EP2655526A2 - Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering - Google Patents

Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering

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Publication number
EP2655526A2
EP2655526A2 EP11797328.9A EP11797328A EP2655526A2 EP 2655526 A2 EP2655526 A2 EP 2655526A2 EP 11797328 A EP11797328 A EP 11797328A EP 2655526 A2 EP2655526 A2 EP 2655526A2
Authority
EP
European Patent Office
Prior art keywords
emulsion
water
pickering emulsion
silver nanoparticles
pickering
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.)
Withdrawn
Application number
EP11797328.9A
Other languages
German (de)
English (en)
Inventor
Stefanie Eiden
Diana Dimova LANDEN
Daniel Gordon Duff
Daniel Rudhardt
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.)
Clariant International Ltd
Original Assignee
Bayer Intellectual Property GmbH
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 Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Priority to EP11797328.9A priority Critical patent/EP2655526A2/fr
Publication of EP2655526A2 publication Critical patent/EP2655526A2/fr
Withdrawn legal-status Critical Current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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention relates to a process for the preparation of a Pickering emulsion containing water, a water-immiscible solvent and, preferably sterically, stabilized syllable nianop modifier for the production of conductive coatings.
  • the invention further relates to a process for the full or partial coating of surfaces, in particular with a Pickering emulsion according to the invention, wherein the coating obtained in particular has a high electrical conductivity and may advantageously additionally be transparent.
  • Plastic components usually have good mechanical properties and sometimes also good optical properties, such as the transparency of polycarbonate. Most engineering plastics are electrical insulators.
  • Xia thus obtained monodisperse dispersions with silver nanoparticles with particle sizes below 10 ⁇ m and narrow particle size distribution.
  • PVP polymeric stabilizer
  • Such sterile polystyrene dispersion stabilizers may optionally reduce the direct contact of the particles with one another and thus the conductivity of the coating in the resulting conductive coatings by the surface coverage of the silver particles. According to Xia, it is not possible to obtain such stable monodisperse dispersions without the use of additional PVP as stabilizer.
  • EP 1493780 A I describes the production of conductive surface coatings comprising a liquid conductive composition comprising a binder and silver particles, wherein the aforementioned silver-containing particles may be silver oxide particles, silver carbonate particles or silver acetate particles, each of which may have a size of 10 .mu.m to 10 .mu.m.
  • the binder is a polyvalent phenolic compound or one of several resins, so in any case at least one additional polyun component.
  • a conductive layer is obtained from this composition after application to a surface with heating, the heating preferably being carried out at temperatures of 140 ° C. to 200 ° C.
  • 493 780 A 1 are dispersions in a dispersion medium selected from among alcohols such as methanol, ethanol and propanol, isophorones, terpineols, triethylene glycol monobutyl ether acetate and triethylene glycol monobutyl ether acetate.
  • alcohols such as methanol, ethanol and propanol
  • isophorones such as terpineol
  • triethylene glycol monobutyl ether acetate triethylene glycol monobutyl ether acetate
  • triethylene glycol monobutyl ether acetate triethylene glycol monobutyl ether acetate.
  • dispersion stabilizers such as hydroxypropylcellulose, polyvinylpyrrolidone and polyvinyl alcohol.
  • These dispersion stabilizers are also polymeric components.
  • the silver-containing particles are stabilized in the dispersant always steri sch by the aforementioned dispersion stabilizers and the binder as a
  • a method for producing transparent leitfohigen metal nanoparticle-based Be laminations is disclosed in WO2006 / 13735 A2 and in US 7,566,360 B2.
  • a nano-metal powder with several additives such as surface-active substances, binders. Polymers. Buffers, dispersing aids. and coupling reagents, processed in organic solvents to a homogeneous mixture.
  • the nano-metal powders can also
  • a disadvantage of the abovementioned water-in-oil emulsions is, in particular, that they must be washed at least twice with water before they can be used, so that the desired transparent, conductive metal nanoparticle-based coatings can be produced from these.
