EP2513369B1 - Method for producing metalized surfaces, metalized surface, and the use thereof - Google Patents

Method for producing metalized surfaces, metalized surface, and the use thereof 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
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EP10790438.5A
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German (de)
French (fr)
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EP2513369A2 (en
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)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Laminated Bodies (AREA)
  • Printing Methods (AREA)
  • Continuous Casting (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer metallisierten Oberfläche, dadurch gekennzeichnet, dass man

  1. (A) musterförmig oder flächig eine Formulierung aufbringt, die als Komponente mindestens ein Metallpulver (a) enthält,
  2. (B) ein weiteres Metall auf der textilen Oberfläche abscheidet und
  3. (C) eine weitere Schicht aufbringt, welche Kohlenstoff in der Modifikation als Ruß oder Kohlenstoff-Nanoröhren oder Graphen enthält.
The present invention relates to a method for producing a metallized surface, characterized in that
  1. (A) applying a formulation in a pattern or area which contains as component at least one metal powder (a),
  2. (B) depositing another metal on the textile surface and
  3. (C) applying another layer containing carbon in the modification as carbon black or carbon nanotubes or graphene.

Weiterhin betrifft die vorliegende Erfindung Oberflächen, die nach dem erfindungsgemäßen Verfahren hergestellt sind. Weiterhin betrifft die vorliegende Erfindung die Verwendung von metallisierten Oberflächen.Furthermore, 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.

Die Herstellung von metallisierten Flächengebilden ist ein Arbeitsgebiet mit großem Wachstumspotenzial. Metallisierte Flächengebilde, beispielsweise Folien und metallisierte Textilien, finden zahlreiche Anwendungsgebiete. Insbesondere metallisierte textile Flächengebilde lassen sich beispielsweise als Heizmäntel einsetzen, weiterhin als Modeartikel, beispielsweise für leuchtende Textilien, oder zur Herstellung von Textilien, die in der Medizin einschließlich der Prophylaxe eingesetzt werden können, beispielsweise zur Überwachung von Organen und ihrer Funktion. Weiterhin kann man metallisierte textile Flächengebilde zur Abschirmung von elektromagnetischer Strahlung einsetzen.The production of metallized fabrics is a field of activity with great growth potential. Metallised fabrics, for example films and metallized textiles, find numerous fields of application. In particular, 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. Furthermore, it is possible to use metallized textile fabrics for shielding electromagnetic radiation.

Insbesondere bisherige Verfahren zur Herstellung von derartigen metallisierten Textilien sind jedoch noch sehr aufwändig und nicht flexibel. Man benötigt spezielle Geräte und kann herkömmliche Apparaturen wie beispielsweise konventionelle Webstühle nicht verwenden. So ist es beispielsweise bekannt, Metallfäden in Textil einzuarbeiten. Insbesondere ist bekannt, Kohlenstoff-, Silber- oder Stahlfasern auf Gewebe aufzubringen oder Silber- oder Kupferfasern einzuweben. Es ist jedoch in vielen Fällen nicht möglich, beispielsweise Kupferfäden und Polyesterfäden in einer befriedigenden Weise miteinander zu Geweben kombinieren, weil man spezielle Webstühle benötigt. außerdem muss von Anfang des Produktionsprozesses an feststehen, in welcher Form Metall einzuarbeiten ist. Ein flexibles Eingehen auf Kundenwünsche ist so nicht möglich.However, previous methods for producing such metallized textiles are still very complicated and not flexible. You need special equipment and can not use conventional equipment such as conventional looms. For example, it is known to incorporate metal threads in textile. In particular, it is known to apply carbon, silver or steel fibers to fabrics or to weave silver or copper fibers. However, in many cases it is not possible, for example, to combine copper threads and polyester threads together in a satisfactory manner into fabrics, because special looms are required. In addition, it must be clear from the beginning of the production process on which form of metal is to be incorporated. A flexible response to customer requirements is not possible.

In WO 2007/074090 ist ein Verfahren zur Herstellung von metallisierten Textilien offenbart. Das offenbarte Verfahren erlaubt eine einfache Herstellung beispielsweise von erwärmbaren Textilien. Es geht von Textil aus, auf welches ein Metallpulver aufgedruckt wird, vorzugsweise ein Carbonyleisenpulver. In einem weiteren Schritt metallisiert man, beispielsweise durch Galvanisieren. Man kann äußerst leicht komplizierte metallisierte Muster erzeugen.In 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. In a further step, metallizing, for example by electroplating. It is extremely easy to create complicated metallized patterns.

In WO 2008/101917 ist ein Verfahren zur Herstellung von metallisierten Textilien offenbart, die in einem zusätzlichen Arbeitsschritt mit Strom erzeugenden oder Strom verbrauchenden Artikeln versehen werden.In 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 offenbart ein Verfahren zur Herstellung von metallisierten Oberflächen, dadurch gekennzeichnet, dass man (A) flächig oder musterförmig eine Formulierung aufbringt, die als Komponente mindestens ein Metallpulver enthält, und (B) ein weiteres Metall auf der textilen Oberfläche abscheidet. 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 offenbart wässrige Formulierungen geeignet zum Drucken, enthaltend Graphen, einen Rheologiemodifizierer und ein Dispergiermittel. WO 2009/123771 discloses aqueous formulations suitable for printing containing graphene, a rheology modifier and a dispersant.

Beide offengelegte Methoden erlauben ein äußerst einfaches und kostengünstiges Vorgehen bei der Metallisierung von Textilien. In einigen Fällen werden jedoch auch Nachteile beobachtet. So stellt man fest, dass im Falle des Bruchs oder Knickeris einer der aufgedruckten Leitungen für elektrischen Strom "Hot Spots" entstehen, die auf den aufgebauten elektrischen Widerstand zurückzuführen sind. Derartige "Hot Spots" können eine Feuergefahr bedeuten, da Brüche und Knicken von Leitungen bei länger gebrauchten und mechanisch beanspruchten metallisierten Textilien in vielen Fällen nicht zu vermeiden sind.Both disclosed methods allow a very simple and cost-effective procedure in the metallization of textiles. In some cases, however, disadvantages are also observed. Thus, it is found that in case of breakage or creasing of one of the printed lines for electric power "hot spots" arise due to the established electrical resistance. Such "hot spots" can be a fire hazard, as breaks and kinking of cables in longer used and mechanically stressed metallized textiles are unavoidable in many cases.

Derartige Nachteile sind auch zu beobachten, wenn man andere Substrate als Textil wählt. Hot Spots können auch in metallisierten Kunststofffolien unerwünscht sein.Such disadvantages can also be observed when choosing substrates other than textile. Hot spots may also be undesirable in metallized plastic films.

Es bestand also die Aufgabe, ein Verfahren bereit zu stellen, durch das sich metallisierte Textilien und auch andere metallisierte Substrate herstellen lassen, die auch bei längerer Beanspruchung keine "Hot Spots" bilden. Weiterhin bestand die Aufgabe, metallisierte Textilien bereit zu stellen, die sich einfach herstellen lassen, aber auch bei längerer mechanischer Beanspruchung keine "Hot Spots" bilden.It was therefore the object to provide a method by which metallized textiles and also other metallized substrates can be produced which do not form "hot spots" even during prolonged use. Furthermore, the object was to provide metallized textiles that are easy to produce, but also do not form "hot spots" under prolonged mechanical stress.

Dementsprechend wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.

Das erfindungsgemäße Verfahren zur Herstellung einer metallisierten Oberfläche ist dadurch gekennzeichnet, dass man

  1. (A) flächig oder vorzugsweise musterförmig eine Formulierung aufbringt, die als Komponente mindestens ein Metallpulver (a) enthält,
  2. (B) ein weiteres Metall auf der textilen Oberfläche abscheidet, und
  3. (C) eine weitere Schicht aufbringt, welche Kohlenstoff in der Modifikation als Ruß oder Kohlenstoff-Nanoröhren oder Graphen enthält.
The inventive method for producing a metallized surface is characterized in that one
  1. (A) flat or preferably patterned applying a formulation containing as component at least one metal powder (a),
  2. (B) depositing another metal on the textile surface, and
  3. (C) applying another layer containing carbon in the modification as carbon black or carbon nanotubes or graphene.

Zur Durchführung des erfindungsgemäßen Verfahrens stellt man eine Oberfläche eines Substrats bereit, die aus beliebigen vorzugsweise säurestabilen Materialien sein kann. Geeignet sind beispielsweise manuell biegsame Substrate, beispielsweise Kunststofffolien wie Folien aus Polyethylen, Polypropylen, Polystyrol und/oder Copolymeren von Polystyrol, beispielsweise ABS oder SAN, weiterhin Polyvinylchlorid.To carry out the process according to the invention, 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.

in einer Ausführungsform ist die Oberfläche des Substrats eine textile Oberfläche, im Rahmen der vorliegenden Erfindung auch kurz als Textil bezeichnet, beispielsweise Gewirke, Bänder, Bändchen, Strickwaren oder bevorzugt Gewebe oder Vliesstoffen (Non-Wovens). Textilien im Sinne der vorliegenden Erfindung können steif oder vorzugsweise flexibel sein. Vorzugsweise handelt es sich um solche Textilien, die man ein- oder mehrmals beispielsweise manuell biegen kann, ohne dass man visuell einen Unterschied zwischen vor dem Biegen und nach der Rückstellung aus dem gebogenen Zustand feststellen kann.In one embodiment, 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. Preferably, these are textiles that can be manually or repeatedly bent, for example, without visually detecting a difference between before bending and after recovery from the bent state.

Textilien im Sinne der vorliegenden Erfindung können aus Naturfasern oder synthetischen Fasern oder Gemischen von Naturfasern und synthetischen Fasern sein. An Naturfasern seien beispielsweise Wolle, Flachs und bevorzugt Baumwolle zu nennen. An synthetischen Fasern seien beispielsweise Polyamid, Polyester, modifiziertes Polyester, Polyestermischgewebe, Polyamidmischgewebe, Polyacrylnitril, Triacetat, Acetat, Polycarbonat, Polypropylen, Polyvinylchlorid, Polyestermikrofasern genannt, bevorzugt sind Polyester und Mischungen von Baumwolle mit synthetischen Fasern, insbesondere Mischungen von Baumwolle und Polyester.Textiles for the purposes of the present invention may be natural fibers or synthetic fibers or mixtures of natural fibers and synthetic fibers. Examples of natural fibers are wool, flax and, preferably, cotton. Examples of 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.

Textil im Sinne der vorliegenden Erfindung kann unbehandelt oder vorzugsweise vorbehandelt sein. Beispiele für Vorbehandlungsmethoden sind Bleichen, Färben, Beschichten und Ausrüsten, beispielsweise Knitterarm-Ausrüstung.Textile according to the present invention may be untreated or preferably pretreated. Examples of pretreatment methods are bleaching, dyeing, coating and finishing, for example crease-arm equipment.

Auf Textil bringt man ein einem ersten Arbeitsschritt (A), kurz auch Schritt (A) genannt, auf Textil flächig oder musterförmig eine Formulierung auf, die als Komponente mindestens ein Metallpulver (a) enthält, wobei das betreffende Metall in der elektrochemischen Spannungsreihe der Elemente vorzugsweise ein stärker negatives Normalpotenzial aufweist als Wasserstoff.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.

Bei Formulierung aus Schritt (A) handelt es sich um eine vorzugsweise flüssige Formulierung, besonders bevorzugt um eine wässrige Formulierung. Dabei werden unter wässrigen Formulierungen solche verstanden, deren kontinuierliche Phase mindestens 50%, bevorzugt mindestens 66% und besonders bevorzugt mindestens 90% Wasser als Lösungsmittel umfasst. In einer speziellen Ausführungsform der vorliegenden Erfindung umfassen wässrige Formulierungen solche, bei denen die kontinuierliche Phase keine organischen Lösungsmittel enthält.The formulation of step (A) is a preferably liquid formulation, more preferably an aqueous formulation. In this case, 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. In a specific embodiment of the present invention, aqueous formulations include those in which the continuous phase contains no organic solvents.

