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EP2513369B1 - Procédé de fabrication de surfaces métallisées, surface métallisée et son utilisation - Google Patents

Procédé de fabrication de surfaces métallisées, surface métallisée et son utilisation Download PDF

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Publication number
EP2513369B1
EP2513369B1 EP10790438.5A EP10790438A EP2513369B1 EP 2513369 B1 EP2513369 B1 EP 2513369B1 EP 10790438 A EP10790438 A EP 10790438A EP 2513369 B1 EP2513369 B1 EP 2513369B1
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EP
European Patent Office
Prior art keywords
metal
process according
textiles
textile
metal powder
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.)
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EP10790438.5A
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German (de)
English (en)
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EP2513369A2 (fr
Inventor
Christian Steinig-Nowakowski
Ralf NÖRENBERG
Sorin Ivanovici
Peter Breyer
Jürgen Reichert
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • 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
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/2481—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including layer of mechanically interengaged strands, strand-portions or strand-like strips
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2098—At least two coatings or impregnations of different chemical composition
    • Y10T442/2107—At least one coating or impregnation contains particulate material

Definitions

  • the present invention relates to surfaces which are produced by the process according to the invention. Furthermore, the present invention relates to the use of metallized surfaces.
  • metallized fabrics for example films and metallized textiles
  • metallized textile fabrics can be used, for example, as heating jackets, furthermore as fashion items, for example for luminous textiles, or for the production of textiles which can be used in medicine including prophylaxis, for example for monitoring organs and their function.
  • metallized textile fabrics for shielding electromagnetic radiation.
  • WO 2007/074090 discloses a method for producing metallized textiles.
  • the disclosed method allows a simple production of, for example, heatable textiles. It is based on textile, on which a metal powder is printed, preferably a carbonyl iron powder.
  • metallizing for example by electroplating. It is extremely easy to create complicated metallized patterns.
  • WO 2008/101917 discloses a method for the production of metallized textiles, which are provided in an additional step with power-generating or power-consuming articles.
  • WO 2008/155350 discloses a method for producing metallized surfaces, characterized by applying (A) in a planar or patterned form a formulation containing as component at least one metal powder, and (B) depositing another metal on the textile surface.
  • WO 2009/123771 discloses aqueous formulations suitable for printing containing graphene, a rheology modifier and a dispersant.
  • Hot spots may also be undesirable in metallized plastic films.
  • a surface of a substrate is prepared, which may be made of any, preferably acid-stable, materials.
  • Suitable, for example, manually flexible substrates such as plastic films such as films of polyethylene, polypropylene, polystyrene and / or copolymers of polystyrene, such as ABS or SAN, polyvinyl chloride.
  • the surface of the substrate is a textile surface, in the context of the present invention also referred to as textile for short, for example knitted fabrics, ribbons, tapes, knitwear or preferably nonwovens or nonwovens.
  • Textiles in the sense of the present invention may be stiff or preferably flexible.
  • Textiles for the purposes of the present invention may be natural fibers or synthetic fibers or mixtures of natural fibers and synthetic fibers.
  • natural fibers are wool, flax and, preferably, cotton.
  • synthetic fibers include polyamide, polyester, modified polyester, polyester blends, polyamide blends, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers, preferably polyester and blends of cotton with synthetic fibers, especially blends of cotton and polyester.
  • Textile according to the present invention may be untreated or preferably pretreated.
  • pretreatment methods are bleaching, dyeing, coating and finishing, for example crease-arm equipment.
  • Textile is brought to a first step (A), also referred to as step (A) on textile surface or patterned a formulation containing as a component at least one metal powder (a), wherein the metal in question in the electrochemical series of the elements preferably has a stronger negative normal potential than hydrogen.
  • the formulation of step (A) is a preferably liquid formulation, more preferably an aqueous formulation.
  • aqueous formulations are understood to mean those whose continuous phase comprises at least 50%, preferably at least 66%, and particularly preferably at least 90%, of water as solvent.
  • aqueous formulations include those in which the continuous phase contains no organic solvents.
  • formulation of step (A) contains in the range of 1 to 70 wt% of metal powder (a).
  • the metal underlying the metal powder (a) has a greater negative normal potential than hydrogen in the electrochemical series of the elements.
  • Metal powder (a) whose metal in the electrochemical series of the elements preferably has a stronger negative normal potential than hydrogen, in the context of the present invention is also referred to for short as metal powder (a).
  • Metal powder (a) is preferably one or more metals in powdered form, the metal (s) being preferably more noble than hydrogen.
  • the metal powder (a) used is preferably silver, tin, nickel, zinc or alloys of one or more of the abovementioned metals.
  • the particles of metal powder (a) have an average diameter in the range of 1 to 250 nm, preferably 10 to 100 nm, particularly preferably 15 to 25 nm.
  • the particles of metal powder (a) have an average particle diameter of 0.01 to 100 .mu.m, preferably from 0.1 to 50 .mu.m, particularly preferably from 1 to 10 .mu.m, determined by laser diffraction measurement, for example on a device Microtrac X100.
  • substrate and especially textile in step (A) are printed with a printing formulation, preferably an aqueous printing formulation containing at least one metal powder (a), wherein the metal in question preferably has a stronger negative normal potential in the electrochemical series of the elements has as hydrogen.
  • printing formulations are printing inks, e.g. As gravure inks, offset inks, printing inks such. As inks for the Valvolineclar and preferably printing pastes, preferably aqueous printing pastes.
  • Metal powder (a) can be selected, for example, from powdered Zn, Ni, Cu, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi, for example pure or in admixture or in the form of alloys of said metals with one another or with other metals ,
  • suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCu, NiP, ZnFe, ZnNi, ZnCo and ZnMn.