  • the invention therefore proposes a process for producing a Pickering emulsion for producing conductive coatings, wherein a) an aqueous dispersion containing, in particular sterically, stabilized silver manoparticles and water is mixed with at least one, water-immiscible solvent and then dispersed to form an emulsion , wherein the content of stabilized silver nanoparticles, based on the total weight of the emulsion obtained, is between 0.5 wt .-% and 7 wt .-%, and b) then during a service life, the emulsion obtained in (a) by a creaming in an upper concentrated emulsion phase and a lower, substantially aqueous, phase is separated, and c) the resulting upper concentrated emulsion phase is isolated, this emulsion phase having a content of Silbemanopumblen up to 7% by weight, preferably up to 4.5 wt .-%, based on the total weight, having.
  • a source emulsion is stabilized from dispersed in aqueous dispersion media or aqueous dispersants
  • Silbemanopellen for example, a silver manoparticle sol, water and a water-immiscible solvent produced.
  • This parent emulsion may preferably be an O / W emulsion.
  • the oil phase of the O / W emulsion in this case is formed by the solvent (s) which is not water-miscible.
  • the silver nanoparticles occupy the surface of the oil droplets and stabilize the oil droplets in the emulsion.
  • the stated content of silver particles in% by weight relates according to the invention to the content of stabilized silver mane particles, ie the silver nanoparticles which are coated with dispersion stabilizer on their surface.
  • the aqueous dispersant (s) is preferably water or mixtures containing water and organic, preferably water-soluble, solvents.
  • the liquid dispersing agent (s) are particularly preferably water or mixtures of water with alcohols, aldehydes and / or ketones, more preferably water or mixtures of water with mono- or polyhydric alcohols having up to four carbon atoms, such as eg Methanol, ethanol, n-propanol, iso-propanol or ethylene glycol, aldehydes of up to four carbon atoms, e.g. Formaldehyde, and / or ketones of up to four carbon atoms, e.g. Acetone or methyl ethyl ketone.
  • Very particularly preferred Dispersionsmittei is water.
  • silver particles are to be understood as meaning those having a d.sub.50 value of less than 100 nm, preferably less than 80 nm, measured by means of dynamic light scattering.
  • a ZetaPius Zeta Potential Analyzer from Brookhaven Instrument Corporation is suitable for the measurement by means of dynamic light scattering.
  • the stabilization of the silver nanoparticles in the aqueous dispersion of silver silipartan particles used, for example silver nanoparticle sol is preferably carried out using a steric dispersing aid such as polyvinyl pyrrolidone, block copolyether and block copolyether with polystyro blocks, very preferably Disperbyk 190 (BYK-Chemie, Wesel).
  • a steric dispersing aid such as polyvinyl pyrrolidone, block copolyether and block copolyether with polystyro blocks, very preferably Disperbyk 190 (BYK-Chemie, Wesel).
  • the silver nanoparticle particles used to produce the Pickering emulsion according to the invention have a high colloid-chemical stability.
  • the choice of the dispersing agent also makes it possible to optimally adjust the surface properties of the particles. For example, dispersing agent adhering to the particle surface can impart a positive or negative surface charge to the particles.
  • at least one electrostatic dispersion stabilizer is added in the preparation of the dispersions.
  • An electrostatic dispersion stabilizer in the context of the invention is to be understood as meaning one by whose presence the silver nanoparticles are provided with repulsive forces and, based on these repulsive forces, no longer tend to aggregate. Consequently, the presence and effect of the electrostatic dispersion stabilizer between the silver nanoparticles provides repelling electrostatic forces which counteract van der Waals forces acting on the aggregation of the silver nanoparticles.
  • Particularly preferred electrostatic dispersion stabilizers are citric acid and / or citrates, e.g. Lithium, sodium, potassium or tetramethylammonium citrate.
  • citric acid and / or citrates e.g. Lithium, sodium, potassium or tetramethylammonium citrate.