In einer Ausführungsform der vorliegenden Erfindung enthält Formulierung aus Schritt (A) im Bereich von 1 bis 70 Gew.-% Metallpulver (a).In one embodiment of the present invention, formulation of step (A) contains in the range of 1 to 70 wt% of metal powder (a).

In einer Ausführungsform der vorliegenden Erfindung weist das dem Metallpulver (a) zu Grunde liegende Metall in der elektrochemischen Spannungsreihe der Elemente ein stärker negatives Normalpotenzial auf als Wasserstoff. Metallpulver (a), dessen Metall in der elektrochemischen Spannungsreihe der Elemente vorzugsweise ein stärker negatives Normalpotenzial aufweist als Wasserstoff, wird im Rahmen der vorliegenden Erfindung auch kurz als Metallpulver (a) bezeichnet.In one embodiment of the present invention, 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).

Metallpulver (a) ist vorzugsweise ein Metall oder mehrere Metalle in pulveriger Form, wobei das oder die Metalle vorzugsweise edler sind als Wasserstoff. Bevorzugt wählt man als Metallpulver (a) Silber, Zinn, Nickel, Zink oder Legierungen von einem oder mehreren der vorstehend genannten Metalle.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.

In einer Ausführungsform der vorliegenden Erfindung haben die Partikel von Metallpulver (a) einen mittleren Durchmesser im Bereich von 1 bis 250 nm, bevorzugt 10 bis 100 nm, besonders bevorzugt 15 bis 25 nm.In one embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung haben die Partikel von Metallpulver (a) einen mittleren Teilchendurchmesser von 0,01 bis 100 µm, bevorzugt von 0,1 bis 50 µm, besonders bevorzugt von 1 bis 10 µm, bestimmt durch Laserbeugungsmessung, beispielsweise an einem Gerät Microtrac X100.In one embodiment of the present invention, 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.

In einer Ausführungsform des erfindungsgemäßen Verfahrens bedruckt man Substrat und insbesondere Textil in Schritt (A) mit einer Druckformulierung, vorzugsweise einer wässrigen Druckformulierung, die mindestens ein Metallpulver (a) enthält, wobei das betreffende Metall in der elektrochemischen Spannungsreihe der Elemente vorzugsweise ein stärker negatives Normalpotenzial aufweist als Wasserstoff.In one embodiment of the process according to the invention, 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.

Beispiele für Druckformulierungen sind Druckfarben, z. B. Tiefdruckfarben, Offsetdruckfarben, Drucktinten wie z. B. Tinten für das Valvolineverfahren und bevorzugt Druckpasten, vorzugsweise wässrige Druckpasten.Examples of printing formulations are printing inks, e.g. As gravure inks, offset inks, printing inks such. As inks for the Valvolineverfahren and preferably printing pastes, preferably aqueous printing pastes.

Metallpulver (a) kann beispielsweise gewählt werden aus pulverförmigem Zn, Ni, Cu, Sn, Co, Mn, Fe, Mg, Pb, Cr und Bi, beispielsweise rein oder als Gemisch oder in Form von Legierungen der genannten Metalle untereinander oder mit anderen Metallen. Geeignete Legierungen sind beispielsweise CuZn, CuSn, CuNi, SnPb, SnBi, SnCu, NiP, ZnFe, ZnNi, ZnCo und ZnMn. Bevorzugt einsetzbare Metallpulver (a) umfassen nur ein Metall, besonders bevorzugt sind Eisenpulver und Kupferpulver, ganz besonders bevorzugt Eisenpulver.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 , Examples of 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.

In einer Ausführungsform der vorliegenden Erfindung hat Metallpulver (a) einen mittleren Teilchendurchmesser von 0,01 bis 100 µm, bevorzugt von 0,1 bis 50 µm, besonders bevorzugt von 1 bis 10 µm (bestimmt durch Laserbeugungsmessung, beispielsweise an einem Gerät Microtrac X100).In one embodiment of the present invention, metal powder (a) has an average particle diameter of from 0.01 to 100 μm, preferably from 0.1 to 50 μm, particularly preferably from 1 to 10 μm (determined by laser diffraction measurement, for example on a Microtrac X100 device). ,

In einer Ausführungsform ist Metallpulver (a) durch seine Partikeldurchmesserverteilung gekennzeichnet. Beispielsweise kann der Wert d10 im Bereich von 0,01 bis 5 µm liegen, der Wert für d50 im Bereich von 1 bis 10 µm und der Wert für d90 im Bereich von 3 bis 100 µm, wobei gilt: d10 < d50 < d90. Dabei hat vorzugsweise kein Partikel einen größeren Durchmesser als 100 µm.In one embodiment, metal powder (a) is characterized by its particle diameter distribution. For example, the value d 10 can be in the range of 0.01 to 5 μm, the value for d 50 in the range of 1 to 10 μm and the value for d 90 in the range of 3 to 100 μm, where d 10 <d 50 <d 90 . In this case, preferably no particle has a larger diameter than 100 microns.

Metallpulver (a) kann man in passivierter Form einsetzen, beispielsweise in einer zumindest partiell beschichteten ("gecoateten") Form. Als geeignete Beschichtungen seien beispielsweise anorganische Schichten wie Oxid des betreffenden Metalls, SiO2 bzw. SiO2·aq oder Phosphate beispielsweise des betreffenden Metalls genannt.Metal powder (a) can be used in passivated form, for example in an at least partially coated ("coated") form. Examples of 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.

Die Partikel von Metallpulver (a) können grundsätzlich jede beliebige Form aufweisen, beispielsweise sind nadelförmige, plattenförmige oder kugelförmige Partikel einsetzbar, bevorzugt sind kugel- und plattenförmige.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.

In besonders bevorzugter Weise werden Metallpulver (a) mit kugelförmigen Partikeln, bevorzugt überwiegend mit kugelförmigen Partikeln, ganz besonders bevorzugt sogenannte Carbonyleisenpulver mit kugelförmigen Partikeln, verwendet.In a particularly preferred manner, metal powders (a) with spherical particles, preferably predominantly with spherical particles, very particularly preferably so-called carbonyl iron powders with spherical particles, are used.

Die Herstellung von Metallpulvern (a) ist an sich bekannt. Man kann beispielsweise gängige Handelswaren oder nach an sich bekannten Verfahren hergestelltes Metallpulver (a) einsetzen, beispielsweise durch elektrolytische Abscheidung oder chemische Reduktion aus Lösungen von Salzen der betreffenden Metalle oder durch Reduktion eines oxidischen Pulvers beispielsweise mittels Wasserstoff, durch Versprühen oder Verdüsen einer Metallschmelze, insbesondere in Kühlmedien, beispielsweise Gasen oder Wasser.The production of metal powders (a) is 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.

Besonders bevorzugt verwendet man solches Metallpulver (a), das durch thermische Zersetzung von Eisenpentacarbonyl hergestellt wurde, im Rahmen der vorliegenden Erfindung auch Carbonyleisenpulver genannt.Particular preference is given to using such 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.

Die Herstellung von Carbonyleisenpulver durch thermische Zersetzung von insbesondere Eisenpentacarbonyl Fe(CO)5 wird beispielsweise in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, Seite 599, beschrieben. Die Zersetzung des Eisenpentacarbonyls kann beispielsweise bei Normaldruck und beispielsweise bei erhöhten Temperaturen, z. B. im Bereich von 200 bis 300°C, z. B. in einem beheizbaren Zersetzer erfolgen, der ein Rohr aus einem hitzebeständigen Material wie Quarzglas oder V2A-Stahl in vorzugsweise vertikaler Position umfasst, das von einer Heizeinrichtung, beispielsweise bestehend aus Heizbändern, Heizdrähten oder aus einem von einem Heizmedium durchströmten Heizmantel, umgeben ist.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.

Der mittlere Teilchendurchmesser von Carbonyleisenpulver kann durch die Verfahrensparameter und Reaktionsführung bei der Zersetzung in weiten Bereichen gesteuert werden und liegt (Zahlenmittel) in der Regel bei 0,01 bis 100 µm, bevorzugt von 0,1 bis 50 µm, besonders bevorzugt von 1 bis 8 µm.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.

Metallpulver (a) kann man in einer Ausführungsform von Schritt (A) so verdrucken, dass die Partikel von Metallpulver so dicht liegen, dass sie bereits zum Leiten von Strom in der Lage sind. In einer anderen Ausführungsform von Schritt (A) kann man so verdrucken, dass die Partikel von Metallpulver (a) so weit voneinander entfernt sind, dass sie nicht zum Leiten des Stroms in der Lage sind.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.

Bevorzugt bringt man in Schritt (A) Metallpulver (a) so auf, dass man eine Interdigitalstruktur erzeugt. Unter einer Interdigitalstruktur versteht man ein Muster, bei dem die Elemente fingerartig ineinander greifen, ohne sich zu berühren.Preferably, in 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.

In einer Ausführungsform der vorliegenden Erfindung kann Formulierung aus Schritt (A) ein Bindemittel (b) enthalten. bevorzugt mindestens eine wässrige Dispersion von mindestens einem Film bildenden Polymer, beispielsweise Polyacrylat, Polybutadien, Copolymere von mindestens einem Vinylaromaten mit mindestens einem konjugierten Dien und gegebenenfalls weiteren Comonomeren, beispielsweise Styrol-Butadien-Bindemittel. Weitere geeignete Bindemittel sind gewählt aus Polyurethan, vorzugsweise anionischem Polyurethan, oder Ethylen-(Meth)acrylsäure-Copolymer. Bindemittel (b) können im Rahmen der vorliegenden Erfindung auch als Binder (b) bezeichnet werden.In one embodiment of the present invention, 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. 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.

Als Binder (b) geeignete Polyacrylate im Sinne der vorliegenden Erfindung sind beispielsweise erhältlich durch Copolymerisation von mindestens einem (Meth)acrylsäure-C1-C10-Alkylester, beispielsweise Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-Butylester, Methacrylsäure-n-butylester, Acrylsäure-2-ethylhexylester, mit mindestens einem weiteren Comonomer, beispielsweise einem weiteren (Meth)acrylsäure-C1-C10-Alkylester, (Meth)acrylsäure, (Meth)acrylamid, N-Methylol(meth)acrylamid, Glycidyl(meth)acrylat oder einer vinylaromatischen Verbindung wie beispielsweise Styrol.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.

Als Binder (b) geeignete vorzugsweise anionische Polyurethane im Sinne der vorliegenden Erfindung sind beispielsweise erhältlich durch Umsetzung von einem oder mehreren aromatischen oder vorzugsweise aliphatischen oder cycloaliphatischen Diisocyanat mit einem oder mehreren Polyesterdiolen und vorzugsweise einer oder mehreren Hydroxycarbonsäuren, z. B Hydroxyessigsäure, oder vorzugsweise Dihydroxycarbonsäuren, beispielsweise 1,1-Dimethylolpropionsäure, 1,1-Dimethylolbuttersäure oder 1,1-Dimethylolethansäure, oder einer Diaminocarbonsäure, beispielsweise dem Michael-Additionsprodukt von Ethylendiamin an (Meth)acrylsäure.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.

Als Bindemittel (b) besonders geeignete Ethylen-(Meth)acrylsäure-Copolymere sind beispielsweise durch Copolymerisation von Ethylen, (Meth)acrylsäure und gegebenenfalls mindestens einem weiteren Comonomer wie beispielsweise (Meth)acrylsäure-C1-C10-Alkylester, Maleinsäureanhydrid, Isobuten oder Vinylacetat erhältlich, vorzugsweise durch Copolymerisation bei Temperaturen im Bereich von 190 bis 350°C und Drücken im Bereich von 1500 bis 3500, bevorzugt 2000 bis 2500 bar.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.

Als Bindemittel (b) besonders geeignete Ethylen-(Meth)acrylsäure-Copolymere können beispielsweise bis zu 90 Gew.-% Ethylen einpolymerisiert enthalten und eine Schmelzeviskosität v im Bereich von 60 mm2/s bis 10.000 mm2/s auf, bevorzugt 100 mm2/s bis 5.000 mm2/s aufweisen, gemessen bei 120°C.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.