  • Preferably usable metal powders (a) comprise only one metal, particularly preferred are iron powder and copper powder, most preferably iron powder.
  • metal powder (a) has an average particle diameter of from 0.01 to 100 ⁇ m, preferably from 0.1 to 50 ⁇ m, particularly preferably from 1 to 10 ⁇ m (determined by laser diffraction measurement, for example on a Microtrac X100 device).
  • metal powder (a) is characterized by its particle diameter distribution.
  • the value d 10 can be in the range of 0.01 to 5 ⁇ m, the value for d 50 in the range of 1 to 10 ⁇ m and the value for d 90 in the range of 3 to 100 ⁇ m, where d 10 ⁇ d 50 ⁇ d 90 .
  • no particle has a larger diameter than 100 microns.
  • Metal powder (a) can be used in passivated form, for example in an at least partially coated (“coated") form.
  • suitable coatings include inorganic layers such as the oxide of the metal in question, SiO 2 or SiO 2 .alpha., Or phosphates, for example, of the metal in question.
  • the particles of metal powder (a) can in principle have any desired shape, for example acicular, plate-shaped or spherical particles can be used; spherical and plate-shaped are preferred.
  • metal powders (a) with spherical particles preferably predominantly with spherical particles, very particularly preferably so-called carbonyl iron powders with spherical particles, are used.
  • metal powders (a) are known per se. It is possible, for example, to use common commercial goods or metal powder (a) prepared by processes known per se, for example by electrolytic deposition or chemical reduction from solutions of salts of the metals concerned or by reduction of an oxidic powder, for example by means of hydrogen, by spraying or atomizing a molten metal, in particular in cooling media, for example gases or water.
  • metal powder (a) which has been prepared by thermal decomposition of iron pentacarbonyl, also called carbonyl iron powder in the context of the present invention.
  • the preparation of carbonyl iron powder by thermal decomposition of iron pentacarbonyl in particular Fe (CO) 5 is described for example in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599.
  • the decomposition of iron pentacarbonyl can be carried out, for example, at atmospheric pressure and, for example, at elevated temperatures, eg. B. in the range of 200 to 300 ° C, z. B. in a heatable decomposer, which is a tube made of a refractory material such as quartz glass or V2A steel in a preferably vertical position, which is surrounded by a heating device, for example consisting of heating bands, heating wires or from a heating medium through which flows heating jacket.
  • a heating device for example consisting of heating bands, heating wires or from a heating medium through which flows heating jacket.
  • the mean particle diameter of carbonyl iron powder can be controlled by the process parameters and reaction behavior in the decomposition in wide ranges and is (number average) usually from 0.01 to 100 .mu.m, preferably from 0.1 to 50 .mu.m, more preferably from 1 to 8 microns.
  • Metal powder (a) can be printed in one embodiment of step (A) so that the particles of metal powder are so close that they are already capable of conducting electricity. In another embodiment of step (A) one can print so that the particles of metal powder (a) are so far apart that they are not capable of conducting the flow.
  • step (A) metal powder (a) is applied so as to produce an interdigital structure.
  • An interdigital structure is understood to mean a pattern in which the elements intermesh with one another without touching each other.
  • the formulation of step (A) may contain a binder (b). preferably at least one aqueous dispersion of at least one film-forming polymer, for example polyacrylate, polybutadiene, copolymers of at least one vinyl aromatic with at least one conjugated diene and optionally further comonomers, for example styrene-butadiene binders.
  • a binder (b) preferably at least one aqueous dispersion of at least one film-forming polymer, for example polyacrylate, polybutadiene, copolymers of at least one vinyl aromatic with at least one conjugated diene and optionally further comonomers, for example styrene-butadiene binders.
  • Other suitable binders are selected from polyurethane, preferably anionic polyurethane, or ethylene (meth) acrylic acid copolymer.
  • Binder (b) can also be referred to as binder (b) in the context of the present invention.
  • Suitable polyacrylates for the purposes of the present invention as binders (b) are obtainable, for example, by copolymerization of at least one (meth) acrylic acid C 1 -C 10 -alkyl ester, for example methyl acrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, with at least one further comonomer, for example a further (meth) acrylic C 1 -C 10 -alkyl ester, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, glycidyl (meth) acrylate or a vinyl aromatic compound such as styrene.
  • at least one (meth) acrylic acid C 1 -C 10 -alkyl ester for example methyl acrylate, ethyl acrylate, n-butyl acrylate, n-buty
  • Suitable binders (b) for the purposes of the present invention are preferably anionic polyurethanes obtainable, for example, by reacting one or more aromatic or preferably aliphatic or cycloaliphatic diisocyanates with one or more polyester diols and preferably one or more hydroxycarboxylic acids, eg. B hydroxyacetic acid, or preferably dihydroxycarboxylic acids, for example, 1,1-dimethylolpropionic acid, 1,1-dimethylolbutyric acid or 1,1-dimethylolethanoic acid, or a diaminocarboxylic acid, for example the Michael addition product of ethylenediamine to (meth) acrylic acid.
  • hydroxycarboxylic acids eg. B hydroxyacetic acid
  • dihydroxycarboxylic acids for example, 1,1-dimethylolpropionic acid, 1,1-dimethylolbutyric acid or 1,1-dimethylolethanoic acid, or a diamino
  • Ethylene (meth) acrylic acid copolymers which are particularly suitable as binders (b) are, for example, by copolymerization of ethylene, (meth) acrylic acid and optionally at least one further comonomer, such as (meth) acrylic acid C 1 -C 10 -alkyl ester, maleic anhydride, isobutene or vinyl acetate, preferably by copolymerization at temperatures in the range of 190 to 350 ° C and pressures in the range of 1500 to 3500, preferably 2000 to 2500 bar.