  • the salt-like electrostatic dispersion stabilizers are largely dissociated into their ions, the respective anions causing the electrostatic stabilization.
  • step (b) the source emulsion of step (a) is subjected to creaming.
  • the original emulsion separates into an upper concentrated emulsion phase and into a lower, essentially aqueous, emulsion phase.
  • the upper concentrated emulsion phase according to the invention is also referred to as cream phase or cream layer.
  • the cream phase advantageously contains a higher concentration of drops of the oil phase, since the oil drops rise during the service life.
  • the cream phase is finally isolated.
  • the cream phase may contain a content of stabilized silver nanoparticles of up to 7% by weight, preferably up to 4.5% by weight, based on the total weight of the isolated Pickering emulsion.
  • the Pickering emulsion according to the invention is formed by the cream phase.
  • the oil drops in the cream phase are further occupied by the Siibernanopitate on its surface, thereby advantageously a sufficient concentration of silver enters the cream phase.
  • the resulting coating material is suitable for the production of conductive coatings.
  • the concentration of silver nanoparticles in the cream phase can advantageously also be increased according to the invention compared with the concentration in the original emulsion. This is particularly advantageous with regard to a cost-efficient coating process, since according to the invention it is possible to obtain suitable coating compositions for the production of conductive coatings with comparatively low use of silver nanoparticles.
  • the inventive method for the preparation of the coating composition, so the Pickering emulsion is easy and inexpensive to perform. It has surprisingly been found that the Pickering emulsions provided by the method according to the invention are furthermore particularly stable and can be stored, for example, for several days.
  • a further advantage of the method according to the invention is that the Pickering emulsion obtained in step (c) is outstandingly suitable as a coating agent for the production of electrically conductive, in particular also transparent, coatings on substrates.
  • step (c) it is advantageously possible to dispense with the use of additional additives, such as binders, dispersing aids and film formers, which slow down or even increase the drying and / or sintering of a surface coating obtained from a Pickering emulsion according to the invention from step (c) Temperature require until drying and / or sintering and thus a conductivity of the surface coating occurs by sintering of the silver particles.
  • additional additives such as binders, dispersing aids and film formers
  • the service life under (b) is 1 h to 5 d, preferably 6 h to 3 d, more preferably 12 h to 36 h, for example 24 h. These service lives have been found to be particularly suitable for the formation of stable Pickering emulsions with good properties for the production of conductive coatings.
  • a Pickering emulsion for producing conductive coatings is furthermore proposed for achieving the object according to the invention, the emulsion being stabilized
  • the present invention provided Pickering emulsion. is suitable as a coating agent for the production of electrically conductive structures, in particular for the formation of reticulated honeycomb structures by Directorgani organization of silver nanoparticles and can also be used for the production of transparent electrically conductive structures, in particular of continuously connected transparent conductive networks.
  • the Pickering emulsion according to the invention preferably contains small sterically stabilized silver nanoparticles as coating agent. which have a dso of approximately 80 nm in the main and are colloidally stable in the silver nanoparticle sol used.
  • the stabilized silver nanoparticles are having a low concentration according to the invention of from 0.5% by weight to 7% by weight, preferably from 0.5 to 5% by weight, particularly preferably up to 4.5% by weight, for example up to 3, 5 wt .-%, without additional dispersing agent in the Pickering emulsion.
  • a low after-treatment temperature of 140 ° C is sufficient to achieve surprisingly high conductivities of the formed structures after application and drying of the Pickering emulsion as a coating agent on egg nem substrate.
  • the Pickering emulsion according to the invention it is thus provided that it contains no additional surface-active compounds, binders, polymers, buffers, film formers or dispersants.
  • Advantage haftcnvci sc the inventive Pickering emulsion is therefore free of additional substances which could reduce the conductivity of a coating produced therefrom.