Als Bindemittel (b) besonders geeignete Ethylen-(Meth)acrylsäure-Copolymere können beispielsweise bis zu 90 Gew.-% Ethylen einpolymerisiert enthalten und eine Schmelzemassefließrate (MFR) im Bereich von 1 bis 50 g/10 min, bevorzugt 5 bis 20 g/10 min, besonders bevorzugt 7 bis 15 g/10 min aufweisen, gemessen bei 160°C und einer Belastung von 325 g nach EN ISO 1133.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.

Als Bindemittel (b) besonders geeignete Copolymere von mindestens einem Vinylaromaten mit mindestens einem konjugierten Dien und gegebenenfalls weiteren Comonomeren, beispielsweise Styrol-Butadien-Bindemittel, enthalten mindestens eine ethylenisch ungesättigte Carbonsäure oder Dicarbonsäure oder ein geeignetes Derivat, beispielsweise das entsprechende Anhydrid, einpolymerisiert. Besonders geeignete Vinylaromaten sind para-Methylstyrol, α-Methylstyrol und insbesondere Styrol. Besonders geeignete konjugierte Diene sind Isopren, Chloropren und insbesondere 1,3-Butadien. Als besonders geeignete ethylenisch ungesättigte Carbonsäuren oder Dicarbonsäuren oder geeignete Derivate davon seien (Meth)acrylsäure, Maleinsäure, Itaconsäure, Maleinsäureanhydrid bzw. Itaconsäureanhydrid beispielhaft genannt.Particularly suitable as 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.

In einer Ausführungsform der vorliegenden Erfindung enthalten als Bindemittel (b) besonders geeignete Copolymere von mindestens einem Vinylaromaten mit mindestens einem konjugierten Dien und gegebenenfalls weiteren Comonomeren einpolymerisiert:
19,9 bis 80 Gew.-% Vinylaromat,
19,9 bis 80 Gew.-% konjugiertes Dien,
0,1 bis 10 Gew.-% ethylenisch ungesättigte Carbonsäure oder Dicarbonsäure oder ein geeignetes Derivat, beispielsweise das entsprechende Anhydrid.In one embodiment of the present invention, as 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.

In einer Ausführungsform der vorliegenden Erfindung wählt man Bindemittel (b) aus solchen, die bei 23°C eine dynamische Viskosität im Bereich von 10 bis 100 dPa·s, bevorzugt 20 bis 30 dPa·s aufweisen, bestimmt beispielsweise durch Rotationsviskosimetrie, beispielsweise mit einem Haake-Viskosimeter.In one embodiment of the present invention, 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.

Formulierung aus Schritt (A) kann weiterhin ein oder mehrere Zusätze enthalten, beispielsweise einen oder mehrere Emulgatoren oder einen oder mehrere Verdicker oder einen oder mehrere Fixierer. Emulgatoren, Verdicker, Fixierer und gegebenenfalls weitere einzusetzende Zusätze sind weiter unten beschrieben.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, thickeners, fixers and optionally further additives to be used are described below.

In einer Ausführungsform der vorliegenden Erfindung hat Formulierung aus Schritt (A) einen Feststoffgehalt im Bereich von 1 bis 90%, bevorzugt im Bereich von 30 bis 80%.In one embodiment of the present invention, the formulation of step (A) has a solids content in the range of 1 to 90%, preferably in the range of 30 to 80%.

In einer Ausführungsform der vorliegenden Erfindung bringt man in Schritt (A) so viel Formulierung auf, dass die Belegung von Substrat und insbesondere von Textil mit Metallpulver (a) im Bereich von 20 bis 200 g/m2, bevorzugt 40 bis 80 g/m2 liegt.In one embodiment of the present invention, in 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.

Nach dem Aufbringen von Formulierung aus Schritt (A) kann man härten, beispielsweise photochemisch oder vorzugsweise durch thermische Behandlung, und zwar in einem oder mehreren Schritten. Wünscht man mehrere Schritte zur thermischen Behandlung durchzuführen, so kann man mehrere Schritte bei der gleichen oder vorzugsweise bei verschiedenen Temperaturen durchführen.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.

Zum Zwecke der Härtung kann man beispielsweise bei Temperaturen im Bereich von 50 bis 200°C behandeln.For the purpose of curing, for example, at temperatures in the range of 50 to 200 ° C treat.

Zum Zwecke der Härtung kann man beispielsweise über einen Zeitraum von 10 Sekunden bis 15 Minuten, bevorzugt 30 Sekunden bis 10 Minuten behandeln.For the purpose of curing, it is possible to treat, for example, over a period of 10 seconds to 15 minutes, preferably 30 seconds to 10 minutes.

Besonders bevorzugt behandelt man in einem ersten Schritt zur thermischen Behandlung bei Temperaturen im Bereich von beispielsweise 50 bis 110°C über einen Zeitraum von 30 Sekunden bis 3 Minuten und in einem zweiten Schritt anschließend bei Temperaturen im Bereich von 130°C bis 200°C über einen Zeitraum von 30 Sekunden bis 15 Minuten.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.

Natürlich passt man die Temperatur, bei der man die thermische Behandlung durchführt, an den Schmelzpunkt von Substrat an.Of course, the temperature at which the thermal treatment is carried out is adjusted to the melting point of the substrate.

Man kann jeden einzelnen Schritt zum Zwecke der Härtung in an sich bekannten Geräten durchführen, zum Beispiel in Trockenschränken, Spannrahmen oder Vakuumtrockenschränken.It is possible to carry out each individual step for the purpose of curing in devices known per se, for example in drying cabinets, clamping frames or vacuum drying cabinets.

In einer Ausführungsform der vorliegenden Erfindung setzt man in Schritt (A) eine vorzugsweise wässrige Druckformulierung ein, die enthält:

  1. (a) mindestens ein Metallpulver, wobei das betreffende Metall in der elektrochemischen Spannungsreihe der Elemente vorzugsweise ein stärker negatives Normalpotenzial aufweist als Wasserstoff, bevorzugt ist Carbonyleisenpulver,
  2. (b) mindestens ein Bindemittel,
  3. (c) mindestens einen Emulgator, der anionisch, kationisch oder bevorzugt nichtionisch sein kann,
  4. (d) gegebenenfalls mindestens einen Rheologiemodifizierer.
In one embodiment of the present invention, in step (A), a preferably aqueous printing formulation is used, which contains:
  1. (a) at least one metal powder, wherein the metal in question in the electrochemical series of the elements preferably has a greater negative normal potential than hydrogen, carbonyl iron powder is preferred,
  2. (b) at least one binder,
  3. (c) at least one emulsifier, which may be anionic, cationic or, preferably, nonionic,
  4. (d) optionally at least one rheology modifier.

Druckformulierungen aus Schritt (A) können mindestens ein Bindemittel (b) enthalten, bevorzugt mindestens eine wässrige Dispersion von mindestens einem filmbildenden Polymer, beispielsweise Polyacrylat, Polybutadien, Copolymere von mindestens einem Vinylaromaten mit mindestens einem konjugierten Dien und gegebenenfalls weiteren Comonomeren, beispielsweise Styrol-Butadien-Bindemittel. Weitere geeignete Bindemittel (b) sind gewählt aus Polyurethan, vorzugsweise anionischem Polyurethan, oder Ethylen-(Meth)acrylsäure-Copolymer. Bindemittel (b) können im Rahmen der vorliegenden Erfindung auch als Binder (b) bezeichnet werden. bPrinting 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. Other 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. b

Als Emulgator (c) kann man anionische, kationische oder vorzugsweise nicht-ionische oberflächenaktive Substanzen verwenden.As emulsifier (c) it is possible to use anionic, cationic or preferably nonionic surface-active substances.

Beispiele für geeignete kationische Emulgatoren (c) sind beispielsweise einen C6-C18-Alkyl-, C7-C18-Aralkyl- oder einen heterocyclischen Rest aufweisende primäre, sekundäre, tertiäre oder quartäre Ammoniumsalze, Alkanolammoniumsalze, Pyridiniumsalze, Imidazoliniumsalze, Oxazoliniumsalze, Morpholiniumsalze, Thiazoliniumsalze sowie Salze von Aminoxiden, Chinoliniumsalze, Isochinoliniumsalze, Tropyliumsalze, Sulfoniumsalze und Phosphoniumsalze. Beispielhaft genannt seien Dodecylammoniumacetat oder das entsprechende Hydrochlorid, die Chloride oder Acetate der verschiedenen 2-(N,N,N-Trimethylammonium)ethylparaffinsäureester, N-Cetylpyridiniumchlorid, N-Laurylpyridiniumsulfat sowie N-Cetyl-N,N,N-trimethylammoniumbromid, N-Dodecyl-N,N,N-trimethylammoniumbromid, N,N-Distearyl-N,N-dimethylammoniumchlorid sowie das Gemini-Tensid N,N'-(Lauryldimethyl)ethylendiamindibromid.Examples of 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) ethylparaffinsäureester, 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.

Beispiele für geeignete anionische Emulgatoren (c) sind Alkalimetall- und Ammoniumsalze von Alkylsulfaten (Alkylrest: C8 bis C12), von Schwefelsäurehalbestern ethoxylierter Alkanole (Ethoxylierungsgrad: 4 bis 30, Alkylrest: C12-C18) und ethoxylierter Alkylphenole (Ethoxylierungsgrad: 3 bis 50, Alkylrest: C4-C12), von Alkylsulfonsäuren (Alkylrest: C12-C18), von Alkylarylsulfonsäuren (Alkylrest: C9-C18) und von Sulfosuccinaten wie beispielsweise Sulfobernsteinsäuremono- oder diestern. Bevorzugt sind aryl- oder alkylsubstituierte Polyglykolether, weiterhin Substanzen, die in US 4,218,218 beschrieben sind, und Homologe mit y (aus den Formeln aus US 4,218,218 ) im Bereich von 10 bis 37.Examples of 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. 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.

Besonders bevorzugt sind nichtionische Emulgatoren (c) wie beispielsweise ein- oder vorzugsweise mehrfach alkoxylierte C10-C30-Alkanole, bevorzugt mit drei bis hundert Mol C2-C4-Alkylenoxid, insbesondere Ethylenoxid alkoxylierte Oxo- oder Fettalkohole.Particular preference is given to 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.

Beispiele für besonders geeignete mehrfach alkoxylierte Fettalkohole und Oxoalkohole sind
n-C18H37O-(CH2CH2O)80-H, n-C18H37O-(CH2CH2O)70-H, n-C18H37O-(CH2CH2O)60-H, n-C18H37O-(CH2CH2O)50-H, n-C18H37O-(CH2CH2O)25-H, n-C18H37O-(CH2CH2O)12-H, n-C16H33O-(CH2CH2O)80-H, n-C16H33O-(CH2CH2O)70-H, n-C16H33O-(CH2CH2O)60-H, n-C16H33O-(CH2CH2O)50-H, n-C16H33O-(CH2CH2O)25-H, n-C16H33O-(CH2CH2O)12-H, n-C12H25O-(CH2CH2O)11-H, n-C12H25O-(CH2CH2O)18-H, n-C12H25O-(CH2CH2O)25-H, n-C12H25O-(CH2CH2O)50-H, n-C12H25O-(CH2CH2O)80-H, n-C30H61O-(CH2CH2O)8-H, n-C10H21O-(CH2CH2O)9-H, n-C10H21O-(CH2CH2O)7-H, n-C10H21O-(CH2CH2O)5-H, n-C10H21O-(CH2CH2O)3-H, und Mischungen der vorstehend genannten Emulgatoren, beispielsweise Mischungen von n-C18H37O-(CH2CH2O)50-H und n-C16H33O-(CH2CH2O)50-H,
wobei die Indices jeweils als Mittelwerte (Zahlenmittel) aufzufassen sind.Examples of particularly suitable polyalkoxylated fatty alcohols and oxo alcohols are
nC 18 H 37 O- (CH 2 CH 2 O) 80 -H, nC 18 H 37 O- (CH 2 CH 2 O) 70 -H, nC 18 H 37 O- (CH 2 CH 2 O) 60 -H , nC 18 H 37 O- (CH 2 CH 2 O) 50 -H, nC 18 H 37 O- (CH 2 CH 2 O) 25 -H, nC 18 H 37 O- (CH 2 CH 2 O) 12 - H, nC 16 H 33 O- (CH 2 CH 2 O) 80 -H, nC 16 H 33 O- (CH 2 CH 2 O) 70 -H, nC 16 H 33 O- (CH 2 CH 2 O) 60 -H, nC 16 H 33 O- (CH 2 CH 2 O) 50 -H, nC 16 H 33 O- (CH 2 CH 2 O) 25 -H , nC 16 H 33 O- (CH 2 CH 2 O) 12 -H, nC 12 H 25 O- (CH 2 CH 2 O) 11 -H, nC 12 H 25 O- (CH 2 CH 2 O) 18 -H, nC 12 H 25 O- (CH 2 CH 2 O ) 25 -H, nC 12 H 25 O- (CH 2 CH 2 O) 50 -H, nC 12 H 25 O- (CH 2 CH 2 O) 80 -H, nC 30 H 61 O- (CH 2 CH 2 O) 8 -H, nC 10 H 21 O- (CH 2 CH 2 O) 9 -H, nC 10 H 21 O- (CH 2 CH 2 O) 7 -H, nC 10 H 21 O- (CH 2 CH 2 O) 5 -H, nC 10 H 21 O- (CH 2 CH 2 O) 3 -H, and mixtures of the above emulsifiers, for example mixtures of nC 18 H 37 O- (CH 2 CH 2 O) 50 -H and nC 16 H 33 O- (CH 2 CH 2 O) 50 -H,
where the indices are to be understood as mean values (number average).