  • Ethylene (meth) acrylic acid copolymers which are particularly suitable as binders (b) may comprise, for example, up to 90% by weight of ethylene in copolymerized form and have a melt viscosity v in the range from 60 mm 2 / s to 10,000 mm 2 / s, preferably 100 mm 2 / s to 5,000 mm 2 / s, measured at 120 ° C.
  • Ethylene (meth) acrylic acid copolymers which are particularly suitable as binder (b) may comprise, for example, up to 90% by weight of ethylene in copolymerized form and have a melt flow rate (MFR) in the range from 1 to 50 g / 10 min, preferably 5 to 20 g / 10 min, more preferably 7 to 15 g / 10 min, measured at 160 ° C and a load of 325 g according to EN ISO 1133.
  • MFR melt flow rate
  • binders (b) are copolymers of at least one vinylaromatic with at least one conjugated diene and optionally further comonomers, for example styrene-butadiene binders, at least one ethylenically unsaturated carboxylic acid or dicarboxylic acid or a suitable derivative, for example the corresponding anhydride, in copolymerized form.
  • Particularly suitable vinylaromatics are para-methylstyrene, .alpha.-methylstyrene and in particular styrene.
  • Particularly suitable conjugated dienes are isoprene, chloroprene and in particular 1,3-butadiene.
  • Particularly suitable ethylenically unsaturated carboxylic acids or dicarboxylic acids or suitable derivatives thereof are exemplified by (meth) acrylic acid, maleic acid, itaconic acid, maleic anhydride or itaconic anhydride.
  • binders (b) particularly suitable copolymers of at least one vinyl aromatic compound are copolymerized with at least one conjugated diene and optionally further comonomers: 19.9 to 80% by weight of vinyl aromatic, 19.9 to 80% by weight of conjugated diene, 0.1 to 10% by weight of ethylenically unsaturated carboxylic acid or dicarboxylic acid or a suitable derivative, for example the corresponding anhydride.
  • binder (b) is selected from those which have a dynamic viscosity in the range from 10 to 100 dPa.s, preferably from 20 to 30 dPa.s at 23 ° C., determined for example by rotational viscometry, for example with a Haake viscometer.
  • Formulation of step (A) may further comprise one or more additives, for example one or more emulsifiers or one or more thickeners or one or more fixers.
  • emulsifiers for example one or more emulsifiers or one or more thickeners or one or more fixers.
  • Emulsifiers, thickeners, fixers and optionally further additives to be used are described below.
  • the formulation of step (A) has a solids content in the range of 1 to 90%, preferably in the range of 30 to 80%.
  • step (A) so much formulation is applied that the coverage of substrate and in particular of textile with metal powder (a) in the range of 20 to 200 g / m 2 , preferably 40 to 80 g / m 2 lies.
  • step (A) After applying the formulation of step (A), it is possible to cure, for example photochemically or preferably by thermal treatment, in one or more steps. If one wishes to carry out several steps for the thermal treatment, then one can carry out several steps at the same or preferably at different temperatures.
  • Particular preference is given to treating in a first step for thermal treatment at temperatures in the range of, for example, 50 to 110 ° C over a period of 30 seconds to 3 minutes and then in a second step at temperatures in the range of 130 ° C to 200 ° C. a period of 30 seconds to 15 minutes.
  • the temperature at which the thermal treatment is carried out is adjusted to the melting point of the substrate.
  • Printing formulations from step (A) may comprise at least one binder (b), preferably at least one aqueous dispersion of at least one film-forming polymer, for example polyacrylate, polybutadiene, copolymers of at least one vinylaromatic with at least one conjugated diene and optionally further comonomers, for example styrene-butadiene -Binder.
  • suitable binders (b) are selected from polyurethane, preferably anionic polyurethane, or ethylene (meth) acrylic acid copolymer. Binder (b) can also be referred to as binder (b) in the context of the present invention.
  • emulsifier (c) it is possible to use anionic, cationic or preferably nonionic surface-active substances.
  • Suitable cationic emulsifiers (c) are, for example, C 6 -C 18 -alkyl, C 7 -C 18 -aralkyl or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, Morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklareester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide.
  • Suitable anionic emulsifiers (c) are alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: C 12 -C 18 ) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C 4 -C 12 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ), of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ) and of sulfosuccinates, such as, for example, sulfosuccinic mono- or diesters.
  • alkyl sulfates alkyl radical: C 8 to C 12
  • sulfuric monoesters of ethoxylated alkanols degree of ethoxy
  • aryl- or alkyl-substituted polyglycol ethers Preference is given to aryl- or alkyl-substituted polyglycol ethers, furthermore substances which in US 4,218,218 and homologues with y (from the formulas US 4,218,218 ) in the range of 10 to 37.
  • nonionic emulsifiers (c) such as, for example, mono- or preferably polyalkoxylated C 10 -C 30 -alkanols, preferably with three to one hundred mol of C 2 -C 4 -alkylene oxide, in particular ethylene oxide alkoxylated oxo or fatty alcohols.
  • aqueous printing formulations used in step (A) may contain at least one rheology modifier (d) selected from thickeners (d1), which may also be referred to as thickeners, and the viscosity reducing agents (d2).
  • Suitable thickeners (d1) are, for example, natural thickeners or preferably synthetic thickeners.
  • Natural thickeners are those thickeners which are natural products or can be obtained by work-up such as, for example, cleaning operations, in particular extraction of natural products.
  • inorganic natural thickeners are phyllosilicates such as bentonite.
  • organic natural thickeners are preferably proteins such as casein or preferably polysaccharides.
  • Particularly preferred natural thickening agents are selected from agar-agar, carrageenan, gum arabic, alginates such as sodium alginate, potassium alginate, ammonium alginate, calcium alginate and propylene glycol alginate, pectins, polyoses, carob bean gum and dextrins.
