl mercaptan. The weight ratio of AgNCUCNT was 10.2:1 or Ag:CNT was 6.4:1. The silver nanoparticles were weakly bound to the surfaces of the CNT by the aromatic hydrocarbon group via p-p interactions between the benzyl and CNT surfaces. The silver nanoparticles were not attached to the CNT by covalent bonds.
  • Example 5 The 0.1 wt% Ag NP metallized CNT in Example 5 was replaced with 0.1 wt% CNT non-covalently bonded with silver particles prepared in this Example.
  • the print prepared from this ink had a thickness of 16 pm and cracks were continually present in the prints similar to those shown in Figure 8. The result indicates that a strong covalent chemical bond is needed between Ag and the CNT surfaces.
  • the bonding of Ag to CNT surfaces via weak p- p interactions of the aromatic hydrocarbon groups did not eliminate print cracks, and it did not improve the mechanical properties, such as stretchability or thermoform elongation on plastic substrates after curing.
  • Example 8 Evaluation of the thermoform elongation of printed lines
  • Electrically conductive lines were printed on flat polycarbonate (PC) substrates using the ink composition described in Example 3.
  • the printed PC was then heated to about 185°C for about 80 seconds and a vacuum was applied over an arc-shaped porous mold to form a 3D curved shape.
  • the process is illustrated by the block diagram in Figure 10.
  • the printed lines were stretched in the range of 0-20% depending on the line position on the 3D arc, as shown in Figure 11.
  • the printed lines prepared from this ink composition exhibited, in the unstretched state, electrical conductivity of 11% relative to that of bulk silver.
  • the printed lines exhibited thermoform elongation of 15%, meaning that the electrical conductivity was maintained in the printed lines until the elongation exceeded 15%.
  • Conductive lines were also printed using the ink composition of Example 3, after further processing the ink by three-roll milling. After three-roll milling of the ink, the elongation of the printed lines increased to 18.3-20%.
  • Three of the ink batches (B - D) contained one of three types of polymeric organic binders, including polyurethane, polyether polyol, or ethyl cellulose, which was added respectively to the ink composition at 1 wt% relative to the total weight of Ag particles (NP + FP) .
  • the fifth batch of silver ink (E) was formulated as in Example 3, but containing 0.07 wt% Ag-metallized CNT without organic binder.
  • Table 1 Composition and properties of five batches of silver-based inks containing polymeric organic binder and metallized CNT.
  • Conductivity of pure bulk silver is 6.3 x 10 5 S/cm.
  • Each ink was stencil printed onto a flat PC substrate and the conductivity and thermoform elongation of the resulting prints were determined.
  • the silver ink without Ag- metallized CNT or binder showed electrical conductivity of 18.7% of that of bulk silver and thermoform elongation of about 1%.
  • Adding 1% polymeric binder reduced the conductivity considerably to 12.2-13.4% of that of bulk silver and slightly increased the thermoform elongation to about 2%.
  • the inks showed a high conductivity of 16% of that of bulk silver and high thermoform elongation of 9%.
  • Example 10 Comparison of commercial silver inks (with or without polymeric organic binder) with the ink of the present invention
  • Example 3 showed both high electrical conductivity (11.0% of that of bulk Ag) and high thermoform elongation (18.3%).
  • Table 2 Comparison of commercial silver inks (with or without polymeric organic binder) with ink of the present invention comprising Ag-metallized CNT.
  • Figure 12 shows electrical line resistance vs. thermoform elongation for typical printed lines of different Ag-based inks, after undergoing a thermoforming process.
  • a silver ink is formulated containing 55 wt% silver particles (consisting of silver nanoparticles and silver flake particles in a 1:1 ratio), 0.4 wt% (relative to the weight of silver) Ag-metallized SWCNT, and about 44.6 wt% solvent.
  • the length of the SWCNT strands after dispersion is in the range of 1-500 pm.
  • High quality 1 mm wide printed lines with high electrical conductivity (-10% of that of bulk silver) and high thermoform elongation (-20%) are produced from the ink by using a stencil printing process. The results indicate that inks appropriate for stencil printing are formulated with CNT having strands up to 500 pm in length, possibly longer.
  • Example 12 Silver ink with short CNT strands for screen printing
  • a silver ink is formulated with the same composition as that of Example 11, except the CNT used is a commercial variety having a shorter strand length of ⁇ 40 pm, with average strand length of about 5 pm.
  • the length of the SWCNT strands after dispersion is in the range of 1 - 30 pm.
  • High quality 1 mm wide printed lines with high electrical conductivity (11% of that of bulk silver) and good thermoform elongation (18%) are continuously produced from this ink by using a screen-printing process.
  • the screen used for printing is a size 200 mesh with a wire diameter of 38 pm and mesh opening of 89 pm.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une composition d'encre comprenant : (a) Des nanotubes de carbone (NTC) métallisés à l'argent (Ag) comprenant des NTC et des nanoparticules d'argent liées par liaison covalente aux NTC, (b) des particules d'argent et (c) un solvant. La présente composition d'encre produit des composants imprimés présentant un bon allongement par thermoformage et un conductivité électrique élevée, sans la présence de liants organiques polymères. La présente invention concerne également un procédé de préparation de NTC métallisés à l'Ag et un procédé de préparation d'une encre comprenant des NTC métallisés à l'Ag.
EP22753556.4A 2021-02-11 2022-02-10 Composition d'encre conductrice à base d'un composite nanotube de carbone-argent Pending EP4291614A1 (fr)

Applications Claiming Priority (2)

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US202163148272P 2021-02-11 2021-02-11
PCT/US2022/070612 WO2022174244A1 (fr) 2021-02-11 2022-02-10 Composition d'encre conductrice à base d'un composite nanotube de carbone-argent

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EP4291614A1 true EP4291614A1 (fr) 2023-12-20

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Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6875274B2 (en) * 2003-01-13 2005-04-05 The Research Foundation Of State University Of New York Carbon nanotube-nanocrystal heterostructures and methods of making the same
KR101078079B1 (ko) * 2008-12-10 2011-10-28 엘에스전선 주식회사 은 수식 탄소 나노튜브 함유 전도성 페이스트 조성물
KR101724064B1 (ko) * 2010-02-18 2017-04-10 삼성전자주식회사 전도성 탄소나노튜브-금속 복합체 잉크
JP6300731B2 (ja) * 2011-12-23 2018-03-28 ザ ボード オブ トラスティーズ オブ ザ ユニバーシティ オブ イリノイ 導電性銀構造を形成するためのインク組成物
EP3149092B1 (fr) * 2014-05-30 2020-04-01 Electroninks Writeables Inc. Encre conductrice pour stylo à bille roulante et tracé conducteur formé sur un substrat
MY175446A (en) * 2015-01-27 2020-06-29 Teikoku Printing Inks Mfg Co Ltd Ink composition for high-quality/high-definition screen printing, printed matter produced by the screen printing ink composition, and method for producing the printed matter
KR20180037444A (ko) * 2016-10-04 2018-04-12 주식회사 랩311 탄소나노튜브 및 금속 나노입자가 분산된 잉크젯 프린터용 전도성 잉크 조성물 및 이의 제조 방법
TW201842088A (zh) * 2017-02-08 2018-12-01 加拿大國家研究委員會 可印刷分子油墨
CN110655831A (zh) * 2019-11-15 2020-01-07 合肥映山红材料科技有限公司 一种纳米银碳纳米管复合导电油墨的制备方法

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