In einer Ausführungsform der vorliegenden Erfindung können in Schritt (A) eingesetzte vorzugsweise wässrige Druckformulierungen mindestens einen Rheologiemodifizierer (d) enthalten, ausgewählt aus Verdickungsmitteln (d1), die auch als Verdicker bezeichnet werden können, und die Viskosität senkenden Mitteln (d2).In one embodiment of the present invention, preferably 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).

Geeignete Verdickungsmittel (d1) sind beispielsweise natürliche Verdickungsmittel oder vorzugsweise synthetische Verdickungsmittel. Natürliche Verdickungsmittel sind solche Verdickungsmittel, die Naturprodukte sind oder durch Aufarbeitung wie beispielsweise Reinigungsoperationen, insbesondere Extraktion von Naturprodukten erhalten werden können. Beispiele für anorganische natürliche Verdickungsmittel sind Schichtsilikate wie beispielsweise Bentonit. Beispiele für organische natürliche Verdickungsmittel sind vorzugsweise Proteine wie beispielsweise Casein oder bevorzugt Polysaccharide. Besonders bevorzugte natürliche Verdickungsmittel sind gewählt aus Agar-Agar, Carrageen, Gummi arabicum, Alginaten wie beispielsweise Natriumalginat, Kaliumalginat, Ammoniumalginat, Calciumalginat und Propylengycolalginat, Pektinen, Polyosen, Johannisbrotbaum-Kernmehl (Carubin) und Dextrinen.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. Examples of inorganic natural thickeners are phyllosilicates such as bentonite. Examples of 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.

Bevorzugt ist der Einsatz von synthetischen Verdickungsmitteln, die gewählt sind aus im Allgemeinen flüssigen Lösungen von synthetischen Polymeren, insbesondere Acrylaten, in beispielsweise Weißöl oder als wässrige Lösungen, und aus synthetischen Polymeren in getrockneter Form, beispielsweise als durch Sprühtrocknung hergestelltem Pulver. Als Verdickungsmittel (d1) eingesetzte synthetische Polymere enthalten Säuregruppen, die vollständig oder zu einem gewissen Prozentsatz mit Ammoniak neutralisiert werden. Beim Fixierprozess wird Ammoniak freigesetzt, wodurch der pH-Wert gesenkt wird und die eigentliche Fixierung beginnt. Das für die Fixierung notwendige Absenken des pH-Wertes kann alternativ durch Zusatz von nichtflüchtigen Säuren wie z.B. Zitronensäure, Bernsteinsäure, Glutarsäure oder Äpfelsäure erfolgen.Preference is given to the use of synthetic thickeners, which 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.

Ganz besonders bevorzugte synthetische Verdickungsmittel sind gewählt aus Copolymeren von 85 bis 95 Gew.-% Acrylsäure, 4 bis 14 Gew.-% Acrylamid und 0,01 bis maximal 1 Gew.-% des (Meth)acrylamidderivats der Formel I

Figure imgb0001
mit Molekulargewichten Mw im Bereich von 100.000 bis 2.000.000 g/mol, in denen die Reste R1 gleich oder verschieden sein können und Methyl oder Wasserstoff bedeuten können.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.
Figure imgb0001
 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.

Weitere geeignete Verdickungsmittel (d1) sind gewählt aus Reaktionsprodukten von aliphatischen Diisocyanaten wie beispielsweise Trimethylendiisocyanat, Tetramethylendiisocyanat, Hexamethylendiisocyanat oder Dodecan-1,12-diisocyanat mit vorzugsweise 2 Äquivalenten mehrfach alkoxyliertem Fettalkohol oder Oxoalkohol, beispielsweise 10 bis 150-fach ethoxyliertem C10-C30-Fettalkohol oder C11-C31-Oxoalkohol.Further suitable 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.

Geeignete die Viskosität senkende Mittel (d2) sind beispielsweise organische Lösungsmittel wie Dimethylsulfoxid (DMSO), N-Methylpyrrolidon (NMP), N-Ethylpyrrolidon (NEP), Ethylenglykol, Diethylenglykol, Butylykol, Dibutylglykol, und beispielsweise Restalkohol-freiem alkoxyliertem n-C4-C8-Alkanoi, bevorzugt Restalkohol-freiem ein- bis 10-fach, besonders bevorzugt 3- bis 6-fach ethoxyliertem n-C4-C8-Alkanol. Dabei ist unter Restalkohol das jeweils nicht alkoxylierte n-C4-C8-Alkanol zu verstehen.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. In this case, residual alcohol is to be understood as meaning the respective non-alkoxylated nC 4 -C 8 -alkanol.

In einer Ausführungsform der vorliegenden Erfindung enthält in Schritt (A) eingesetzte Druckformulierung
im Bereich von 10 bis 90 Gew.-%, bevorzugt 50 bis 85 Gew.-%, besonders bevorzugt 60 bis 80 Gew.-% Metallpulver (a),
im Bereich von 1 bis 20 Gew.-%, bevorzugt 2 bis 15 Gew.-% Bindemittel (b),
im Bereich von 0,1 bis 4 Gew.-%, bevorzugt bis 2 Gew.-% Emulgator (c),
im Bereich von 0 bis 5 Gew.-%, bevorzugt 0,2 bis 1 Gew.-% Rheologiemodifizierer (d), wobei Angaben in Gew.-% jeweils auf die gesamte in Schritt (A) eingesetzte Druckformulierung bezogen sind und sich bei Bindemittel (b) auf den Feststoffgehalt des jeweiligen Bindemittels (b) beziehen.In one embodiment of the present invention, 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).

In einer Ausführungsform der vorliegenden Erfindung kann man in Schritt (A) des erfindungsgemäßen Verfahrens mit einer Druckformulierung bedrucken, die zusätzlich zu Metallpulver (a) und gegebenenfalls Bindemittel (b), Emulgator (c) und gegebenenfalls Rheologiemodifizierer (d) mindestens ein Hilfsmittel (e) enthält. Als Hilfsmittel (e) seien Griffverbesserer, Entschäumer, Netzmittel, Egalisiermittel, Harnstoff, Wirkstoffe wie beispielsweise Biozide oder Flammfestmittel, beispielhaft genannt:In one embodiment of the present 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. 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.

Geeignete Entschäumer sind beispielsweise silikonhaltige Entschäumer wie beispielsweise solche der Formel HO-(CH2)3-Si(CH3)[OSi(CH3)3]2 und HO-(CH2)3-Si(CH3)[OSi(CH3)3][OSi(CH3)2OSi(CH3)3], nicht alkoxyliert oder mit bis zu 20 Äquivalenten Alkylenoxid und insbesondere Ethylenoxid alkoxyliert. Auch Silikon-freie Entschäumer sind geeignet wie beispielsweise mehrfach alkoxylierte Alkohole, z.B. Fettalkoholalkoxylate, bevorzugt 2 bis 50-fach ethoxylierte vorzugsweise unverzweigte C10-C20-Alkanole, unverzweigte C10-C20-Alkanole und 2-Ethylhexan-1-ol. Weitere geeignete Entschäumer sind Fettsäure-C8-C20-alkylester, bevorzugt Stearinsäure-C10-C20-alkylester, bei denen C8-C20-Alkyl, bevorzugt C10-C20-Alkyl unverzweigt oder verzweigt sein kann.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.

Geeignete Netzmittel sind beispielsweise nichtionische, anionische oder kationische Tenside, insbesondere Ethoxylierungs- und/oder Propoxylierungsprodukte von Fettalkoholen oder Propylenoxid-Ethylenoxid-Blockcopolymere, ethoxylierte oder propoxylierte Fett- oder Oxoalkohole, weiterhin Ethoxylate von Ölsäure oder Alkylphenolen, Alkylphenolethersulfate, Alkylpolyglycoside, Alkylphosphonate, Alkylphenylphosphonate, Alkylphosphate, oder Alkylphenylphosphate.Examples of 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.

Geeignete Egalisiermittel sind beispielsweise Blockcopolymerisate von Ethylenoxid und Propylenoxid mit Molekulargewichten Mn im Bereich von 500 bis 5000 g/mol, bevorzugt 800 bis 2000 g/mol. Ganz besonders besonders bevorzugt sind Blockcopolymerisate aus Propylenoxid/Ethylenoxid beispielsweise der Formel EO8PO7EO8, wobei EO für Ethylenoxid und PO für Propylenoxid steht.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. Very particular preference is given to 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.

Geeignete Biozide sind beispielsweise als Proxel-Marken im Handel befindlich. Beispielhaft seien genannt: 1,2-Benzisothiazolin-3-on ("BIT"), kommerziell erhältlich als Proxet®-Marken der Fa. Avecia Lim., und dessen Alkalimetallsalze; andere geeignete Biozide sind 2-Methyl-2H-isothiazol-3-on ("MIT") und 5-Chlor-2-methyl-2H-isothiazol-3-on ("CIT").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").

In einer Ausführungsform der vorliegenden Erfindung enthält in Schritt (A) eingesetzte Druckformulierung bis zu 30 Gew.-% Hilfsmittel (e), bezogen auf die Summe aus Metallpulver (a), Bindemittel (b), Emulgator (c) und gegebenenfalls Rheologiemodifizierer (d).In one embodiment of the present invention, 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. ).

In einer Ausführungsform der vorliegenden Erfindung bedruckt man in Schritt (A) vollflächig mit Druckformulierung, die mindestens ein Metallpulver (a) enthält. In einer anderen Ausführungsform druckt man ein Muster von Metallpulver (a) auf, indem man Substrat und insbesondere Textil an einigen Stellen mit Druckformulierung bedruckt, die Metallpulver (a) enthält, und an anderen Stellen nicht. Vorzugsweise verdruckt man solche Muster, bei denen Metallpulver (a) in Form von geraden oder vorzugsweise gebogenen Streifenmustern oder Linienmustern auf Substrat und insbesondere Textil angeordnet sind, wobei die genannten Linien beispielsweise eine Breite und Dicke jeweils im Bereich von 0,1 µm bis 5 mm und die genannten Streifen eine Breite im Bereich von 5,1 mm bis beispielsweise 10 cm oder gegebenenfalls mehr und eine Dicke von 0,1 µm bis 5 mm haben können.In one embodiment of the present invention, in step (A) full-surface printing is carried out with a printing formulation containing at least one metal powder (a). In another embodiment, 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. Preferably, 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 μm 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 μm to 5 mm.