  • Synthetic thickeners are selected from generally liquid solutions of synthetic polymers, in particular acrylates, in, for example, white oil or as aqueous solutions, and of synthetic polymers in dried form, for example as a powder prepared by spray-drying.
  • Synthetic polymers used as thickeners (d1) contain acid groups that are completely or partially neutralized with ammonia. Ammonia is released during the fixation process, which lowers the pH and starts the fixation process. The lowering of the pH necessary for fixation can alternatively be effected by addition of nonvolatile acids such as citric acid, succinic acid, glutaric acid or malic acid.
  • Very particularly preferred synthetic thickeners are selected from copolymers of 85 to 95% by weight of acrylic acid, 4 to 14% by weight of acrylamide and 0.01 to at most 1% by weight of the (meth) acrylamide derivative of the formula I. with molecular weights M w in the range of 100,000 to 2,000,000 g / mol, in which the radicals R 1 may be identical or different and may denote methyl or hydrogen.
  • thickeners (d1) are selected from reaction products of aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or dodecane-1,12-diisocyanate with preferably 2 equivalents of polyalkoxylated fatty alcohol or oxo alcohol, for example 10 to 150-fold ethoxylated C 10 -C 30 Fatty alcohol or C 11 -C 31 oxo alcohol.
  • aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or dodecane-1,12-diisocyanate with preferably 2 equivalents of polyalkoxylated fatty alcohol or oxo alcohol, for example 10 to 150-fold ethoxylated C 10 -C 30 Fatty alcohol or C 11 -C 31 oxo alcohol.
  • Suitable viscosity-lowering agents (d2) are, for example, organic solvents such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), ethylene glycol, diethylene glycol, butyl glycol, dibutyl glycol, and, for example, residual alcohol-free alkoxylated nC 4 -C 8- alkanoi, preferably residual alcohol-free one to 10-fold, particularly preferably 3 to 6-fold ethoxylated nC 4 -C 8 -alkanol.
  • residual alcohol is to be understood as meaning the respective non-alkoxylated nC 4 -C 8 -alkanol.
  • the printing formulation used in step (A) contains in the range from 10 to 90% by weight, preferably from 50 to 85% by weight, particularly preferably from 60 to 80% by weight, of metal powder (a), in the range of 1 to 20% by weight, preferably 2 to 15% by weight of binder (b), in the range from 0.1 to 4% by weight, preferably up to 2% by weight, of emulsifier (c), in the range of 0 to 5 wt .-%, preferably 0.2 to 1 wt .-% rheology modifier (d), wherein in wt .-% in each case on the total in step (A) used pressure formulation and are based on binder (b) refer to the solids content of the respective binder (b).
  • step (A) of the process according to the invention can be printed in step (A) of the process according to the invention with a printing formulation which in addition to metal powder (a) and optionally binder (b), emulsifier (c) and optionally rheology modifier (d) at least one adjuvant (e ) contains.
  • a printing formulation which in addition to metal powder (a) and optionally binder (b), emulsifier (c) and optionally rheology modifier (d) at least one adjuvant (e ) contains.
  • Auxiliaries (e) which may be mentioned by way of example are handle improvers, defoamers, wetting agents, leveling agents, urea, active substances such as, for example, biocides or flameproofing agents.
  • Suitable defoamers are, for example, silicone-containing defoamers such as, for example, those of the formula HO- (CH 2 ) 3 -Si (CH 3 ) [OSi (CH 3 ) 3 ] 2 and HO- (CH 2 ) 3 -Si (CH 3 ) [OSi ( CH 3 ) 3 ] [OSi (CH 3 ) 2 OSi (CH 3 ) 3 ], not alkoxylated or alkoxylated with up to 20 equivalents of alkylene oxide and in particular ethylene oxide.
  • Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-times ethoxylated preferably unbranched C 10 -C 20 -alkanols, unbranched C 10 -C 20 -alkanols and 2-ethylhexan-1-ol.
  • Further suitable defoamers are fatty acid C 8 -C 20 -alkyl esters, preferably C 10 -C 20 -alkyl stearates, in which C 8 -C 20 -alkyl, preferably C 10 -C 20 -alkyl, may be unbranched or branched.
  • suitable wetting agents are nonionic, anionic or cationic surfactants, in particular ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, furthermore ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenylphosphonates, Alkyl phosphates, or alkylphenyl phosphates.
  • nonionic, anionic or cationic surfactants in particular ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, furthermore ethoxylates of oleic acid or alkylphenols, alkylphenol ether s
  • Suitable leveling agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M n in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol.
  • block copolymers of propylene oxide / ethylene oxide for example of the formula EO 8 PO 7 EO 8 , where EO is ethylene oxide and PO is propylene oxide.
  • Suitable biocides are, for example, commercially available as Proxel brands. Examples include: 1,2-Benzisothiazolin-3-one ("BIT”), commercially available as Proxet® brands from. Avecia Lim., And its alkali metal salts; other suitable biocides are 2-methyl-2H-isothiazol-3-one (“MIT”) and 5-chloro-2-methyl-2H-isothiazol-3-one (“CIT”).
  • BIT 1,2-Benzisothiazolin-3-one
  • MIT 2-methyl-2H-isothiazol-3-one
  • CIT 5-chloro-2-methyl-2H-isothiazol-3-one
  • the printing formulation used in step (A) contains up to 30% by weight of adjuvant (s), based on the sum of metal powder (a), binder (b), emulsifier (c) and optionally rheology modifier (i.e. ).
  • step (A) full-surface printing is carried out with a printing formulation containing at least one metal powder (a).
  • a pattern of metal powder (a) is printed by printing substrate and especially textile in some places with pressure formulation containing metal powder (a) and not elsewhere.
