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WO2009015493A1 - Compositions comprenant des nanoparticules de métal non noble, enrobées de carbone - Google Patents

Compositions comprenant des nanoparticules de métal non noble, enrobées de carbone Download PDF

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Publication number
WO2009015493A1
WO2009015493A1 PCT/CH2007/000372 CH2007000372W WO2009015493A1 WO 2009015493 A1 WO2009015493 A1 WO 2009015493A1 CH 2007000372 W CH2007000372 W CH 2007000372W WO 2009015493 A1 WO2009015493 A1 WO 2009015493A1
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WIPO (PCT)
Prior art keywords
layer
polymer
composition according
composition
nanoparticles
Prior art date
Application number
PCT/CH2007/000372
Other languages
English (en)
Inventor
Evagelos Athanassiou
Norman A. Lüchinger
Wendelin Jan Stark
Original Assignee
Eth Zurich
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 Eth Zurich filed Critical Eth Zurich
Priority to PCT/CH2007/000372 priority Critical patent/WO2009015493A1/fr
Publication of WO2009015493A1 publication Critical patent/WO2009015493A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • C09D7/45—Anti-settling agents
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • B05D5/068—Metallic effect achieved by multilayers
    • 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
    • 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

Definitions

  • compositions comprising carbon coated, non-noble metal nanopartides
  • the present invention relates to dispersions and ink formulations ("compositions") of carbon-coated non-noble metal nanoparticles, to the manufacture of such compositions, to devices containing such compositions, to the manufacture of such devices and to uses of such compositions and devices.
  • compositions are stable against oxidation by air (“air-stable”) or by chemical treatment.
  • Rickerby et. al. 18 describe the use of hexafluoro-acetyl-acetone- Cu (I) poly-vinyl siloxanes as precursor for the deposition and writing of copper. While the authors managed to deposit copper the method suffers from toxic chemistry and the use of expensive materials. Further, the deposition shows a strong tendency of hollowing. This makes deposition of defined pattern a difficult and/or costly issue.
  • WO2005/044451 describes a method for electroless plating of metals using direct-write technologies.
  • a substrate is selectively coated with metallic copper by depositing a reaction solution of palladium ions and a reducing agent on the surface by ink-jet printing.
  • the reaction is aided by the presence of an activator, which may be deposited also by ink-jet printing.
  • the palladium film is further used as a catalyst for a second metal deposition reaction of copper.
  • Main drawbacks of this process are the control of the thickness of the catalyst layer as thick layers have the tendency to de-laminate from the substrate due to induced stresses and that it concerns a time- intensive multi-step preparation process (3 different layers applied by ink-jet printing on a single surface).
  • WO03/038002 discloses a method for the deposition of metals on surfaces involving the use of simultaneous reduction and delivering of a reducible metal precursor. This document speculates on the use of copper nanoparticles for coatings having a high electrical conductivity. The exemplified coatings have a conductivity of about 0.002 S/cm only.
  • Athanassiou et. al. 2 describe the preparation of carbon-coated copper nanoparticles that are air-stable and their subsequent application for the manufacturing of pressure and temperature sensing materials. This document, however, does not disclose any liquid composition nor any use in relation to liquid compositions.
  • Luechinger et. al. 19 describe porous metal films and their application for optical humidity sensing. This document discloses use of such paint or printable copper- based porous films as ultra-low cost optical humidity sensors. The document further describes the preparation of stable dispersion of carbon-coated copper in water using specific dispersion agents (BYK 348 and Disperbyk 190). No reference is made for electrical properties of these films beyond color changes of the material upon exposure to solvent or water vapor. The disclosed compositions are not wear-resistant, e.g. they can be rinsed off with water and are therefore considered unsuitable for commercial applications . WO2007/028267 discloses carbon coated nanoparticles and their manufacturing.
  • the nanoparticles have preferable primary particle sizes of .10 - 50 nm, most preferred 20 - 50 nm and exhibit high air stability.
  • this document fails to disclose suitable inks / laquers that can be readily applied. Further, no specific uses of the described compositions are provided.
  • compositions that overcome one or more of the above identified problems and to provide corresponding manufacturing processes. It is a further aim of the present invention to provide devices fully or partly coated with the compositions as described herein and to provide corresponding manufacturing processes. Further, it is an aim to provide new uses and applications of the compositions and devices as disclosed herein.
  • nanoparticles are particles having a diameter in the submicron size range and can be either crystalline or amorphous.