In einer speziellen Ausführungsform der vorliegenden Erfindung verdruckt man solche Streifenmuster oder Linienmuster von Metallpulver (a), bei denen sich die Streifen bzw. Linien weder berühren noch schneiden. Ganz besonders bevorzugt verdruckt man solche Muster, die eine Interdigitalstruktur darstellen. Dabei können die Streifen oder Linien einen Mindestabstand im Bereich von 2 bis 3 mm aufweisen.In a specific embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung bedruckt man in Schritt (A) nach Verfahren, die an sich bekannt sind. In einer Ausführungsform der vorliegenden Erfindung verwendet man eine Schablone, durch die man die Druckformulierung, die Metallpulver (a) enthält, mit einer Rakel presst. Das vorstehend beschriebene Verfahren gehört zu den Siebdruckverfahren. Weitere geeignete Druckverfahren sind Tiefdruckverfahren und Flexodruckverfahren. Ein weiteres geeignetes Druckverfahren ist gewählt aus Valve-Jet-Verfahren. Bei Valve-Jet-Verfahren verwendet man solche Druckformulierung, die vorzugsweise keine Verdickungsmittel (d1) enthält.In one embodiment of the present invention, in step (A), methods are printed which are known per se. In one embodiment of the present invention, 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).

Zur Durchführung des erfindungsgemäßen Verfahrens scheidet man in Schritt (B) ein weiteres Metall auf der Oberfläche von Substrat und insbesondere dem textilen Flächengebilde ab. Unter "dem textilen Flächengebilde" ist dabei das zuvor in Schritt (A) bearbeitete Textil zu verstehen.To carry out the process according to the invention, in step (B), a further metal is deposited on the surface of the substrate and in particular the textile fabric. By "the textile fabric" is meant the textile previously processed in step (A).

Man kann in Schritt (B) mehrere weitere Metalle abscheiden, bevorzugt ist es jedoch, nur ein weiteres Metall abzuscheiden.It is possible to deposit several further metals in step (B), but it is preferable to deposit only one more metal.

In einer Ausführungsform der vorliegenden Erfindung wählt man als Metallpulver (a) Carbonyleisenpulver und als weiteres Metall Silber, Gold und insbesondere Kupfer.In one embodiment of the present invention, the metal powder selected is (a) carbonyl iron powder and, as further metal, silver, gold and in particular copper.

In einer Ausführungsform der vorliegenden Erfindung, im Folgenden auch als Schritt (B1) bezeichnet, geht man so vor, dass man in Schritt (B1) ohne externe Spannungsquelle arbeitet und dass das weitere Metall in Schritt (B1) in der elektrochemischen Spannungsreihe der Elemente, in alkalischer oder vorzugsweise in saurer Lösung, ein stärker positives Normalpotenzial aufweist als Metall, das Metallpulver (a) zugrunde liegt, und als Wasserstoff.In one embodiment of the present invention, hereinafter also referred to as 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.

Dazu kann man beispielsweise so vorgehen, dass zuvor in Schritt (A) und in Schritt (B) bearbeitetes Substrat und insbesondere Textil mit einer basischen, neutralen oder vorzugsweise sauren vorzugsweise wässrigen Lösung von Salz von weiterem Metall und gegebenenfalls einem oder mehreren Reduktionsmitteln behandelt, beispielsweise indem man es in die betreffende Lösung einlegt.This can be done, for example, so that previously in 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.

In einer Ausführungsform der vorliegenden Erfindung behandelt man in Schritt (B1) im Bereich von 0,5 Minuten bis zu 12 Stunden, bevorzugt bis zu 30 Minuten.In one embodiment of the present invention, in step (B1), in the range of 0.5 minutes, up to 12 hours, preferably up to 30 minutes, are treated.

In einer Ausführungsform der vorliegenden Erfindung behandelt man in Schritt (B1) mit einer basischen, neutralen oder vorzugsweise sauren Lösung von Salz von weiterem Metall, die eine Temperatur im Bereich von 0 bis 100°C, bevorzugt 10 bis 80°C aufweist.In one embodiment of the present invention, in 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.

Zusätzlich kann man in Schritt (B1) ein oder mehrere Reduktionsmittel zusetzen. Wählt man beispielsweise Kupfer als weiteres Metall, so kann man als Reduktionsmittel beispielsweise Aldehyde, insbesondere reduzierende Zucker oder Formaldehyd als Reduktionsmittel zusetzen. Wählt man beispielsweise Nickel als weiteres Metall, so kann man beispielsweise Alkalihypophosphit, insbesondere NaH2PO2·2H2O, oder Boranate, insbesondere NaBH4, als Reduktionsmittel zusetzen.In addition, one can add one or more reducing agents in step (B1). If, for example, copper is selected as a further metal, then it is possible to add, for example, aldehydes, in particular reducing sugars or formaldehyde, as a reducing agent, as a reducing agent. If, for example, nickel is selected as a further metal, it is possible, for example, to add alkali hypophosphite, in particular NaH 2 PO 2 .2H 2 O, or boranates, in particular NaBH 4 , as reducing agent.

In einer anderen Ausführungsform, im Folgenden auch als Schritt (B2) bezeichnet, der vorliegenden Erfindung geht man so vor, dass man in Schritt (B2) mit externer Spannungsquelle arbeitet und dass das weitere Metall in Schritt (B2) in der elektrochemischen Spannungsreihe der Elemente in saurer oder alkalischer Lösung ein stärker oder schwächer positives Normalpotenzial aufweisen kann als Metall, das Metallpulver (a) zugrunde liegt. Vorzugsweise kann man dazu als Metallpulver (a) Carbonyleisenpulver und als weiteres Metall Nickel, Zink oder insbesondere Kupfer wählen. Dabei beobachtet man für den Fall, dass das weitere Metall in Schritt (B2) in der elektrochemischen Spannungsreihe der Elemente ein stärker positives Normalpotenzial aufweist als Wasserstoff und als Metall, das Metallpulver (a) zugrunde liegt, dass zusätzlich weiteres Metall in Analogie zu Schritt (B1) abgeschieden wird.In another embodiment, hereinafter also referred to as 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. Preferably, one can choose as metal powder (a) carbonyl iron powder and as another metal nickel, zinc or especially copper. In this case, in the case where 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.

Zur Durchführung von Schritt (B2) kann man beispielsweise einen Strom mit einer Stärke im Bereich von 10 bis 100 A, bevorzugt 12 bis 50 A anlegen.To carry out 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.

Zur Durchführung von Schritt (B2) kann man beispielsweise über einen Zeitraum von 1 bis 60 Minuten unter Verwendung einer externen Spannungsquelle arbeiten.For performing step (B2), it is possible to operate, for example, over a period of 1 to 60 minutes using an external power source.

In einer Ausführungsform der vorliegenden Erfindung kombiniert man Schritt (B1) und Schritt (B2) in der Weise, dass man zunächst ohne und danach mit externer Spannungsquelle arbeitet und dass das weitere Metall in Schritt (B) in der elektrochemischen Spannungsreihe der Elemente ein stärker positives Normalpotenzial aufweist kann als Metall, das Metallpulver (a) zugrunde liegt.In one embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung setzt man der Lösung von weiterem Metall einen oder mehrere Hilfsstoffe zu. Als Hilfsstoffe seien beispielhaft genannt: Puffer, Tenside, Polymere, insbesondere partikelförmige Polymere, deren Partikeldurchmesser im Bereich von 10 nm bis 10 µm liegt, Entschäumer, ein oder mehrere organische Lösungsmittel, ein oder mehrere Komplexbildner.In one embodiment of the present invention, one or more auxiliaries are added to the solution of further metal. Examples of adjuvants include buffers, surfactants, polymers, in particular particulate polymers whose particle diameter is in the range from 10 nm to 10 μm, defoamers, one or more organic solvents, one or more complexing agents.

Besonders geeignete Puffer sind Essigsäure/Acetat-Puffer.Particularly suitable buffers are acetic acid / acetate buffer.

Besonders geeignete Tenside sind gewählt aus kationischen, anionischen und insbesondere nicht-ionischen Tensiden.Particularly suitable surfactants are selected from cationic, anionic and in particular nonionic surfactants.

Als kationische Tenside seien beispielhaft genannt: C6-C18-Alkyl-, -Aralkyl- oder heterocyclischen Rest aufweisende primäre, sekundäre, tertiäre oder quartäre Ammoniumsalze, Alkanolammoniumsalze, Pyridiniumsalze, Imidazoliniumsalze, Oxazoliniumsalze, Morpholiniumsalze, Thiazoliniumsalze sowie Salze von Aminoxiden, Chinoliniumsalze, Isochinoliniumsalze, Tropyliumsalze, Sulfoniumsalze und Phosphoniumsalze. Beispielhaft genannt seien Dodecylammoniumacetat oder das entsprechende Hydrochlorid, die Chloride oder Acetate der verschiedenen 2-(N,N,N-Trimethylammonium)ethylparäffinsäureester, N-Cetylpyridiniumchlorid, N-Laurylpyridiniumsulfat sowie N-Cetyl-N,N,N-trimethylammoniumbromid, N-DodecylN,N,N-trimethylammoniumbromid, N,N-Distearyl-N,N-dimethylammoniumchlorid sowie das Gemini-Tensid N,N'-(Lauryldimethyl)ethylendiamindibromid.Examples of 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. 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.

Beispiele für geeignete anionische Tenside sind Alkalimetall- und Ammoniumsalze von Alkylsulfaten (Alkylrest: C8 bis C12), von Schwefelsäurehalbestern ethoxylierter Alkanole (Ethoxylierungsgrad: 4 bis 30, Alkylrest: C12-C18) und ethoxylierter Alkylphenole (Ethoxylierungsgrad: 3 bis 50, Alkylrest: C4-C12), von Alkylsulfonsäuren (Alkylrest: C12-C18), von Alkylarylsulfonsäuren (Alkylrest: C9-C18) und von Sulfosuccinaten wie beispielsweise Sulfobernsteinsäuremono- oder diestern. Bevorzugt sind aryl- oder alkylsubstituierte Polyglykolether, weiterhin Substanzen, die in US 4,218,218 beschrieben sind, und Homologe mit y (aus den Formeln aus US 4,218,218 ) im Bereich von 10 bis 37.Examples of 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. 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.

Besonders bevorzugt sind nichtionische Tenside wie beispielsweise ein- oder vorzugsweise mehrfach alkoxylierte C10-C30-Alkanole, bevorzugt mit drei bis hundert Mol C2-C4-Alkylenoxid, insbesondere Ethylenoxid alkoxylierte Oxo- oder Fettalkohole.Particularly preferred are 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.

Geeignete Entschäumer sind beispielsweise silikonhaltige Entschäumer wie beispielsweise solche der Formel HO-(CH2)3-Si(CH3)[OSi(CH3)3]2 und HO-(CH2)3-Si(CH3)[OSi(CH3)3][OSi(CH3)2OSi(CH3)3], nicht alkoxyliert oder mit bis zu 20 Äquivalenten Alkylenoxid und insbesondere Ethylenoxid alkoxyliert. Auch Silikon-freie Entschäumer sind geeignet wie beispielsweise mehrfach alkoxylierte Alkohole, z.B. Fettalkoholalkoxylate, bevorzugt 2 bis 50-fach ethoxylierte vorzugsweise unverzweigte C10-C20-Alkanole, unverzweigte C10-C20-Alkanole und 2-Ethylhexan-1-ol. Weitere geeignete Entschäumer sind Fettsäure-C8-C20-alkylester, bevorzugt Stearinsäure-C10-C20-alkylester, bei denen C8-C20-Alkyl, bevorzugt C10-C20-Alkyl unverzweigt oder verzweigt sein kann.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.

Geeignete Komplexbildner sind solche Verbindungen, die Chelate bilden. Bevorzugt sind solche Komplexbildner, die gewählt sind aus Aminen, Diaminen und Triaminen, die mindestens eine Carbonsäuregruppe tragen. Beispielhaft seien Nitrilotriessigsäure, Ethylendiamintetraessigsäure und Diethylenpentaaminpentaessigsäure sowie die korrespondierenden Alkalimetallsalze genannt.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 Diethylenpentaaminpentaessigsäure and the corresponding alkali metal salts mentioned.

In einer Ausführungsform der vorliegenden Erfindung scheidet man so viel weiteres Metall ab, dass man eine Schichtdicke im Bereich von 100 nm bis 100 µm, bevorzugt von 1 µm bis 10 µm erzeugt.In one embodiment of the present invention, 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.