  • the Pickering emulsion according to the invention has the further advantage that it is not only less expensive, but also easier to prepare compared to coating compositions containing additional additives, such as surface-active compounds, other dispersing aids or polymers. It is also advantageous that steric hindrance of the silver particles is avoided by such additional additives and good conductivity of a coating produced from the Pickering emulsion according to the invention, in particular also comparatively low after-treatment temperatures, can be ensured.
  • the organic solvent is at least one linear or branched alkane. an optionally alkyl-substituted cycloalkane, an alkyl acetate or a ketone, benzene or toluene.
  • organic solvents suitable according to the invention si nd cyclohexane, methylcyclohexane, n-hexane, octadecane, ethyl acetate, butyl acetate, acetophenone and cyclohexanone, this list is not exhaustive.
  • the organic solvent and the water in the emulsion preferably in a ratio (in wt .-%) of 1: 4 to 1: 2, for example in a ratio of 1: 3, are included.
  • those in the Pickering emulsion are, for example, in the form of a silver nanoparticle sol. contributed
  • the dispersing aid for the stable stabilizer is preferably selected from the series: polyvinylpyrrolidone, block copolymer and block copolyether with polystyrene blocks.
  • polyvinylpyrrolidone having a molecular weight of about 10000 amu (for example PVP K15 from Fluka) and polyvinylpyrrolidone having a molecular weight of about 360000 amu (for example PV K90 from Fluka) and more preferably block copolyether with polystyrene blocks having 62 are preferred Wt.% C: -Pol> ethcr. 23 wt 0 "CVPolvether and 15 wt 0" polystyrene, based on the dried dispersion aids, with a ratio of the block lengths CVPolvether to CVPolvether of 7: 2
  • the dispersing aid in an amount of 10 wt .-% is up, preferably from 3 wt 0 "to 6 wt .-%, based on the silver content of the particles present.
  • the selection of such a concentration range ensures that the particles are covered with dispersing assistant so far that the desired properties, such as stability of the emulsion, are ensured.
  • this avoids excessive enclosure of the particles with the dispersing assistant. An unnecessary excess of dispersing agent could undesirably affect the properties of the Pickering emulsion to be produced and the coatings to be produced therefrom.
  • the invention further relates to a method for fully or partially compliant Besch
  • the thus covered, coated top surface is then dried to remove the water and the organic solvent at least at a temperature of less than 40 ° C, AD), the thus dried coating is then sintered in the presence or absence of the cover.
  • step (AA) can be carried out, for example, by spray coating, dipping. Floods or knife coating done.
  • the Pickering emulsion can also be applied by means of a pipette.
  • Pickering Emulsion has surprisingly been found to retain the oil droplets coated with silver nanoparticles, which advantageously influences the separation of silver particles and the formation of honeycomb structures.
  • a good self-leveling of the silver particles allows the formation of continuous structures, whereby costly printing processes or cost-intensive technologies for their production can advantageously be dispensed with.
  • the cover which is applied in step (AB) to the surface coated with the Pickering emulsion, it is possible, on the one hand, for the speed of the drying of the wet layer to be favorably favored, so that a continuous network of silver nanoparticles can be formed.
  • the cover also promotes the self-organization of the silver manopar particles, in particular to honeycomb structures of the silver particles. Due to the formation of honeycomb structures made of silver nanoparticles, according to the invention, in addition to a good conductivity, advantageously also a good transparency can be achieved.
  • drying is carried out at least at a temperature below 40 ° C. under step (AC).
  • drying conditions which in particular have little thermal stress, and the associated slow evaporation of the water and of the organic solvent. Furthermore, the drying conditions are also suitable for cooking sto ffsu b st rate.
  • the drying takes place under (AC) at at least one temperature of less than 35 ° C., particularly preferably at room temperature.
  • the drying step is thereby very gentle, and it has been advantageously the formation of consistently connected reticulated honeycomb structures by the
  • the drying under (AC) for a period of 15 minutes to 36 hours.
  • the cover can be a glass or plastic plate, a plastic film or a plastic or Tcxtih read, preferably a water and solvent-permeable cover.