  • Such nanoparticles have preferable primary particle sizes of 10 - 50 nm, most preferred 20 - 50 nm of an agglomerate size measured as hydrodynamic particle size distributions below 200 nm. Suitable methods for the determination of primary particle sizes and agglomerate diameter can be found by Limbach et. al . x
  • non-noble metal is known in the field. In particular, it denotes metals or metal alloys, in particular metals.
  • the metal (s), either alone or in an alloy, have a standard potential between +0.52 and -0.41 V as defined in Riedel 1999 3 .
  • Copper is the most electropositive metal within the context of the present invention.
  • Suitable meals are, for example, Cu, Mo, Ni, Co in particular Cu.
  • Suitable alloys are, for example, Ni-Mo, Cu- Ni, Co-Ni.
  • carbon-coated non-noble metal nanoparticles denotes nanoparticles of a core-shell type where the core consists of a non-noble metal as defined above. Such non-noble metal nanoparticles are protected against oxidation by air through deposition of a carbon- coating (the "shell") on their surfaces.
  • Suitable carbon- coatings consist of at least one graphene layer and can contain up to several dozen graphene layers. Most suitable coatings consist of 3 - 10 graphene layers reaching layer thicknesses of 1 - 5 nm carbon. Such coatings are sufficient to protect the non-noble metal core against spontaneous ignition (pyrophoric) or oxidation, e.g. by air or chemical treatment.
  • the invention relates to a composition
  • a composition comprising (i.e. containing or consisting of) carbon-coated non-noble metal nanoparticles; liquid carrier; dispersing additive.
  • the thin carbon coating protects the non-noble nanoparticles from oxidation by air or chemical treatment.
  • Such compositions are sometimes referred to as "dispersion” or "ink”.
  • compositions as described herein may be directly used as a dispersion (e.g. for decorative purposes) or as an ink (e.g. for manufacturing an electrically conductive substrate / surface or printed circuit) .
  • customary additives such as viscosity modifiers, fillers, colorants, humectants, adhesion promoters, may be added to fine-tune the properties of the dispersion / ink to the desired substrate / surface and/or the intended manufacturing process.
  • the metal is selected from the group consisting of Cu, Mo, Ni, Co, in particular Cu. It was found that these metals show particular beneficial optical, electrical and magnetic properties and/or stability. Further, nanoparticles of these metals result in a very robust carbon coating, particular Co and Cu.
  • the carrier contains at least 50 wt-% water, in particular at least 90 wt-% water.
  • Purified water is preferred, for example having an electrical resistivity of > 18M ⁇ cm.
  • the carrier contains at least 50 wt-% water
  • the dispersing additive is a tenside with at least one hydrophilic and one lipohilic group.
  • Advantageous tensides are those, wherein the lipophilic group is selected from the group consisting of aromatic groups (such as styrene-based groups), saturated, unsaturated or partly unsaturated aliphatic groups, siloxane based groups, fluoro-carbon based aliphatic groups.
  • hydrophilic group contains one or more functional moieties selected from the group consisting of sulphonates, phosphonates, substituted and unsubstituted ammonia, hydroxy, hydroxy- (poly) ether (such as glycols), carboxylic acids and its salts.
  • Examples of useful additives for water- based compositions include: Disperbyk, Disperbyk-190 Disperbyk-180, Disperbyk-190, Disperbyk-170, Disperbyk-140, BYK-154, BYK-162, BYK-180, BYK-181, BYK-190, BYK-192, BYK- 333, BYK-348, SMA 1000NA, SMA 100OH, SDS, AOT, Tamol, T1124, Tween 20, Tween 80, L-Il, Betaine, Sodium Laureth Sulfosuccinate and Sulfate, Tego 735W, Tego 740 W, Tego 750 W, Disperbyk, PDAC (poly (diallyldimethylammonium chloride)), Nonidet, CTAC, Daxad 17 and 19 (sodium salt of naphthalene sulfonate formaldehyde condensate), BASF 104, Solspers 43000, Sol
  • the carrier contains at least 50 wt-% water
  • the composition further contains a humectant.
  • Humectants are known in the field, suitable humectants for water-based compositions include: PMA, glycerol, DPM, diethylene glycol, SuIfolam, triethanolamine, Dowanol DB, DMF (dimethyl formamide) , isopropanol, n-propanol, PM (l-methoxy-2-propanol) , Diglyme (di (ethylene glycol) diethyl ether), NMP (1-methyl pyrrolidinone) .
  • the carrier contains at least 50 wt-% organic solvent, preferably at least 90 wt-% organic solvent.