Bei der Durchführung von Schritt (B) wird Metallpulver (a) in den meisten Fällen partiell oder vollständig durch weiteres Metall ersetzt, wobei die Morphologie von weiterem abgeschiedenem Metall nicht identisch mit der Morphologie von Metallpulver (a) zu sein braucht.In performing step (B), 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).

In einer Ausführungsform des erfindungsgemäßen Verfahrens kann man nach (B) thermisch behandeln, und zwar in einem oder mehreren Schritten. Wünscht man mehrere Schritte zur thermischen Behandlung durchzuführen, so kann man mehrere Schritte bei der gleichen oder vorzugsweise bei verschiedenen Temperaturen durchführen. Die thermische Behandlung nach Schritt (B) kann man analog zur thermischen Behandlung durchführen, wie sie für den Anschluss an Schritt (A) vorstehend beschrieben ist.In one embodiment of the process according to the invention, 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).

In Schritt (C) des erfindungsgemäßen Verfahrens bringt man flächig eine Formulierung auf, die Kohlenstoff in der Modifikation als Ruß oder vorzugsweise Kohlenstoff-Nanoröhren oder besonders bevorzugt in Form von Graphen enthält. Dabei wird unter "flächig" vollflächig oder in weiten Bereichen verstanden, beispielsweise in mindestens 1 cm breiten Streifen, bevorzugt in mindestens 2 cm breiten Streifen.In 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. In this case, "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.

Das Aufbringen kann beispielsweise mit einer Rakel erfolgen. Andere Möglichkeiten des Aufbringens sind Siebdruck, beispielsweise als Rotationsdruck oder Flachbettdruck, und/oder Foulardieren eines Textils.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.

In einer Ausführungsform der vorliegenden Erfindung bringt man flächig eine Formulierung, vorzugsweise eine wässrige Formulierung auf, die Kohlenstoff in der Modifikation als Ruß oder vorzugsweise in Form von Graphen enthält.In one embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung bringt man flächig eine Formulierung auf, die Kohlenstoff in der Modifikation als Ruß enthält, beispielsweise Ofenruß oder Lampenruß, bevorzugt Flammruß, Thermalruß, Acetylenruß, insbesondere Furnace-Ruß.In one embodiment of the present invention, 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.

In einer speziellen Ausführungsform der vorliegenden Erfindung bringt man flächig eine Formulierung auf, die Kohlenstoff-Nanoröhren (Kohlenstoffnanoröhren, kurz CNT oder englisch Carbon nanotubes) enthält, beispielsweise einwandige Kohlenstoffnanoröhren (englisch single-walled carbon nanotubes, SW CNT) und bevorzugt mehrwandige Kohlenstoffnanoröhren (englisch multi-walled carbon nanotubes, MW CNT).In a specific embodiment of the present invention, 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).

Kohlenstoff-Nanoröhren sind an sich bekannt. Ein Verfahren zu ihrer Herstellung und Eigenschaften wird beispielsweise von A. Jess et al. in Chemie Ingenieur Technik 2006, 78, 94 -100 beschrieben.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.

In einer Ausführungsform der vorliegenden Erfindung haben Kohlenstoffnanoröhren einen Durchmesser im Bereich von 0,4 bis 50 nm, bevorzugt 1 bis 25 nm.In one embodiment of the present invention, carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.

In einer Ausführungsform der vorliegenden Erfindung haben Kohlenstoffnanoröhren eine Länge im Bereich von 10 nm bis 1 mm, bevorzugt 100 nm bis 500 nm.In one embodiment of the present invention, carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.

Kohlenstoff-Nanoröhren kann man nach an sich bekannten Verfahren herstellen. Beispielsweise kann man eine flüchtige Kohlenstoff-haltige Verbindung wie beispielsweise Methan oder Kohlenmonoxid, Acetylen oder Ethylen, oder ein Gemisch von flüchtigen Kohlenstoff-haltigen Verbindungen wie beispielsweise Synthesegas in Gegenwart von einem oder mehreren Reduktionsmitteln wie beispielsweise Wasserstoff und/oder einem weiteren Gas wie beispielsweise Stickstoff zersetzen. Ein anderes geeignetes Gasgemisch ist eine Mischung von Kohlenmonoxid mit Ethylen. Geeignete Temperaturen zur Zersetzung liegen beispielsweise im Bereich von 400 bis 1000°C, bevorzugt 500 bis 800°C. Geeignete Druckbedingungen für die Zersetzung sind beispielsweise im Bereich von Normaldruck bis 100 bar, bevorzugt bis 10 bar.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.

Ein- oder mehrwandige Kohlenstoffnanoröhren kann man beispielsweise durch Zersetzung von Kohlenstoff-haltigen Verbindungen im Lichtbogen erhalten, und zwar in Anwesenheit bzw. Abwesenheit eines Zersetzungskatalysators.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.

In einer Ausführungsform führt man die Zersetzung von flüchtiger Kohlenstöff-haltiger Verbindung bzw. Kohlenstoff-haltigen Verbindungen in Gegenwart eines Zersetzungskatalysators durch, beispielsweise Fe, Co oder bevorzugt Ni.In one embodiment, the decomposition of volatile carbonaceous compound or carbon-containing compounds in the presence of a decomposition catalyst, for example Fe, Co or preferably Ni.

Besonders bevorzugt handelt es sich bei Kohlenstoff in Schritt (C) um Graphen. Bei Graphen im Sinne der vorliegenden Erfindung handelt es sich um eine Kohlenstoffmodifikation, die im Wesentlichen sp2-hybridisierte Kohlenstoffatome in Schichten umfasst, die etwa ein bis 500 C-Atome dick sind.More preferably, 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.

In einer Ausführungsform der vorliegenden Erfindung wird Graphen aus solchen Materialien gewählt, welches eine Länge und Breite jeweils im Bereich von 10 nm bis 1000 µm aufweist und eine Dicke im Bereich von 0,3 nm bis 1 µm, bevorzugt bis 1 bis 50 nm und besonders bevorzugt bis 5 nm.In one embodiment of the present invention, graphene is selected from those having a length and a width each in the range of 10 nm to 1000 μm and a thickness in the range of 0.3 nm to 1 μm, preferably 1 to 50 nm, and especially preferably up to 5 nm.

In einer Ausführungsform der vorliegenden Erfindung wird Graphen aus solchen Materialien gewählt, die ein Atomverhältnis Kohlenstoff : Fremdatome im Bereich von 50 : 1, bevorzugt 100 : 1, besonders bevorzugt 200 : 1 und ganz besonders bevorzugt 500 : 1 aufweisen. Dabei sind Fremdatome gleich oder verschieden und im Wesentlichen gewählt aus Sauerstoff, Schwefel, Stickstoff, Phosphor und Wasserstoff, bevorzugt Schwefel und Sauerstoff und insbesondere Wasserstoff. Der Anteil an Fremdatomen ist im Wesentlichen durch den Herstellungsprozess des betreffenden Graphens bestimmt.In one embodiment of the present invention, 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. In this case, 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.

In einer Ausführungsform der vorliegenden Erfindung wählt man Graphen aus solchen Materialien, die man durch mechanische oder chemische Exfoliation (Abtrennung von blättchenförmigen Teilchen, Abblätterung von einer oder weniger Schichten, vorzugsweise bis zu 500 Kohlenstoff-Monoschichten) von Graphit erhalten kann.In one embodiment of the present invention, 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.

In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Graphen aus solchen Materialien, die man durch partielle Oxidation von Graphit zu Graphitoxid, mechanische Exfoliation und anschließende Reduktion herstellen kann.In another embodiment of the present invention, graphene is selected from those materials which can be prepared by partial oxidation of graphite to graphite oxide, mechanical exfoliation, and subsequent reduction.

In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Graphen aus solchen Materialien, die man durch Expansion von Graphit oder Graphit-Interkalationsverbindungen mit Alkalimetall, Wasserstoffperoxid, Halogen oder Butyllithium, beispielsweise n-Butyllithium, gefolgt von Exfoliation von Schichten erhalten kann.In another embodiment of the present invention, 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.

Dabei wird im Rahmen der vorliegenden Erfindung unter Exfoliation eine Abtrennung von blättchenförmigen Teilchen oder eine Abblätterung von einer oder weniger Schichten, vorzugsweise 2 bis zu 1000, besonders bevorzugt 3 bis zu 500 Kohlenstoff-Monoschichten verstanden.In the context of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung weist Graphen eine elektrische Leitfähigkeit im Bereich von 1 bis 200 Ω, vorzugsweise 15 bis 40 Ω auf. Diese Leitfähigkeit wird beispielsweise über die gesamte beschichtete Oberfläche, beispielsweise über die gesamte Schicht nach Schritt (C) bestimmt.In one embodiment of the present invention, graphene has an electrical conductivity in the range of 1 to 200 Ω, preferably 15 to 40 Ω. This conductivity is determined, for example, over the entire coated surface, for example over the entire layer after step (C).

In einer Ausführungsform der vorliegenden Erfindung bringt man in Schritt (C) eine vorzugsweise wässrige Formulierung auf, beispielsweise durch Aufrakeln, Aufdrucken, Aufsprühen, Foulardieren oder Auflaminieren, bevorzugt ist Aufrakeln und Aufdrucken. Die wässrige Formulierung enthält Ruß, Kohlenstoff-Nanoröhren bzw. Graphen.In one embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung bringt man in Schritt (C) eine wässrige Formulierung auf, die im Bereich von 1 bis 300 g Ruß, Kohlenstoff-Nanoröhren bzw. Graphen/kg Formulierung, vorzugsweise 30 bis 60 g/kg enthält.In one embodiment of the present invention, in step (C), an aqueous formulation is added which contains in the range from 1 to 300 g carbon black, carbon nanotubes or graphene / kg formulation, preferably 30 to 60 g / kg.

In einer Ausführungsform der vorliegenden Erfindung bringt man in Schritt (C) wässrige Formulierung auf, die neben Ruß bzw. Kohlenstoff-Nanoröhren oder Graphen mindestens einen Zusatz enthält, beispielsweise ein oder mehrere Dispergiermittel (g), einen oder mehrere Rheologiemodifizierer, Fixierer oder Emulgatoren.In one embodiment of the present invention, in 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.

In einer Ausführungsform der vorliegenden Erfindung kann in Schritt (C) eingesetzte wässrige Formulierung mindestens ein Bindemittel (b) enthalten.In one embodiment of the present invention, an aqueous formulation used in step (C) may contain at least one binder (b).

Beispiele für geeignete Dispergiermittel sind Kondensationsprodukte von aromatischen Mono- oder Disulfonsäuren mit einem oder mehreren Aldehyden, insbesondere mit Formaldehyd, und zwar als freie Säuren oder insbesondere als Alkalimetallsalz. Ein bevorzugtes Beispiel für Dispergiermittel sind Kondensationsprodukte von Naphthalinsulfonsäure mit Formaldehyd, und zwar als Kalium- oder als Natriumsalz.Examples of 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.

In einer Ausführungsform der vorliegenden Erfindung kann man Dispergiermittel (g) in erfindungsgemäßer wässriger Formulierung ganz oder teilweise durch einen oder mehrere Emulgatoren (c) ersetzen.In one embodiment of the present invention, dispersing agent (g) in aqueous formulation according to the invention can be completely or partially replaced by one or more emulsifiers (c).

In einer Ausführungsform der vorliegenden Erfindung enthält im Schritt (C) eingesetzte wässrige Formulierung insgesamt im Bereich von 0,5 bis 20 Gew.-% Zusätze, bevorzugt 1 bis 15 Gew.-%.In one embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung bringt man in Schritt (C) 1 bis 50 g Ruß, Kohlenstoff-Nanoröhren bzw. Graphen pro m2 Oberfläche von Substrat, insbesondere von Textil auf.In one embodiment of the present invention, in step (C), 1 to 50 g of carbon black, carbon nanotubes or graphene per m 2 surface of substrate, in particular textile, are applied.

In einer Ausführungsform der vorliegenden Erfindung kann man nach dem Aufbringen von Ruß oder Kohlenstoff-Nanoröhren oder insbesondere Graphen thermisch behandeln. Bedingungen für eine thermische Behandlung sind vorstehend beschrieben.In one embodiment of the present invention, 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.