  • such patterns are printed in which metal powders (a) are arranged in the form of straight or preferably curved strip patterns or line patterns on substrate and in particular textile, the lines mentioned for example having a width and thickness in the range from 0.1 ⁇ m to 5 mm and said strips may have a width in the range of 5.1 mm to, for example, 10 cm, or optionally more, and a thickness of 0.1 ⁇ m to 5 mm.
  • such striped patterns or line patterns of metal powder (a) are printed as those in which the stripes do not touch or intersect. Most preferably, such patterns are printed, which represent an interdigital structure.
  • the strips or lines may have a minimum distance in the range of 2 to 3 mm.
  • step (A) methods are printed which are known per se.
  • a stencil is used by means of which the pressure formulation containing metal powders (a) is pressed with a doctor blade.
  • the method described above belongs to the screen printing method.
  • Other suitable printing processes are gravure printing and flexographic printing.
  • Another suitable printing method is selected from valve jet method. Valve-jet processes use such a printing formulation, which preferably contains no thickening agent (d1).
  • step (B) a further metal is deposited on the surface of the substrate and in particular the textile fabric.
  • the textile fabric is meant the textile previously processed in step (A).
  • step (B) It is possible to deposit several further metals in step (B), but it is preferable to deposit only one more metal.
  • the metal powder selected is (a) carbonyl iron powder and, as further metal, silver, gold and in particular copper.
  • step (B1) the procedure is to operate in step (B1) without an external voltage source and that the further metal in step (B1) in the electrochemical series of the elements, in alkaline or preferably in acidic solution, has a more positive normal potential than metal, which is based on metal powder (a), and as hydrogen.
  • step (A) and in step (B) processed substrate and in particular textile treated with a basic, neutral or preferably acidic preferably aqueous solution of salt of further metal and optionally one or more reducing agents, for example by inserting it in the solution in question.
  • step (B1) in the range of 0.5 minutes, up to 12 hours, preferably up to 30 minutes, are treated.
  • step (B1) a basic, neutral or preferably acidic solution of further metal salt is treated which has a temperature in the range of 0 to 100 ° C, preferably 10 to 80 ° C.
  • alkali hypophosphite in particular NaH 2 PO 2 .2H 2 O
  • boranates in particular NaBH 4
  • step (B2) the present invention proceeds by operating in step (B2) with external voltage source and that the additional metal in step (B2) in the electrochemical series of the elements in acidic or alkaline solution may have a stronger or weaker positive normal potential than metal, the metal powder (a) is based.
  • the metal powder (a) is based.
  • the further metal in step (B2) has a more positive normal potential in the electrochemical series of the elements than hydrogen, and the metal which is based on metal powder (a) is that additional metal is used in analogy to step ( B1) is deposited.
  • step (B2) it is possible, for example, to apply a current having a strength in the range from 10 to 100 A, preferably 12 to 50 A.
  • step (B2) it is possible to operate, for example, over a period of 1 to 60 minutes using an external power source.
  • step (B1) and step (B2) are combined by operating first with and without external voltage source and the other metal in step (B) in the electrochemical series of the elements being more positive Normal potential may have as a metal, the metal powder (a) is based.
  • auxiliaries are added to the solution of further metal.
  • adjuvants include buffers, surfactants, polymers, in particular particulate polymers whose particle diameter is in the range from 10 nm to 10 ⁇ m, defoamers, one or more organic solvents, one or more complexing agents.
  • Particularly suitable buffers are acetic acid / acetate buffer.
  • Particularly suitable surfactants are selected from cationic, anionic and in particular nonionic surfactants.
  • cationic surfactants which may be mentioned are: primary, secondary, tertiary or quaternary ammonium salts having C 6 -C 18 -alkyl, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, Isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • dodecylammonium acetate or the corresponding hydrochloride examples which may be mentioned are dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paracetic acid esters, N-cetylpyridinium chloride, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium bromide, N- DodecylN, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide.
  • Suitable anionic surfactants are alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric acid monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C 12 -C 18 ) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50 , Alkyl radical: C 4 -C 12 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ), of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ) and of sulfosuccinates, such as, for example, sulfosuccinic mono- or diesters.
  • alkyl sulfates alkyl radical: C 8 to C 12
  • sulfuric acid monoesters of ethoxylated alkanols degree of ethoxylation: 4 to
  • aryl- or alkyl-substituted polyglycol ethers Preference is given to aryl- or alkyl-substituted polyglycol ethers, furthermore substances which in US 4,218,218 and homologues with y (from the formulas US 4,218,218 ) in the range of 10 to 37.
  • nonionic surfactants such as, for example, mono- or preferably polyalkoxylated C 10 -C 30 alkanols, preferably with three to one hundred moles of C 2 -C 4 -alkylene oxide, in particular ethylene oxide alkoxylated oxo or fatty alcohols.
  • Suitable defoamers are, for example, silicone-containing defoamers such as, for example, those of the formula HO- (CH 2 ) 3 -Si (CH 3 ) [OSi (CH 3 ) 3 ] 2 and HO- (CH 2 ) 3 -Si (CH 3 ) [OSi ( CH 3 ) 3 ] [OSi (CH 3 ) 2 OSi (CH 3 ) 3 ], not alkoxylated or alkoxylated with up to 20 equivalents of alkylene oxide and in particular ethylene oxide.
  • Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-times ethoxylated preferably unbranched C 10 -C 20 -alkanols, unbranched C 10 -C 20 -alkanols and 2-ethylhexan-1-ol.
  • Further suitable defoamers are fatty acid C 8 -C 20 -alkyl esters, preferably C 10 -C 20 -alkyl stearates, in which C 8 -C 20 -alkyl, preferably C 10 -C 20 -alkyl, may be unbranched or branched.