  • organic solvent is advantageously selected from the group consisting of alcohols (including glycols), ethers, esters, ketones, glycols or combinations thereof.
  • organic solvents include: ethanol, DPM (di (propyleneglycol) methyl ether), ethyleneglycol, PMA (1, 2-propanediol monomethyl ether acetate) , 2-butoxyethanol, n-butanol, 2-ethylhexanol and its mixtures.
  • the dispersing additive is a dispersing polymer.
  • Advantageous dispersing polymers are selected from the group consisting of a PVP polymer, an acrylic polymer, a PVP co-Polymer, an acrylic copolymer and mixtures thereof.
  • useful additives for solvent-based compositions include: BYK-9077, Disperbyk-163, PVP K-15.
  • compositions may be applied on substrates (i.e. to the surface of a substrate) by a variety of methods such as by roll coating, drop on demand printing techniques, gravure printing, planographic printing, offset printing screen printing, most preferred by ink-jet printing or brush applications as described in further detail below.
  • substrates i.e. to the surface of a substrate
  • methods such as by roll coating, drop on demand printing techniques, gravure printing, planographic printing, offset printing screen printing, most preferred by ink-jet printing or brush applications as described in further detail below.
  • substrates including flexible, rigid, elastic ones. Specific examples include paper, polymer films, textiles, plastics, glass, fabrics, printed circuit boards, epoxy resins, ceramic and metallic substrates.
  • the invention in a second aspect, relates to a method for manufacturing a composition as described herein, comprising the steps of combining at least one liquid carrier and at least one dispersing additive until a homogeneous phase is obtained; dispersing the nanoparticles as defined herein until a stable dispersion is obtained; optionally removing agglomerates and/or other impurities from the obtained dispersion.
  • the individual steps of this process are known in the field.
  • the first step obtaining a homogeneous phase from a carrier and one or more dispersing additives may be achieved by using standard laboratory / manufacturing equipment, such as a conventional stirrer or ultrasonication. Typically, the additive is added to the stirred carrier.
  • the third step, removal of impurities is also known in the field, and may be achieved by filtration or centrifugation, preferably by centrifugation.
  • the invention relates to a method as described herein, wherein the stable dispersion is obtained by means of ultrasonication.
  • an ultrasonication step for dispersing the nanoparticles (2 nd step of the method as described above) either alone or in combination with conventional mixing, provides very stable dispersions.
  • the invention in a third aspect, relates to a device (article) consisting of: at least a substrate and a further layer comprising a composition as described herein. It is further understood that said article may contain additional layers below said layer (e.g. a primer) or on top of said layer (e.g. a protection layer or other functional layer) .
  • a device / article partly or fully coated with a composition as described in the "first aspect”. Said device / article may have a number of applications as further described in this specification.
  • the device / article comprises a substrate ; a first layer comprising either an amorphous polymer layer or a mixture of a polymer and a surface-active additive; a second layer comprising a composition as described herein; whereby said second layer is directly adjacent to said first layer.
  • the polymers of the first layer may be amorphous, crystalline or partly crystalline.
  • the terms are known in the field; such properties may be identified according to standard processes. It is believed that additives are not necessary when amorphous polymers are used; this is attributed to the smooth surface of amorphous polymers. In turn, when crystalline or partly crystalline polymers are used, additives are beneficial. Acrylic based polymers are a typical example for amorphous polymers.
  • polyether modified silicon tensides, fluoro-carbon tensides or modified acrylic tensides are typical examples of suitable additives in this context.
  • said article may contain additional layers below said first layer (e.g. a primer) or on top said 2 nd layer (e.g. a protection layer or other functional layer) .
  • a 1 st layer as described herein results in articles with an improved wear resistance. At the same time, it is possible to maintain the beneficial optical and electrical properties of the coating. Furhter, it is possible to manufacture such articles with standard equipment, making it suitable for large scale production.
  • the substrate and first layer of the article as described herein are identical. Consequently, the invention relates to an article, wherein the substrate comprises or consists of an amorphous polymer layer or a mixture of a polymer and a surface-active additive; and a layer comprising a composition as described herein; whereby said layer is directly adjacent to the substrate .
  • a composition as described herein may be directly applied to a substrate having all the beneficial properties as described above, in particular wear resistance, high gloss and electrical conductivity. Articles made of such specific substrates are in particular suitable for mass production. It was found that a polymer layer results in a substantially improved coating of a substrate when the applied composition is additionally heated.