Nach der Beendigung des Abscheidens von weiterem Metall und Aufbringen von Kohlenstoff in der Modifikation Ruß, Nanoröhren oder vorzugsweise Graphen erhält man erfindungsgemäß metallisiertes Substrat und insbesondere erfindungsgemäßes metallisiertes textiles Flächengebilde. Man kann erfindungsgemäß metallisiertes Substrat und insbesondere erfindungsgemäßes metallisiertes textiles Flächengebilde noch einoder mehrmals spülen, beispielsweise mit Wasser.After completion of the deposition of further metal and application of carbon in the modification of carbon black, 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.

Zur Herstellung von solchen textilen Flächengebilden, die beispielsweise zur Herstellung von elektrisch beheizbaren Autositzen verwendet werden sollen, kann man noch an den Enden auf an sich bekannte Weise Stromkabel befestigen, beispielsweise anlöten.For the production of such textile fabrics, which are to be used, for example, for the production of electrically heatable car seats, it is still possible to fasten, for example solder, power cables at the ends in a manner known per se.

In einer speziellen Ausführungsform der vorliegenden Erfindung führt man nach Schritt

  • (C) mindestens einen weiteren Schritt aus, gewählt aus
  • (D) Aufbringen einer korrosionsinhibierenden Schicht oder
  • (E) Aufbringen einer flexiblen Schicht,
wobei die korrosionsinhibierende Schicht starr, beispielsweise nicht biegsam, oder flexibel sein kann.In a specific embodiment of the present invention, the procedure is followed by step
  • (C) at least one further step selected from
  • (D) applying a corrosion-inhibiting layer or
  • (E) applying a flexible layer,
wherein the corrosion inhibiting layer may be rigid, for example, non-flexible, or flexible.

Als korrosionsinhibierende Schichten sind beispielsweise Schichten aus einem oder mehreren der folgenden Materialien zu nennen: Wachse, insbesondere Polyethylenwachse, Lacke, beispielsweise Wasserbasislacke, 1,2,3-Benzotriazol und Salze, insbesondere Sulfate und Methosulfate von quaternierten Fettaminen, beispielsweise Lauryl/Myristyl-trimethylammoniummethosulfat.Examples of 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 ,

Als flexible Schichten sind beispielsweise Folien, insbesondere Polymerfolien, beispielsweise aus Polyester, Polyvinylchlorid, thermoplastischem Polyurethan (TPU) oder insbesondere Polyolefinen wie beispielsweise Polyethylen oder Polypropylen zu nennen, wobei unter Polyethylen und Polypropylen jeweils auch Copolymere von Ethylen bzw. Propylen zu verstehen sind.As flexible layers are, 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.

In einer anderen Ausführungsform der vorliegenden Erfindung bringt man als flexible Schicht ein Bindemittel (b) auf, das gleich oder verschieden von gegebenenfalls aufgedrucktem Bindemittel (b) aus Schritt (B) sein kann.In another embodiment of the present invention, a flexible layer is a binder (b) which may be the same or different from optionally printed binder (b) from step (B).

Das Aufbringen kann jeweils erfolgen durch Auflaminieren, Aufkleben, Verschweißen, Aufrakeln, Drucken, Sprühen oder Gießen.The application can be carried out in each case by lamination, gluing, welding, doctoring, printing, spraying or pouring.

Wenn man in Schritt (E) ein Bindemittel aufgebracht hat, so kann man danach erneut thermisch behandeln.If you have applied a binder in step (E), then you can then treat again thermally.

Ein weiterer Gegenstand der vorliegenden Erfindung sind metallisierte Flächengebilde, insbesondere metallisierte textile Flächengebilde, umfassend
mindestens ein textiles Substrat,
mindestens eine Schicht eines weiteren Metalls, das in einem Muster aufgebracht ist, vorzugsweise in einem interdigitalen Muster, und
mindestens eine Schicht, enthaltend Kohlenstoff in der Modifikation als Ruß oder vorzugsweise Graphen.Another object of the present invention are 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.

Ein weiterer Gegenstand der vorliegenden Erfindung sind metallisierte Flächengebilde bzw. Substrate und insbesondere metallisierte textile Flächengebilde, erhältlich nach dem vorstehend beschriebenen Verfahren. Erfindungsgemäße metallisierte Flächengebilde lassen sich nicht nur gut und gezielt herstellen, so kann man beispielsweise durch die Art des aufgedruckten Musters von Metallpulver (a) und durch die Menge an abgeschiedenem weiteren Metall beispielsweise die Flexibilität und die elektrische Leitfähigkeit gezielt beeinflussen. Erfindungsgemäße metallisierte Flächengebilde sind auch flexibel einsetzbar, beispielsweise in Anwendungen für elektrisch leitfähige Textilien.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.

In einer Ausführungsform der vorliegenden Erfindung weisen erfindungsgemäße mit einem Linien- oder Streifenmuster bedruckte metallisierte Flächengebilde einen spezifischen Widerstand im Bereich von 1 mΩ/cm2 bis 1 MΩ/cm2 bzw. im Bereich von 1 µΩ/cm bis 1 MΩ/cm auf, gemessen bei Zimmertemperatur und entlang der betreffenden Streifen bzw. Linien.In one embodiment of the present invention, metallized sheets printed with a line or stripe pattern have a resistivity in the range of 1 mΩ / cm 2 to 1 MΩ / cm 2 and in the range of 1 μΩ / cm to 1 MΩ / cm, respectively. measured at room temperature and along the respective strips or lines.

In einer Ausführungsform der vorliegenden Erfindung umfassen erfindungsgemäße mit einem Linien- oder Streifenmuster bedruckte metallisierte Flächengebilde mindestens zwei Kabel, die an den jeweiligen Enden von Linien oder Streifen auf an sich bekannte Weise befestigt sind, beispielsweise angelötet.In one embodiment of the present invention, 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.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen metallisierten textilen Flächengebilden beispielsweise zur Herstellung von beheizbaren Textilen, insbesondere beheizbaren Autositzen und beheizbaren Teppichen, Tapeten und Bekleidung.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.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen metallisierten textilen Flächengebilden als oder zur Herstellung von solchen Textilien, die Strom in Wärme umwandeln, weiterhin von solchen Textilien, die natürliche oder künstliche elektrische Felder abschirmen können, von Textil-integrierter Elektronik und von RFID-Textilien. Unter RFID-Textilien sind beispielsweise Textilien zu verstehen, die eine Radiofrequenz identifizieren können, z.B. mit Hilfe eines Geräts, das als Transponder oder englisch RFID tag bezeichnet wird. Derartige Geräte benötigen keine interne Stromquelle.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. By 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.

Beispiele für Textil-integrierte Elektronik sind mit Textil integrierte Sensoren, Transistoren, Chips, LED's (Licht-emittierende Dioden, englisch: light emitting diodes), Solarmodule, Solarzellen und Peltier-Elemente. So sind mit Textil integrierte Sensoren beispielsweise geeignet, um die Körperfunktionen von Säuglingen oder älteren Menschen zu überwachen. Geeignete Anwendungen sind weiterhin Warnbekleidung wie z. B. Warnwesten.Examples of textile-integrated electronics are textile-integrated sensors, transistors, chips, LEDs (light-emitting diodes), solar modules, solar cells and Peltier elements. For example, textile-integrated sensors are suitable for monitoring the body functions of infants or the elderly. Suitable applications are still warning clothing such. B. safety vests.

Gegenstand der vorliegenden Erfindung sind deshalb Verfahren zur Herstellung von beheizbaren Textilien, beispielsweise beheizbaren Tapeten, Teppichen und Vorhängen, beheizbaren Autositzen und beheizbaren Teppichen, weiterhin zur Herstellung von solchen Textilien, die Strom in Wärme umwandeln, weiterhin von solchen Textilien, die elektrische Felder abschirmen können, Textil-integrierte Elektronik und von RFID-Textilien unter Verwendung von erfindungsgemäßen metallisierten textilen Flächengebilden. Erfindungsgemäße Verfahren zur Herstellung von beheizbaren Textilien, von solchen Textilien, die Strom in Wärme umwandeln, weiterhin für solche Textilien, die elektrische Felder abschirmen können, und von RFID-Textilien unter Verwendung von erfindungsgemäßen metallisierten textilen Flächengebilden kann man beispielsweise so durchführen, dass man erfindungsgemäßes metallisiertes textiles Flächengebilde konfektioniert.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.

Ein spezieller Gegenstand der vorliegenden Erfindung sind beheizbare Autositze, hergestellt unter Verwendung von erfindungsgemäßem metallisiertem Textil. Erfindungsgemäße beheizbare Autositze benötigen beispielsweise wenig Strom, um eine angenehme Sitztemperatur zu erzeugen, und schonen daher die Autobatterie, was insbesondere im Winter vorteilhaft ist. Weiterhin lassen sich nach dem erfindungsgemäßen Verfahren beheizbare Autositze mit flexiblem Design herstellen, was für eine komfortable Wärmeverteilung sorgt. Auch nach längerer Benutzung weisen erfindungsgemäße metallisierte Textilien noch vorzügliche Eigenschaften auf, beispielsweise nur wenige "hot spots".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. Furthermore, can be produced by the inventive method heated car seats with a flexible design, which ensures a comfortable heat distribution. Even after prolonged use, metallized textiles according to the invention still have excellent properties, for example only a few "hot spots".

Ein spezieller Gegenstand der vorliegenden Erfindung sind Tapeten, Teppiche und Vorhänge, hergestellt unter Verwendung von oder bestehend aus erfindungsgemäßem metallisiertem Textil.A special subject of the present invention are wallpapers, carpets and curtains made using or consisting of metallized textile according to the invention.

In einer Ausführungsform der vorliegenden Erfindung enthalten zum Aufbringen von Graphen geeignete wässrige Formulierungen
im Bereich von 0,01 bis 5 Gew.-%, bevorzugt von 0,1 bis 3,5 Gew.-%, besonders bevorzugt von 2 bis 3 Gew.-% Graphen,
gegebenenfalls im Bereich von 0,1 bis 20 Gew.-% bevorzugt 4% bis 8 Gew.-% Rheologiemodifzierer (d) und
gegebenenfalls im Bereich von 0,1 bis 10 Gew.-%, bevorzugt 1 bis 6 Gew.-% Dispergiermittel.In one embodiment of the present 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.

Die Erfindung wird durch Arbeitsbeispiele erläutert.The invention will be explained by working examples.

Arbeitsbeispieleworking examples

Allgemeine Bemerkungen:

  • Angaben in Prozent bezeichnen Gewichtsprozent, wenn nicht ausdrücklich anders angegeben.
  • Angaben in Gew.-Teilen der Comonomere in den Bindemitteln sind jeweils bezogen auf gesamten Feststoff.
  • Angaben in g bei Dispersionen sind stets tel qu'el.
General remarks:
  • Percentages are percents by weight unless expressly stated otherwise.
  • Data in parts by weight of the comonomers in the binders are in each case based on the total solids.
  • Data in g for dispersions are always tel qu'el.

I. Herstellung von DruckpastenI. Preparation of printing pastes Ingredienzien:ingredients:

Metallpulver (a.1): Carbonyleisenpulver, d10 3 µm, d50 4,5 µm, d90 9 µm, passiviert mit einer mikroskopisch dünnen EisenoxidschichtMetal powder (a.1): carbonyl iron powder, d 10 3 μm, d 50 4.5 μm, d 90 9 μm, passivated with a microscopically thin iron oxide layer

Graphen: Länge nm, Durchmesser nm.Graphene: length nm, diameter nm.