  • Suitable complexing agents are those compounds which form chelates. Preference is given to those complexing agents which are selected from amines, diamines and triamines which carry at least one carboxylic acid group. Examples include nitrilotriacetic acid, ethylenediaminetetraacetic acid and Diethylenpentaaminpentaessigklare and the corresponding alkali metal salts mentioned.
  • as much additional metal is deposited as to produce a layer thickness in the range from 100 nm to 100 .mu.m, preferably from 1 .mu.m to 10 .mu.m.
  • metal powder (a) is in most cases partially or completely replaced by additional metal, wherein the morphology of further deposited metal need not be identical to the morphology of metal powder (a).
  • step (B) it is possible to treat thermally according to (B), in one or more steps. If one wishes to carry out several steps for the thermal treatment, then one can carry out several steps at the same or preferably at different temperatures.
  • the thermal treatment according to step (B) can be carried out analogously to the thermal treatment as described above for the connection to step (A).
  • step (C) of the process according to the invention a formulation comprising carbon in the modification as carbon black or, preferably, carbon nanotubes or particularly preferably in the form of graphene is applied over a wide area.
  • "flat” is understood to mean full area or in a wide range, for example in strips at least 1 cm wide, preferably in strips at least 2 cm wide.
  • the application can be done for example with a squeegee.
  • Other ways of applying are screen printing, for example as rotary printing or flatbed printing, and / or padding a textile.
  • a formulation preferably an aqueous formulation, containing carbon in the modification as carbon black or, preferably, in the form of graphene, is applied over the entire surface.
  • a composition comprising carbon in the modification as carbon black, for example furnace black or lampblack, preferably flame black, thermal black, acetylene black, in particular furnace black, is applied over a wide area.
  • carbon black for example furnace black or lampblack, preferably flame black, thermal black, acetylene black, in particular furnace black
  • a formulation comprising carbon nanotubes (carbon nanotubes, in short CNT or English carbon nanotubes), for example single-walled carbon nanotubes (SW CNT) and preferably multi-walled carbon nanotubes (English multi-walled carbon nanotubes, MW CNT).
  • carbon nanotubes carbon nanotubes, in short CNT or English carbon nanotubes
  • SW CNT single-walled carbon nanotubes
  • MW CNT MW CNT
  • Carbon nanotubes are known per se. A method for their preparation and properties, for example by Jess et al. in Chemical Engineering Technology 2006, 78, 94 -100 described.
  • carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
  • Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon monoxide with ethylene.
  • Suitable temperatures for decomposition for example, in the range of 400 to 1000 ° C, preferably 500 to 800 ° C.
  • Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
  • Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
  • the decomposition of volatile carbonaceous compound or carbon-containing compounds in the presence of a decomposition catalyst for example Fe, Co or preferably Ni.
  • carbon in step (C) is graphene.
  • Graphene in the context of the present invention is a carbon modification which comprises substantially sp 2 -hybridized carbon atoms in layers which are about one to 500 carbon atoms thick.
  • graphene is selected from those having a length and a width each in the range of 10 nm to 1000 ⁇ m and a thickness in the range of 0.3 nm to 1 ⁇ m, preferably 1 to 50 nm, and especially preferably up to 5 nm.
  • graphene is selected from those materials having an atomic ratio of carbon: impurity in the range of 50: 1, preferably 100: 1, more preferably 200: 1, and most preferably 500: 1.
  • foreign atoms are the same or different and are substantially selected from oxygen, sulfur, nitrogen, phosphorus and hydrogen, preferably sulfur and oxygen and in particular hydrogen. The proportion of foreign atoms is essentially determined by the manufacturing process of the relevant graphene.
  • graphene is selected from those materials which can be obtained by mechanical or chemical exfoliation (delamination of platelet particles, delamination of one or less layers, preferably up to 500 carbon monolayers) of graphite.
  • graphene is selected from those materials which can be prepared by partial oxidation of graphite to graphite oxide, mechanical exfoliation, and subsequent reduction.
  • graphene is selected from such materials obtained by expansion of graphite or graphite intercalation compounds with alkali metal, hydrogen peroxide, halogen or butyllithium, for example n-butyllithium, followed by exfoliation of layers.
  • exfoliation means a separation of platelet-shaped particles or an exfoliation of one or a few layers, preferably 2 to 1000, particularly preferably 3 to 500 carbon monolayers.
  • graphene has an electrical conductivity in the range of 1 to 200 ⁇ , preferably 15 to 40 ⁇ . This conductivity is determined, for example, over the entire coated surface, for example over the entire layer after step (C).
  • a preferably aqueous formulation is applied in step (C), for example by knife coating, printing, spraying, padding or lamination, preference being given to doctoring and printing.
  • the aqueous formulation contains carbon black, carbon nanotubes or graphene.
  • an aqueous formulation which contains in the range from 1 to 300 g carbon black, carbon nanotubes or graphene / kg formulation, preferably 30 to 60 g / kg.
  • step (C) an aqueous formulation is obtained which contains at least one additive in addition to carbon nanotubes or graphene, for example one or more dispersants (g), one or more rheology modifiers, fixers or emulsifiers.
  • one or more dispersants (g) for example one or more rheology modifiers, fixers or emulsifiers.
  • an aqueous formulation used in step (C) may contain at least one binder (b).
  • suitable dispersants are condensation products of aromatic mono- or disulfonic acids with one or more aldehydes, in particular with formaldehyde, as free acids or in particular as alkali metal salt.
  • a preferred example of dispersants are condensation products of naphthalenesulfonic acid with formaldehyde, as potassium or as sodium salt.
  • dispersing agent (g) in aqueous formulation according to the invention can be completely or partially replaced by one or more emulsifiers (c).
  • the aqueous formulation used in step (C) contains in total in the range from 0.5 to 20% by weight of additives, preferably from 1 to 15% by weight.