  • the thus obtained devices / articles are substantially stable against removal with water (“water proof”),, they are substantially stable against mechanical stress ("wear resistant", no wipe- off with finger) , they show a homogeneous gloss ("mirror- type”) and a very high distinctiveness of image (DOI) .
  • This can be measured quantitatively by measuring diffuse scattering reflectivity.
  • a suitable measurement for such surfaces includes measuring the intensity of the reflected light under specific angles. Such measurement is preferably done on a surface of more than 3 cm 2 and on several spots. Suitable instruments to measure the quality of such surfaces are Gardco glossmeters (Micro-Wave-Scan) according to DIN EN ISO 2813, DIN 67530.
  • the invention relates to a device as described herein wherein the substrate/article is a chassis or body of a vehicle or of a consumer electronics device or a part thereof.
  • vehicle in the context of this invention relates to any vehicle suitable for transportation of humans or goods, such as cars, trucks, bikes, motorbikes, planes, ships, submarines, in particular chassis or rims of a car.
  • consumer electronics device in the context of this invention relates to all electrical equipment used in private, commercial and public environment, such as phones (in particular mobile phones), home electronics (such as mobile players or TV sets) , kitchen equipment, surgical equipment and the like.
  • any surface of a device / article may be coated with a composition as described herein.
  • Particular suitable substrates are selected from the group consisting of glass, plastic, metal, paper, textile, ceramic, polymer, rubber, wood materials and the like as well as circuit boards.
  • Decorative surfaces on devices / articles obtainable by the use of this invention are characterized by complete loss of graininess where the unaided human eye can not distinguish any features in the here accessible surfaces.
  • Such surfaces have been called liquid metal surfaces since they can not be distinguished from molten metal or liquid mercury.
  • Such reflectivity can be measured quantitatively by measuring diffuse scattering.
  • a suitable measurement for such surfaces would include measuring the intensity of the reflected light under specific angles. Such measurements should be done on a surface of more than 3 cm 2 and on several spots .
  • Suitable instruments to measure the quality of such surfaces are Gardco glossmeters (Micro-Wave- Scan) according to DIN EN ISO 2813, DIN 67530.
  • the surface of such liquid metal decorative coating appears feature-less e.g. shows a homogeneous smooth surface.
  • Such surfaces appear to the unaided eye like highly polished metal surfaces. Typically, no further process steps, e.g. polishing, are required to obtain the desired surface appearance. In contrast to this, currently existing flake- based pigments show clear features under a conventional optical microscope or when any of the above methods is applied.
  • the invention in a fourth aspect, relates to a method of manufacturing a device as described herein ("third aspect") comprising the step of optionally applying a first layer as described herein on a substrate and applying a second layer, said layer comprising a composition as described herein, on top of said first layer. It was found that the application of said first and second layer may be accomplished by any suitable method known in the art (“conventional application method”) . Further, standard equipment may be used. These methods include, for example hydraulic or pneumatic or electrostatic spray coating methods .
  • the second layer is applied after the first layer is substantially or fully dried.
  • the coated device is subjected to an additional drying step. Drying conditions, for first and second layer, in particular time / temperature may vary on the polymer used, the thickness of said layer and the material of the substrate. Such conditions may be determined by routine experiments. Typical condition are drying temperatures between r.t. and 200 0 C, preferably between 50 0 C and 150 0 C. Drying times may vary between one second and one hour, preferably between lOsec and lOmin.
  • the invention relates to an electrical circuit consisting of a composition as described herein which is deposited, in particular printed, on a substrate.
  • Said substrate may be optionally coated with a polymer layer prior to deposition of the composition as described herein.
  • Said polymer layer is preferably a "first layer" as described above.
  • the present invention thus provides electrically conductive surfaces based on copper or other non-noble metal nanoparticles that are carbon ⁇ coated. Such surfaces being accessible by known deposition techniques, such as conventional ink-jet printing, spray techniques, lithography, drop on demand, roll coating, gravure printing, letter-less printing, planographic printing, offset printing, screen printing or brush application.
  • electrically conductive layers are characterized by the ease of handling during manufacturing, e.g. no protection against air is required during preparation in any step and no precautions against ignition have to be taken during preparation because these non-noble metals are protected against its pyrophoric nature by the suitable carbon layer.
  • Such electrically conductive layers are further characterized by a high stability against abrasion and stability against wash-off by water. Further, such layers are characterized by an electrical conductivity of above 1 S/cm.
  • the invention relates to the manufacture of an electrical circuit as described herein comprising the step of printing a desired pattern on a substrate.