Bindemittel (b.1): wässrige Dispersion, pH-Wert 6,6, Feststoffgehalt 44,8 Gew.-%, eines statistischen Emulsionscopolymerisats von 1 Gew.-Teil Glycidylmethacrylat, 1 Gew.-Teil Acrylsäure, 28,3 Gew.-Teile Styrol, 59,7 Gew.-Teilen n-Butylacrylat, 10 Gew.-Teile 2-Hydroxyethylacrylat, mittlerer Partikeldurchmesser (Gewichtsmittel) 150 nm, bestimmt durch Coulter Counter, Tg: - 19°C, dynamische Viskosität (23°C) 70 mPa·sBinder (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

Bindemittel (b.2):Binder (b.2):

wässrige Dispersion, pH-Wert 7,9, Feststoffgehalt 40%, eines Polyurethans, aufgebaut aus Hexamethylendiisocyanat und Polyesterdiol, hergestellt durch Polykondensation von Adipinsäure, Hexan-1,6-diol und Neopentylglykol (molare Anteile 1 : 0,8 : 0,2), OH-Zahl 55 mg KOH/g nach DIN 53240, und dem Na-Salz der 2'-Aminoethyl-2-aminoethansulfonsäure
mittlerer Partikeldurchmesser (Gewichtsmittel) 100 nm, bestimmt durch Coulter Counter, Tg: -47°C, dynamische Viskosität (23°C) 45 mPa·saqueous 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

Zusätze:Additions:

  • (e.1): Verdicker: statistisches Copolymer aus Acrylsäure (92 Gew.-%), Acrylamid (7,6 Gew.-%), Methylenbisacrylamid, quantitativ neutralisiert mit Ammoniak (25 Gew.-% in Wasser), Molekulargewicht Mw von ca. 150.000g/mol, in einer Wasser-in-Weißöl-Emulsion, Feststoffgehalt 27 %.(e.1): thickener: random copolymer of acrylic acid (92% by weight), acrylamide (7.6% by weight), methylenebisacrylamide, quantitatively neutralized with ammonia (25% by weight in water), molecular weight M w of about 150,000 g / mol, in a water-in-white oil emulsion, solids content 27%.
  • (e.2): Verdicker: 51 Gew.-% Lösung eines Umsetzungsprodukts von Hexamethylendiisocyanat mit n-C18H37(OCH2CH2)15OH in Isopropanol/Wasser (Volumenanteile 2:3)(e.2): thickener: 51% by weight solution of a reaction product of hexamethylene diisocyanate with nC 18 H 37 (OCH 2 CH 2 ) 15 OH in isopropanol / water (volume fractions 2: 3)
  • (e.3) Fixierer (Melamin-Formaldehyd-Kondensat, mit Ethylenglykol verethert)(e.3) fixer (melamine-formaldehyde condensate, etherified with ethylene glycol)
  • (f.1): Verbindung von 2,2',2"-Nitrilotris[ethanol] mit 4-[(2-Ethylhexyl)amino]-4-oxoisocrotonsäure (1:1) (Gehalt (W/W): 30 %), gelöst in: 2,2',2"-Nitrilotriethanol(f.1): Compound of 2,2 ', 2 "-nitrilotris [ethanol] with 4 - [(2-ethylhexyl) amino] -4-oxoisocrotonic acid (1: 1) (content (W / W): 30% ) dissolved in: 2,2 ', 2 "-nitrilotriethanol

Dispergiermittel (g.1): Kondensationsprodukt aus Naphthalinsulfonsäure und Formaldehyd, vollständig neutralisiert mit NaOH.Dispersant (g.1): Condensation product of naphthalenesulfonic acid and formaldehyde, completely neutralized with NaOH.

I.2 Herstellung einer Druckpaste, die Metallpulver (a) enthältI.2 Preparation of a printing paste containing metal powder (a)

Man verrührte miteinander:

  • 54 g Wasser
  • 700 g Metallpulver (a.1).
  • 125 g Bindemittel (b.1)
  • 10 g Fixierer (e.3)
  • 20 g Emulgator (c.1)
  • 20 g Verdicker (e.2)
  • 20 g Korrosionsinhibitor (f.1)
    Figure imgb0002
One mingled with each other:
  • 54 g of water
  • 700 g of metal powder (a.1).
  • 125 g of binder (b.1)
  • 10 g fixer (e.3)
  • 20 g emulsifier (c.1)
  • 20 g thickener (e.2)
  • 20 g corrosion inhibitor (f.1)
    Figure imgb0002

Man rührte über einen Zeitraum von 20 Minuten mit 5000 U/min (Ultra-Thurrax). Man erhielt eine Druckpaste mit einer dynamischen Viskosität von 80 dPa·s bei 23°C, gemessen mit einem Rotationsvikosimeter nach Haake.The mixture was stirred at 5000 rpm for a period of 20 minutes (Ultra-Thurrax). This gave a printing paste with a dynamic viscosity of 80 dPa · s at 23 ° C, measured using a Haake rotary viscometer.

Man erhielt wässrige Druckpaste (A.1).Aqueous printing paste (A.1) was obtained.

II. Herstellung einer erfindungsgemäßen Formulierung, die Graphen enthältII. Preparation of a formulation according to the invention containing graphene

In einem Rührgefäß vermischte man:

  • 100 g einer wässrigen Graphen-Formulierung, enthaltend
  • 3 g Graphen,
  • 60 g Bindemittel (b.2)
  • 8 g Verdicker (e.1)
  • 2 g Fixierer (e.3)
  • weitere 27 g Bindemittel (b.3)
  • 4,1 g Dispergiermittel (g.1).
In a stirred vessel were mixed:
  • 100 g of an aqueous graphene formulation containing
  • 3 g of graphene,
  • 60 g of binder (b.2)
  • 8 g thickener (e.1)
  • 2 g fixer (e.3)
  • another 27 g of binder (b.3)
  • 4.1 g of dispersant (g.1).

Man erhielt eine erfindungsgemäße Formulierung.A formulation according to the invention was obtained.

III. Bedrucken von Textil, Schritt (A), und thermische BehandlungIII. Printing on textile, step (A), and thermal treatment

Man bedruckte mit Druckpaste aus I.2 ein Polyestergewebe mit einem Sieb, mesh 80 mit einem Streifenmuster. Das Muster findet sich schematisch in Abbildung 1.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 ,

Anschließend trocknete man in einem Trockenschrank über einen Zeitraum von 10 Minuten bei 100°C und fixierte 5 Minuten bei 150 °C. Man erhielt bedrucktes und thermisch behandeltes Polyestergewebe.

  • IV. Abscheiden eines weiteren Metalls, Schritt (B), und Aufbringen von einer weiteren Schicht, Schritt (C)
  • IV.1 Abscheiden von Kupfer ohne externe Spannungsquelle
It was then dried in a drying oven over a period of 10 minutes at 100 ° C and fixed at 150 ° C for 5 minutes. This gave printed and thermally treated polyester fabric.
  • IV. Separation of another metal, step (B), and application of another layer, step (C)
  • IV.1 Separation of copper without external voltage source

Bedrucktes und thermisch behandeltes Polyestergewebe aus II. wurde über einen Zeitraum von 30 Minuten in einem Bad (Zimmertemperatur) behandelt, das wie folgt zusammengesetzt war:

  • 1,47 kg CuSOa·S H2O
  • 382 g H2SO4
  • 5,1 l destilliertes Wasser
  • 1,1 g NaCl
  • 5 g C13/C15-Alkyl-O-(EO)10(PO)5-CH3
  • (EO: CH2-CH2-O, PO: CH2-CH(CH3)-O)
Printed and thermally treated polyester fabric of II. Was treated over a period of 30 minutes in a bath (room temperature) composed as follows:
  • 1.47 kg of CuSOa · SH 2 O
  • 382 g H 2 SO 4
  • 5.1 liters of distilled water
  • 1.1 g NaCl
  • 5 g of C 13 / C 15 -alkyl-O- (EO) 10 (PO) 5 -CH 3
  • (EO: CH 2 -CH 2 -O, PO: CH 2 -CH (CH 3 ) -O)

Man entnahm das Polyestergewebe, spülte zweimal unter fließendem Wasser und trocknete bei 90°C über einen Zeitraum von 15 Minuten.The polyester fabric was removed, rinsed twice under running water and dried at 90 ° C over a period of 15 minutes.

Man erhielt metallisiertes Polyestergewebe PES-1.This gave metallized polyester fabric PES-1.

IV.2 Aufbringen einer Schicht, die Graphen enthältIV.2 Applying a layer containing graphene

Das metallisierte Polyestergewebe PES-1 wurde auf einem Drucktisch mittels einer Siebdruckschablone und einer Rakel mit der Formulierung aus II. flächig zwischen bzw. über die Leiterbahnen bedruckt.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.

Das so bedruckte Gewebe wurde 10 Minuten bei 80 °C getrocknet und anschließend 5 Minuten bei 150 °C fixiert.The thus printed fabric was dried at 80 ° C for 10 minutes and then fixed at 150 ° C for 5 minutes.

Man erhielt ein erfindungsgemäßes metallisiertes Gewebe, bei dem sich nach Anlegen einer elektrischen Spannung die mit erfindungsgemäßer Formulierung, welche Graphen enthält, bedruckte Fläche aufheizte, beispielsweise bei 14,3 V auf etwa 50°C. Es wurden jedoch keine Hot Spots beobachtet, sondern ein gleichmäßiges Aufwärmen.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.

Claims (16)

  1. A process for producing a metalized surface, characterized in that the process comprises:
    (A) applying patternedly a formulation comprising at least one metal powder (a) as a component,
    (B)depositing a further metal on the textile surface,
    (C)applying a further layer comprising carbon in the form of carbon black, carbon nanotubes or graphene.
  2. The process according to claim 1, characterized in that the formulation of step (A) comprises:
    (a) at least one metal powder,
    (b) at least one binder,
    (c) at least one emulsifier,
    (d) optionally at least one rheology modifier.
  3. The process according to any one of claims 1 to 2, characterized in that a printing formulation comprising at least one metal powder (a) is applied in step (A) by printing.
  4. The process according to any one of claims 1 to 3, characterized in that the carbon of step (C) is selected as graphene.
  5. The process according to any one of claims 1 to 4, characterized in that one or more thermal treatment steps (D) are carried out following step (A), (B) or (C).
  6. The process according to any one of claims 1 to 5, characterized in that said at least one metal powder (a) is obtained by thermal decomposition of iron pentacarbonyl.
  7. The process according to any one of claims 1 to 6, characterized in that no external source of voltage is used in step (B) and the further metal in step (B) has a stronger positive standard potential in the electrochemical series of the elements than the metal of the at least one metal powder (a).
  8. The process according to any one of claims 1 to 6, characterized in that no external source of voltage is used in step (B) and the further metal in step (B) has a stronger or weaker positive standard potential in the electrochemical series of the elements than the metal of the at least one metal powder (a).
  9. The process according to any one of claims 1 to 8, characterized in that following step (B) one or more articles needing or generating current are fixed on the surface.
  10. The process according to any one of claims 1 to 9, characterized in that the patterns in step (A) are selected from interdigital structures.
  11. The process according to any one of claims 1 to 10, characterized in that step (C) is followed by at least one further step selected from:
    (D)application of a corrosion-inhibiting layer, and
    (E) application of a flexible layer,
    wherein the corrosion-inhibiting layer is flexible or rigid.
  12. The process according to any one of claims 1 to 11, characterized in that the surface is a textile surface.
  13. Metalized surfaces obtainable by a process according to any one of claim 1 to 12.
  14. Use of a metalized textile surface according to claim 13 as or for production of textiles, which convert current into heat, of textiles, able to screen electrical fields, of textile-integrated electronic systems, of displays, of roof liners of vehicles and of textiles able to produce current.
  15. Textiles, which convert current into heat, textiles, able to screen electrical fields, textile-integrated electronic systems, displays, roof liners of vehicles and of textiles, able to produce current, produced by incorporation of the metalized textile surfaces according to claim 13.
  16. Metalized sheet materials according to claim 13, comprising of
    at least one substrate,
    at least one layer of a metal, applied in a pattern,
    at least one layer of a further metal selected from gold, silver or copper and at least one layer comprising carbon in the form of carbon black, carbon nanotubes or graphene.
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RU2548073C2 (en) 2015-04-10
CA2784220A1 (en) 2011-07-14
WO2011082961A2 (en) 2011-07-14
EP2513369A2 (en) 2012-10-24
WO2011082961A3 (en) 2011-11-24
JP2013513737A (en) 2013-04-22
US20110143107A1 (en) 2011-06-16
RU2012129676A (en) 2014-01-27
ES2556334T3 (en) 2016-01-15

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