  • step (C) 1 to 50 g of carbon black, carbon nanotubes or graphene per m 2 surface of substrate, in particular textile, are applied.
  • thermally treat after the application of carbon black or carbon nanotubes or, in particular, graphene, it is possible to thermally treat. Conditions for a thermal treatment are described above.
  • nanotubes or, preferably, graphene, metallized substrate according to the invention and, in particular, metallized textile fabric according to the invention are obtained. It is possible according to the invention to rinse metallised substrate and in particular metallized textile fabric according to the invention one or more times, for example with water.
  • corrosion-inhibiting layers are layers of one or more of the following materials: waxes, in particular polyethylene waxes, lacquers, for example aqueous base lacquers, 1,2,3-benzotriazole and salts, in particular sulfates and methosulfates of quaternized fatty amines, for example lauryl / myristyltrimethylammonium methosulfate ,
  • films for example, films, in particular polymer films, for example of polyester, polyvinyl chloride, thermoplastic polyurethane (TPU) or in particular polyolefins such as polyethylene or polypropylene, where polyethylene and polypropylene in each case also copolymers of ethylene or propylene are to be understood.
  • TPU thermoplastic polyurethane
  • polyolefins such as polyethylene or polypropylene, where polyethylene and polypropylene in each case also copolymers of ethylene or propylene are to be understood.
  • a flexible layer is a binder (b) which may be the same or different from optionally printed binder (b) from step (B).
  • the application can be carried out in each case by lamination, gluing, welding, doctoring, printing, spraying or pouring.
  • step (E) If you have applied a binder in step (E), then you can then treat again thermally.
  • metallized sheets in particular metallized fabrics, comprising at least one textile substrate, at least one layer of another metal deposited in a pattern, preferably in an interdigital pattern, and at least one layer containing carbon in the modification as carbon black or, preferably, graphene.
  • Another object of the present invention are metallized sheets or substrates and in particular metallized fabrics, obtainable by the method described above.
  • Inventive metallized fabrics can not only be produced well and selectively, for example, the flexibility and the electrical conductivity can be specifically influenced, for example, by the type of printed pattern of metal powder (a) and by the amount of further metal deposited.
  • Metallized fabrics according to the invention can also be used flexibly, for example in applications for electrically conductive textiles.
  • metallized sheets printed with a line or stripe pattern have a resistivity in the range of 1 m ⁇ / cm 2 to 1 M ⁇ / cm 2 and in the range of 1 ⁇ / cm to 1 M ⁇ / cm, respectively. measured at room temperature and along the respective strips or lines.
  • metallized sheets printed with a line or stripe pattern according to the present invention comprise at least two cables fixed to the respective ends of lines or strips in a manner known per se, for example soldered.
  • Another object of the present invention is the use of metallized textile fabrics according to the invention, for example for the production of heated textile, in particular heatable car seats and heated carpets, wallpaper and clothing.
  • Another object of the present invention is the use of metallized fabrics according to the invention as or for the production of such textiles that convert electricity into heat, furthermore of such textiles that can shield natural or artificial electric fields, textile-integrated electronics and RFID -Textiles.
  • RFID textiles are meant, for example, textiles that can identify a radio frequency, e.g. with the help of a device that is called a transponder or english RFID tag. Such devices do not require an internal power source.
  • textile-integrated electronics are textile-integrated sensors, transistors, chips, LEDs (light-emitting diodes), solar modules, solar cells and Peltier elements.
  • textile-integrated sensors are suitable for monitoring the body functions of infants or the elderly. Suitable applications are still warning clothing such.
  • the present invention therefore relates to processes for the production of heatable textiles, such as heatable wallpaper, carpets and curtains, heated car seats and heated carpets, furthermore for the production of such textiles, which convert electricity into heat, and of such textiles, which can shield electric fields , Textile-integrated electronics and RFID textiles using metallized textile fabrics according to the invention.
  • Methods according to the invention for the production of heatable textiles, of textiles which convert electricity into heat, furthermore for textiles which can shield electrical fields, and of RFID textiles using metallized textile fabrics according to the invention can be carried out, for example, in such a way that metallized textile fabric made up.
  • a special object of the present invention are heatable car seats, produced using metallized textile according to the invention.
  • Heatable car seats according to the invention for example, require little power in order to produce a comfortable sitting temperature, and therefore spare the car battery, which is particularly advantageous in winter.
  • metallized textiles according to the invention still have excellent properties, for example only a few "hot spots".
  • a special subject of the present invention are wallpapers, carpets and curtains made using or consisting of metallized textile according to the invention.
  • graphene-containing aqueous formulations are suitable in the range from 0.01 to 5 wt .-%, preferably from 0.1 to 3.5 wt .-%, particularly preferably from 2 to 3 wt .-% graphene, optionally in the range of from 0.1% to 20%, preferably from 4% to 8%, by weight of rheology modifier (d) and optionally in the range of 0.1 to 10 wt .-%, preferably 1 to 6 wt .-% dispersant.
  • Binder (b.1) aqueous dispersion, pH 6.6, solids content 44.8% by weight, of a random emulsion copolymer of 1 part by weight of glycidyl methacrylate, 1 part by weight of acrylic acid, 28.3 parts by weight Parts Styrene, 59.7 parts by weight of n-butyl acrylate, 10 parts by weight of 2-hydroxyethyl acrylate, average particle diameter (weight average) 150 nm, determined by Coulter Counter, T g : -19 ° C., dynamic viscosity (23 ° C.) ) 70 mPa ⁇ s
  • aqueous dispersion pH 7.9, solids content 40%, of a polyurethane composed of hexamethylene diisocyanate and polyester diol prepared by polycondensation of adipic acid, hexane-1,6-diol and neopentyl glycol (molar proportions 1: 0.8: 0.2 ), OH number 55 mg KOH / g according to DIN 53240, and the Na salt of 2'-aminoethyl-2-aminoethanesulfonic acid average particle diameter (weight average) 100 nm, determined by Coulter Counter, T g : -47 ° C, dynamic viscosity (23 ° C) 45 mPa ⁇ s
  • Dispersant (g.1) Condensation product of naphthalenesulfonic acid and formaldehyde, completely neutralized with NaOH.