  • compositions as described herein can be applied using ink-jet printers and other printing technologies and result in electrically conductive layers on various substrates.
  • the thickness of the layers can be varied by printing specific patterns several times. This method is considered very versatile and cost-efficient when compared to standard technologies.
  • Such patterns are applicable for flexible electronic or ultra low-cost electronic or sensing devices.
  • the invention relates to an optical sensor, to the manufacture of such a sensor and to the use of compositions as described herein for the manufacture of such sensors.
  • the use as a humidity sensor is based on the change in color of the dried metallic film as described herein upon exposure to certain conditions, in particular vapor pressure of water or volatile organic substances, such as solvent vapors. It is believed that the coloration mechanism is attributed to the formation of a thin interference layer on top of the metallic film when the humidity or the solvent vapor concentration is increased.
  • This interference layer consists of a mixture of the additive and water (or solvent vapor respectively) . Depending on the humidity or solvent vapor concentration the thickness of the interference layer changes causing a change in the resulting coloration.
  • a suitable composition described herein for the manufacture of an optical sensor comprises at least one surface active additive with a melting temperature lower than 20 °C and a high affinity for water or solvent vapors.
  • a suitable surface active additive with a melting point lower than 20 0 C can be a polyether modified silicone tenside. Such additives are also called slip-additives, leveling agents, wetting agents.
  • compositions suitable for the manufacture of a humidity or solvent vapor sensor see example 1 and example 2.
  • the ink suitable for the manufacture of an optical sensor is applied on a substrate such as glass or on a polymer with a very low surface roughness (i.e. amorphous polymers) .
  • the ink can be applied using ink-jet printing, spray techniques, lithography, drop on demand, roll coating, gravure printing, letter-less printing, planographic printing, offset printing, screen printing or brush application.
  • the composition After application on a smooth substrate the composition is dried, preferably at room temperature, which results in a film with metallic luster and high reflectivity.
  • Such humidity or vapor sensing films are typically not wear-resistant. It is therefore beneficial to protect such films by a transparent spacer from any undesired mechanical contact.
  • a sensitivity of over 50 nm color change per % relative humidity (RH) can be obtained allowing measuring accuracies well below +/- 0.5 % RH when the color is determined by an optical spectrometer.
  • Commercial low-cost humidity sensors in contrast have a low accuracy of +/- 2 % relative humidity (R. H.).
  • This new type of humidity or solvent vapor sensing allows the manufacture of highly sensitive and ultra-low cost sensors without a need of an electric circuit, a display or an energy supply.
  • Suitable applications of such printable or paintable sensors could be in food packaging, consumer goods or pharma industry. Furthermore an application is possible in fluid dynamics visualization for the aerodynamic shape optimization of a vehicle as in automotive or aviation industry.
  • the invention relates to the uses / method of use of a composition as described herein and to the uses / methods of use of devices as described herein.
  • the uses of the compositions basically become apparent when reading the specification. Particular uses of the composition as described herein are the manufacturing
  • composition as described herein can be used as a base material for the preparation of decorative coatings .
  • Such coatings can be made by appropriate spraying of the ink or lacquer on the surface of polymers, glass or metal substrates.
  • the decorative patterns show high reflectivity and uniformity, in particular when applied on substrates with low surface roughness.
  • organic solvent chemical sensors suitable for detection of organic solvents or for visualization of gas fluid dynamics in shape optimization of vehicles or airplanes.
  • printable electronics for the manufacture of printable displays, photovoltaics, radio frequency identification tags (RFID tags), computer memory devices, electronic circuits, processors, photodiodes, high electron mobility transistors (HEMTs) , semiconductor field-effect transistors, printable electronic spools, printable hard-drives .
  • RFID tags radio frequency identification tags
  • HEMTs high electron mobility transistors
  • semiconductor field-effect transistors printable electronic spools
  • printable hard-drives printable hard-drives.
  • dispersions/inks as disclosed herein may be used in numerous industrial applications including the following:
  • UV protective devices • as ultra-violet (UV) protective devices ;
  • the preparation of the carbon coated non-noble nanoparticles is known and described e.g. in WO2007/028267 which is incorporated by reference, in particular example 14 and fig. 20.
  • a stable non-noble metal precursor is dispersed by an oxygen jet (e.g. 5 1/min) in a flame under a nitrogen atmosphere.
  • the flame is encased in a sinter metal tube.
  • This tube is used for cooling of the flame with a mixture of nitrogen (e.g. 30 1/min) and acetylene (e.g. 51/min) .