  • a cover which is not permeable to water and / or solvents, water and / or solvents can escape, for example, via the edge regions between substrate and cover.
  • An example of this is the covering of a Pickering emulsion coated glass slide with another glass slide. If such a substrate cover arrangement is used, in accordance with the invention it is also referred to as a sandwich decay.
  • a water and solvent-permeable cover may be preferred in accordance with the invention
  • Embodiment be a porous filter cloth.
  • a Monodur polyamide (PA) filter cloth (VERSEIDAG) can be used. This is commercially available with different mesh sizes and can be used depending on the solvent used. The advantage of such a filter cloth is that the drying over the surface of the substrate can be carried out more uniformly than with a transparent cover.
  • PA Monodur polyamide
  • VERSEIDAG Monodur polyamide
  • Drying time can be shortened.
  • equally good or even better results with regard to the self-assembly of the silver manoparticles into suitable mesh and honeycomb structures than in a sandwich method can be achieved.
  • the silver particles are relatively less liable to such a cover, so that the risk of destruction of the formed, possibly not yet sintered, silver nanoparticle structures can be significantly reduced.
  • the surface is the surface of a glass, metal.
  • Ceramic or plastic substrates for example, a plastic substrate may be made of polyimide (PI). Polycarbonate (PC) and / or polyethylene terephthalate (PET) polyurethane (PU), polypropylene (PP), which may optionally, for example, to ensure sufficient wettability, pretreated with the inventive Pickering emulsion and / or provided with a primer.
  • the substrate may also be transparent.
  • the invention relates to a further embodiment of the invention
  • Coating may include sintering under (AD) at least at a temperature greater than 40 ° C, preferably at least at a temperature of from 80 ° C to 180 ° C, most preferably from 130 ° C to 160 ° C, for example at 140 ° C , respectively.
  • AD sintering under
  • the invention also for the production of transparent electrically conductive structures on temperature-sensitive substrates, such as Poiycarbonatfolien use.
  • electrically conductive structures are in particular structures which have a resistance of less than 5000 ⁇ / m.
  • the coatings obtained according to the invention can be transparent, which is particularly advantageous for various applications.
  • Another object of the invention are electrically conductive coatings. get through
  • Such electrically conductive transparent coatings can, for example, form conductor tracks, antenna elements, sensor elements or bond connections for contacting with semiconductor components.
  • the transparent and conductive coatings according to the invention can be used, for example, as transparent electrodes for displays, screens and touch panels. are used as electroluminescent displays, as transparent electrodes for touch switches, as transparent shields for electrodes and auxiliary electrodes, for example for solar cells or in OLEDs, in applications for plastic spectacle lenses, as transparent electrodes for electrochromic layer systems or as transparent electromagnetic shielding.
  • the expensive layers and structures of tin-doped indium oxide indium tin oxide, ITO
  • ITO indium tin oxide
  • Measuring device MCR301 SN801 18503
  • Measuring profile 21 measuring points;
  • a 0.054 molar silver nitrate solution was mixed with a mixture of 0.054 molar sodium hydroxide solution and the dispersing aid Disperbyk 190 (manufacturer BYK Chemie, Wesel) (1 g 1) in a volume ratio of 1: 1 and stirred for 10 m.
  • a 4.6 molar aqueous Formaldehvd solution was added with stirring so that the ratio of Ag " to reducing agent was 1: 10.
  • This mixture was heated to 60 ° C., kept at this temperature for 30 minutes and then cooled In a first step, diafiltration separated the unreacted educts, and the mixture was concentrated, using a membrane of 30,000 daltons to give a colloid-stable
  • Dry films detected In order to achieve a conductivity of the coatings with the honeycomb structures, the dry films were sintered after removal of the cover 4-12 h at 140 ° C. The resistance of the resulting coating was measured on the honeycomb film with a multimeter between two approximately 0.3 cm wide and 1 cm long strips at a distance of 1 cm. The transmission was determined by UV-VIS spectrophotometer.