  • Aqueous printing paste (A.1) was obtained.
  • step (A) Printing on textile, step (A), and thermal treatment
  • a polyester fabric with a mesh 80 mesh with a stripe pattern was printed with printing paste of I.2.
  • the pattern is shown schematically in illustration 1 ,
  • polyester fabric was removed, rinsed twice under running water and dried at 90 ° C over a period of 15 minutes.
  • the metallized polyester fabric PES-1 was printed on a printing table by means of a screen printing stencil and a doctor blade with the formulation of II. Flat between or over the conductor tracks.
  • the thus printed fabric was dried at 80 ° C for 10 minutes and then fixed at 150 ° C for 5 minutes.
  • a metallized fabric according to the invention was obtained in which, after applying an electrical voltage, the surface printed with the formulation according to the invention which contains graphene heated up, for example at 14.3 V to about 50 ° C. However, no hot spots were observed, but a steady warm-up.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Continuous Casting (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Printing Methods (AREA)

Claims (16)

  1. Procédé pour la préparation d'une surface métallisée, caractérisé en ce que
    (A) on applique à la manière d'un modèle une formulation, laquelle contient comme constituant au moins une poudre de métal (a),
    (B) on dépose un autre métal sur la surface textile,
    (C) on applique une autre couche, laquelle contient du carbone dans la modification comme suie ou nanotubes de carbone ou graphène.
  2. Procédé selon la revendication 1, caractérisé en ce que la formulation utilisée dans l'étape (A) contient :
    (e) au moins une poudre de métal,
    (f) au moins un liant,
    (g) au moins un émulsionnant,
    (h) éventuellement au moins un agent de modification de rhéologie.
  3. Procédé selon l'une quelconque des revendications 1 à 2, caractérisé en ce que l'on imprime dans l'étape (A) une formulation d'impression, qui contient au moins une poudre de métal (a).
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on choisit le carbone dans l'étape (C) parmi du graphène.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on réalise une ou plusieurs étapes de traitement thermique (D) à la suite de l'étape (A), (B) ou (C).
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il s'agit pour la poudre de métal (a) d'une poudre que l'on a produite par décomposition thermique de pentacarbonyle de fer.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on travaille dans l'étape (B) sans source de tension externe et en ce que l'autre métal dans l'étape (B) présente dans la série de potentiels électrochimiques des éléments un potentiel normal positif plus fort que le métal qui est à la base de la poudre de métal (a).
  8. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on travaille dans l'étape (B) avec une source de tension externe et en ce que l'autre métal dans l'étape (B) présente dans la série de potentiels électrochimiques des éléments un potentiel normal positif plus fort ou plus faible que le métal qui est à la base de la poudre de métal (a).
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'on fixe après l'étape (B) un ou plusieurs articles, qui nécessitent ou produisent un courant électrique, sur la surface.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on choisit le modèle dans l'étape (A) parmi des structures interdigitales.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'on réalise après l'étape (C) au moins une autre étape, choisie parmi
    (D) l'application d'une couche inhibant la corrosion, et
    (E) l'application d'une couche flexible,
    la couche inhibant la corrosion pouvant être flexible ou rigide.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il s'agit de surfaces textiles.
  13. Surface métallisée obtenue selon le procédé selon l'une quelconque des revendications 1 à 12.
  14. Utilisation de surfaces textiles métallisées selon la revendication 13 comme ou pour la préparation de textiles, qui transforment du courant en chaleur, de textiles qui peuvent faire écran aux champs électriques, de textiles à électronique intégrée, d'installations d'affichage, de garnitures de toits de véhicules automobiles et de textiles, qui peuvent produire du courant.
  15. Textiles, qui transforment du courant en chaleur, textiles qui peuvent faire écran aux champs électriques, textiles à électronique intégrée, dispositifs d'affichage, garnitures de toits de véhicules automobiles et textiles, qui peuvent produire du courant, préparés en utilisant des surfaces textiles métallisées selon la revendication 13.
  16. Structure plane métallisée selon la revendication 13, comprenant
    au moins un substrat,
    au moins une couche d'un métal, laquelle est appliquée dans un modèle,
    au moins une couche d'un autre métal choisi parmi l'or, l'argent ou le cuivre,
    et au moins une couche contenant du carbone dans la modification comme suie ou nanotubes de carbone ou graphène.
EP10790438.5A 2009-12-14 2010-12-13 Procédé de fabrication de surfaces métallisées, surface métallisée et son utilisation Not-in-force EP2513369B1 (fr)

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EP10790438.5A EP2513369B1 (fr) 2009-12-14 2010-12-13 Procédé de fabrication de surfaces métallisées, surface métallisée et son utilisation
PCT/EP2010/069459 WO2011082961A2 (fr) 2009-12-14 2010-12-13 Procédé de fabrication de surfaces métallisées, surface métallisée et son utilisation

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US20110143107A1 (en) 2011-06-16
EP2513369A2 (fr) 2012-10-24
WO2011082961A2 (fr) 2011-07-14
WO2011082961A3 (fr) 2011-11-24
CA2784220A1 (fr) 2011-07-14
RU2012129676A (ru) 2014-01-27
JP2013513737A (ja) 2013-04-22
ES2556334T3 (es) 2016-01-15
RU2548073C2 (ru) 2015-04-10

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