  • the application of acetylene promotes the formation of the carbon coating round the particles.
  • Suitable carbon coated nanoparticles to be used in the context of this invention are also obtainable from a range of other preparation methods, such as liquid phase chemical methods, described e.g. in 20 ' 21 which are incorporated by reference.
  • a dispersion was prepared consisting of 7.9 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Milipore, electrical resistivity > 18 M ⁇ cm) and a high-molecular-weight, block-copolymeric additive with acidic, pigment-affinic groups (8.3 wt % relative to C/Cu, Disperbyk 190, BYK Chemie) and an amphiphilic silicon tenside (11.7 wt % relative to C/Cu, BYK 348, a polyether- modified poly (dimethyl siloxane) ) .
  • the dispersion was prepared by manually mixing the 2 additives with the deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra- sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles.
  • the dispersion was applied onto glass using a brush. On glass the obtained copper films exhibited high metallic luster.
  • the glass was placed in a closed glass chamber.
  • 0.1 ml water soaked cotton balls containing various concentrations of MgCl2 ( aq j (21.6 wt%-25.6 wt%, Magnesium chloride purum, Fluka-Chemie AG) resulted in the formation of different levels of relative humidity (R. H.) (73.8-63.7 % R. H.) in the closed glass chamber.
  • R. H. relative humidity
  • the coloration mechanism is attributed to the formation of a thin interference layer on top of the metallic film when the humidity is increased.
  • This interference layer consists of a mixture of the silicone tenside and water. Depending on the humidity the thickness of the interference layer changes which causes a change in the resulting coloration.
  • a dispersion was prepared consisting of 7.2 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Millipore, electrical resistivity > 18 M ⁇ cm) and a high-molecular-weight, block-copolymeric additive with acidic, pigment-affinic groups (7.7 wt % relative to C/Cu, Disperbyk 190, BYK Chemie) and an amphiphilic silicon tenside (10.5 wt % relative to C/Cu, BYK 348, a polyether- modified poly (dimethyl siloxane) ) .
  • the dispersion was prepared by manually mixing the 2 additives with the deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra- sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles.
  • the dispersion was applied onto glass using a brush. On glass the obtained copper films exhibited high metallic luster. Exposure of the glass to a stream of ethanol (Ethanol purum, 96%, Fluka-Chemie AG) vapor resulted in rapid and reversible coloration.
  • ethanol Ethanol purum, 96%, Fluka-Chemie AG
  • a dispersion was prepared consisting of 4 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water and 10 % of the anionic surfactant SDS relative to the C/Cu nanoparticles.
  • the dispersion was prepared by manually mixing the dispersing agent SDS with deionized water (Millipore, electrical resistivity > 18 M ⁇ cm) , then adding the carbon coated copper nanoparticles .
  • the nanoparticles were dispersed by ultra-sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles.
  • the dispersion was printed in a Hewlett-Packard Deskjet 2360 ink-jet printer on glossy photo paper (HP Premium Plus Photo Paper) .
  • the printed pattern produced hereby is printed several times to increase the printed film thickness and electrical conductivity.
  • a dispersion was prepared consisting of 2 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Millipore, electrical resistivity > 18 M ⁇ cm) and 10 % of the non-ionic surfactant BYK-348 relative to the C/Cu nanoparticles.
  • the dispersion was prepared by manually mixing the dispersing agent BYK-348 with deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra-sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles .
  • the dispersion was printed in a Hewlett-Packard Deskjet 2360 ink-jet printer on glossy photo paper (HP Premium Plus Photo Paper) , on overhead projector transparencies (laser/copier transparencies, Type C, Xerox) .
  • the dispersion was also applied onto glass and steel using an airbrush gun (HP-101, Conrad electronics) , a brush or a spreading knife.
  • an airbrush gun HP-101, Conrad electronics
  • a brush or a spreading knife On glass and overhead transparencies the obtained copper films exhibited high metallic luster and a mirror-like appearance.
  • the obtained copper films exhibited a characteristic metallic color, but no mirror-like appearance .
  • a dispersion was prepared consisting of 12 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Millipore, electrical resistivity > 18 M ⁇ cm) and 5 % of the cationic surfactant SMAlOOOH (sartomer, www.sartomer.com) relative to the C/Cu nanoparticles.
  • the dispersion was prepared by manually mixing the dispersing agent with deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra-sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminant like dust particles.