  • the solids content of stabilized silver nanoparticles in the Pickering emulsion and the conductivity and transmission of the coating produced were determined:
  • the solids content of stabilized silver nanoparticles in the Pickering emulsion and the conductivity and transmission of the coating produced were determined:
  • the Feststoffgchalt of stabilized silver nanoparticles in the Pickering emulsion and the conductivity and transmission of the coating produced were determined.
  • ⁇ of the frame phase were pipetted onto a glass slide [25 mm / 75 mm / lmm (b / lh)] and knife-coated with a 50 ⁇ m wet layer.
  • a filter cloth PA ⁇ machine ash On the wet layer, apply a filter cloth PA ⁇ machine ash. Thereafter, the wet film covered with the filter cloth was dried at RT for 30 minutes. The water and the organic solvent were able to escape through the pores of the filter cloth. After removing the filter cloth, the dry film formed was sintered at 140 ° C for 12 h.
  • honeycomb structure could be observed in each case with light microscopy.
  • the solids content of stabilized silver particles in the Pickering emulsion and the conductivity and transmission of the coating produced were determined.
  • Emulsion performed.
  • the formation of a honeycomb structure could be observed by light microscopy.
  • the solids content of stabilized silver particles in the Pickering emulsion and the conductivity and transmission of the coating produced were determined:
  • Example 2 The mixtures listed below were prepared as described in Example 2 and then applied as in Example 3, dried and sintered. The content of silver nanoparticles in the emulsion was determined. Then two silver points with one
  • Cream layer after cream layer Source emulsion [g] [g]

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Abstract

L'invention concerne un procédé de préparation d'une émulsion de Pickering contenant de l'eau, un solvant non miscible avec de l'eau, et des nanoparticules d'argent stabilisées de façon stérique de préférence, pour la fabrication de revêtements conducteurs. L'invention concerne également un procédé pour le revêtement intégral ou partiel de surfaces, notamment au moyen d'une émulsion de Pickering selon l'invention, le revêtement obtenu présentant notamment une conductivité électrique élevée et pouvant par ailleurs être transparent de manière avantageuse.
EP11797328.9A 2010-12-21 2011-12-19 Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering Withdrawn EP2655526A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11797328.9A EP2655526A2 (fr) 2010-12-21 2011-12-19 Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10196109A EP2468826A1 (fr) 2010-12-21 2010-12-21 Emulsion Pickering destinée à la fabrication de revêtements conducteurs d'électricité et procédé de fabrication d'une émulsion Pickering
PCT/EP2011/073276 WO2012084849A2 (fr) 2010-12-21 2011-12-19 Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering
EP11797328.9A EP2655526A2 (fr) 2010-12-21 2011-12-19 Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering

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EP11797328.9A Withdrawn EP2655526A2 (fr) 2010-12-21 2011-12-19 Émulsion de pickering pour la fabrication de revêtements électroconducteurs et procédé de préparation d'une émulsion de pickering