  • the dispersion was printed,., i-n a Hewlett-Packard Deskjet 2360 thermal ink-jet printer on glossy photo paper (HP Premium Plus Photo Paper) .
  • the obtained copper film exhibited a characteristic metallic color, but no mirror-like appearance .
  • example 3 containing 12 wt% carbon coated copper nanoparticles and 5 wt% SMA 1000 H relative to the C/Cu nanoparticles was further modified by manually admixing 0.13 % by weight (1.1 wt% relative to C/Cu) of the radically curable wetting agent- BYK UV 3530 for the enhancement of substrate wetting.
  • the dispersion was applied onto glass and steel using application methods such as an airbrush gun (HP-IOl, Conrad electronics), a brush or a spreading knife.
  • an airbrush gun HP-IOl, Conrad electronics
  • a brush or a spreading knife.
  • the obtained copper films exhibited high metallic luster and a mirror-like appearance.
  • the obtained copper films exhibited a characteristic metallic color, but no mirror-like appearance.
  • the dispersion of example 4 containing SMA 1000 H dispersing agent and BYK UV 3530 uv-curable wetting agent was modified by 30 wt% EG (ethylene-glycol) in order to lower the evaporation rate of the dispersion.
  • EG ethylene-glycol
  • the dispersion was applied onto glass and steel using application methods such as an airbrush gun (HP-101, Conrad electronics), a brush or a spreading knife.
  • a dispersion was prepared consisting of 7.2 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Milipore, electrical resistivity > 18 M ⁇ cm) and 4.5 % of the cationic surfactant SMAlOOOH (sartomer, www.sartomer.com) relative to the C/Cu nanoparticles.
  • the dispersion was prepared by manually mixing the dispersing agent with deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra-sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminant like dust particles. Then 3 wt% of the silicone tenside (BYK 348 ) was added relative to C/Cu. This resulted in improved substrate wetting.
  • the obtained ink was applied onto a polymeric substrate using a spreading knife with a gap of 24 microns.
  • the polymeric substrate was a film of a transparent resin with high gloss (Bricacryl Acryl-Klarlack, www.farbladen.ch) which was applied on a sheet of steel 2 days in advance using a spreading knife with a gap of 50 microns.
  • a heat gun (Steinel HG 3000 SLE, 2000W) was used in order to accelerate the evaporation of water of the wet and black ink film.
  • the air temperature at the position of the ink was kept 70 0 C for about 30 seconds and afterwards HO 0 C for about 15 seconds.
  • the resulting copper film exhibited high metallic gloss and a mirror-like appearance. By using an increased drying temperature the copper film became more wear-resistant and rigid compared to a copper film of the same ink applied directly on a glass substrate.
  • the copper film exhibited a dark layer (very thin tenside film) on the surface resulting in a reduced gloss and reflectance.
  • the dark layer could be removed which caused a higher reflectance and gloss.
  • a dispersion was prepared consisting of 7.2 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267 ) in deionized water (Milipore, electrical resistivity > 18 M ⁇ cm) and a high-molecular-weight, block-copolymeric additive with acidic, pigment-affinic groups (7.7 wt % relative to C/Cu, Disperbyk 190, BYK Chemie) and an amphiphilic silicon tenside (10.5 wt % relative to C/Cu, BYK 348, a p ⁇ lyether- modified poly (dimethyl siloxane) ) .
  • the dispersion was prepared by manually mixing the 2 additives with the deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra- sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles.
  • the obtained ink was applied onto a polymeric substrate using a spreading knife with a gap of 24 microns.
  • the polymeric substrate was a film of a transparent resin with high gloss (Bricacryl Acryl- Klarlack, www.farbladen.ch) which was applied on a sheet of steel 2 days in advance using a spreading knife with a gap of 50 microns.
  • a heat gun (Steinel HG 3000 SLE, 2000W) was used in order to accelerate the evaporation of water of the wet and black ink film.
  • the air temperature at the position of the ink was kept 70 0 C for about 30 seconds and afterwards 110 0 C for about 15 seconds.
  • the resulting copper film exhibited high metallic gloss and a mirror-like appearance.
  • the copper film became more wear-resistant and rigid compared to a copper film of the same ink applied directly on a glass substrate.
  • the copper film is more glossy, has a higher reflectance and exhibits no greyisch and darkening layer.
  • a dispersion was prepared consisting of 7.2 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Milipore, electrical resistivity > 18 M ⁇ cm) and 4.5 % of the cationic surfactant SMAlOOOH (sartomer, www.sartomer.com) relative to the C/Cu nanoparticles.
  • the dispersion was prepared by manually mixing the dispersing agent with deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra-sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles.
  • the examples 12 - 20 all contain inks which are prepared from the ink in example 11 (7.2 wt% C/Cu, 4.5 wt% SMA 1000 H relative to C/Cu) by adding other additives. All of those inks were applied on a glass substrate using a spreading knife with a gap of 12 microns.
  • Example 19 Addition of 10 wt% Diethyleneglycol- monobutylether (Fluka 32250) 2 wt% BYK 340 (fluoro-tenside BYK Chemie, relative to C/Cu) 12 wt% hobby color acryl (water based acrylic paint, hobby color H30, GSI Creos Corporation, Tokyo, Japan, relative co C/Cu)
  • a dispersion was prepared consisting of 7.2 % by weight of carbon coated copper nanoparticles (particles synthesized as described in WO2007/028267) in deionized water (Milipore, electrical resistivity > 18 M ⁇ cm) and a high-molecular-weight, block-copolymeric additive with acidic, pigment-affinic groups (7.7 wt % relative to C/Cu, Disperbyk 190, BYK Chemie) and an amphiphilic silicon tenside (10.5 wt % relative to C/Cu, BYK 348, a polyether- modified poly (dimethyl siloxane) ) .
  • the dispersion was prepared by manually mixing the 2 additives with the deionized water, then adding the carbon coated copper nanoparticles.
  • the nanoparticles were dispersed by ultra- sonication (Dr. Hielscher, UP400S, 80% intensity, 0.2 cycle) for 10 minutes.
  • the dispersion was further centrifuged at 2000 rpm (MSE Mistral 300E) for 2 minutes in order to remove undispersed large agglomerates and other contaminants like dust particles.

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Abstract

La présente invention porte sur des compositions comprenant des nanoparticules de métal non noble, enrobées de carbone, un véhicule liquide et un additif de dispersion ; sur la fabrication de telles compositions ; sur des dispositifs contenant de telles compositions ; sur la fabrication de tels dispositifs et sur des utilisations de telles compositions et de tels dispositifs. Les compositions décrites sont stables lorsqu'elles sont exposées à l'air ou à un traitement chimique.
PCT/CH2007/000372 2007-07-27 2007-07-27 Compositions comprenant des nanoparticules de métal non noble, enrobées de carbone WO2009015493A1 (fr)

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EP2239368A1 (fr) * 2009-04-09 2010-10-13 Cham Paper Group Schweiz AG Substrat plat à base organique, utilisation d'un tel substrat et procédé
WO2011013789A1 (fr) 2009-07-31 2011-02-03 共栄社化学株式会社 Agent de traitement de surface destiné à des agents de revêtement
JP2013529226A (ja) * 2010-04-16 2013-07-18 ヴァルスパー・ソーシング・インコーポレーテッド パッケージ物品用のコーティング組成物及びコーティング方法
WO2016060856A1 (fr) * 2014-10-15 2016-04-21 Eastman Kodak Company Particules métalliques dispersées revêtues de carbone, produits et utilisations
US9409219B2 (en) 2011-02-07 2016-08-09 Valspar Sourcing, Inc. Compositions for containers and other articles and methods of using same
US9475328B2 (en) 2012-08-09 2016-10-25 Valspar Sourcing, Inc. Developer for thermally responsive record materials
US9724276B2 (en) 2012-08-09 2017-08-08 Valspar Sourcing, Inc. Dental materials and method of manufacture
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CN108744041A (zh) * 2018-06-11 2018-11-06 宁波西敦医药包衣科技有限公司 具有药物涂层的植入物及其制备方法
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FR3087729A1 (fr) * 2018-10-26 2020-05-01 Psa Automobiles Sa Procede pour impression de surface complexe avec une encre, produit obtenu et composition d’encre pour ce procede.
US11130835B2 (en) 2015-11-03 2021-09-28 Swimc Llc Liquid epoxy resin composition useful for making polymers
CN113858358A (zh) * 2021-09-24 2021-12-31 中国热带农业科学院橡胶研究所 一种降低橡胶木材中淀粉、蛋白质和糖类含量的处理方法

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US8497335B2 (en) 2009-07-31 2013-07-30 Kyoeisha Chemical Co., Ltd. Surface conditioner for coating agents
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EP2460861A4 (fr) * 2009-07-31 2012-12-19 Kyoeisha Chemical Co Ltd Agent de traitement de surface destiné à des agents de revêtement
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