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EP (2) EP2468826A1 (fr)
JP (1) JP2014505969A (fr)
KR (1) KR20140007359A (fr)
CN (1) CN103429673A (fr)
BR (1) BR112013018452A2 (fr)
CA (1) CA2821844A1 (fr)
SG (1) SG191736A1 (fr)
TW (1) TW201232566A (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115401203A (zh) * 2022-08-12 2022-11-29 浙江工业大学 一种减小以熔盐为介质的金属乳液法所制得的锡微球粒径的方法

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103521778A (zh) * 2013-10-10 2014-01-22 天津工业大学 一维纳米结构的自组装制备
DE102013114572A1 (de) 2013-12-19 2015-06-25 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Verfahren zur Herstellung strukturierter metallischer Beschichtungen
CN104485225B (zh) * 2014-11-14 2016-08-17 哈尔滨工业大学宜兴环保研究院 一种可稳定Pickering乳液的内壁固载贵金属的磁性碳纳米管二维膜片的制备方法
JPWO2016136723A1 (ja) * 2015-02-23 2017-11-30 株式会社フルヤ金属 ナノ粒子の精製方法
KR101757245B1 (ko) 2015-07-28 2017-07-13 한국과학기술원 피커링 에멀젼 및 그 제조 방법
CN105273110B (zh) * 2015-11-25 2017-08-04 北京师范大学 一种制备聚苯乙烯/纳米银复合微球的方法
CN105710386B (zh) * 2016-02-25 2018-04-03 天津工业大学 一维银链纳米结构、自组装制备方法及sers应用
KR101971658B1 (ko) 2016-10-20 2019-04-24 한국과학기술원 기공 표면에 입자가 부착된 다공성 고분자, 이의 제조방법 및 이의 용도
KR102101146B1 (ko) 2016-11-10 2020-05-15 주식회사 엘지화학 전도성 필름 및 그 제조방법
CN108976914B (zh) * 2018-08-14 2021-06-22 重庆文理学院 一种高分散的铜纳米线导电墨水、导电薄膜及其制备方法
CN111205479B (zh) * 2020-01-14 2022-11-18 陕西师范大学 一种改性细菌纤维素纳米纤维稳定的高内相Pickering乳液及其制备方法
CN111471125B (zh) * 2020-05-25 2021-11-09 哈尔滨工程大学 一种Pickering乳液制备透明导电材料的方法
CN111933726B (zh) * 2020-07-31 2023-06-09 浙江晶科能源有限公司 电极、电极制备方法及太阳能电池

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3209816B2 (ja) * 1991-12-28 2001-09-17 平井 英史 金属微粒子及び／又は金属化合物微粒子の非水分散液の調製方法
US6516633B1 (en) * 2000-08-28 2003-02-11 Nano-Tex, Llc Photochromic glass nanoparticles and methods of preparation
TWI251018B (en) 2002-04-10 2006-03-11 Fujikura Ltd Electroconductive composition, electroconductive coating and method of producing the electroconductive coating
US7566360B2 (en) 2002-06-13 2009-07-28 Cima Nanotech Israel Ltd. Nano-powder-based coating and ink compositions
JP2005209350A (ja) * 2004-01-20 2005-08-04 Sumitomo Metal Mining Co Ltd 透明導電膜及び透明導電膜の製造方法
WO2005088652A1 (fr) * 2004-03-10 2005-09-22 Asahi Glass Company, Limited Particule fine contenant un métal, dispersion liquide de particules fines contenant un métal et matériau conducteur contenant un métal
TW200609109A (en) 2004-08-02 2006-03-16 Nippon Denkai Ltd Composite copper foil and method for production thereof
US7270694B2 (en) * 2004-10-05 2007-09-18 Xerox Corporation Stabilized silver nanoparticles and their use
DE102008023882A1 (de) * 2008-05-16 2009-11-19 Bayer Materialscience Ag Druckbare Zusammensetzung auf Basis von Silberpartikeln zur Erzeugung elektrisch leitfähiger Beschichtungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012084849A2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115401203A (zh) * 2022-08-12 2022-11-29 浙江工业大学 一种减小以熔盐为介质的金属乳液法所制得的锡微球粒径的方法
CN115401203B (zh) * 2022-08-12 2024-04-30 浙江工业大学 一种减小基于熔盐金属乳液法所制锡微球粒径的方法

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KR20140007359A (ko) 2014-01-17
SG191736A1 (en) 2013-08-30
EP2468826A1 (fr) 2012-06-27
BR112013018452A2 (pt) 2018-05-22
JP2014505969A (ja) 2014-03-06
WO2012084849A3 (fr) 2012-08-16
CN103429673A (zh) 2013-12-04
TW201232566A (en) 2012-08-01
CA2821844A1 (fr) 2012-06-28
US20130337158A1 (en) 2013-12-19
WO2012084849A2 (fr) 2012-06-28

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