EP2126190B1 - Method for producing metallised textile surfaces using electricity-generating or electricity-consuming elements - Google Patents

Abstract

The present invention relates to a process for producing a metallized textile surface having one or more articles needing or generating electric current. A formulation having at least one metal powder is applied as a component atop a textile surface patternedly or uniformly. At least one article needing or generating electric current is fixed in at least two locations where formulation was applied. A further metal is deposited on the textile surface.

Description

1. (A) auf eine textile Oberfläche musterförmig oder flächig eine Formulierung aufbringt, die als Komponente mindestens ein Metallpulver (a) enthält,
2. (B) an mindestens zwei Stellen, an denen in Schritt (A) Formulierung aufgebracht wurde, mindestens einen Artikel fixiert, der elektrischen Strom benötigt oder erzeugt,
3. (C) ein weiteres Metall auf der textilen Oberfläche abscheidet.

The present invention relates to a process for preparing a metallized textile surface comprising one or several products which require or generate electric power, characterized in that

1. (A) applying on a textile surface in a pattern or surface a formulation containing as component at least one metal powder (a),
2. (B) at least two locations where formulation has been applied in step (A) fixes at least one article that requires or generates electrical power,
3. (C) depositing another metal on the textile surface.

Furthermore, the present invention relates to metallized textile surfaces produced by the process according to the invention and to the use of metallized textile surfaces.

The production of metallized textile fabrics is a field of activity with great growth potential. Metallized textile surfaces find numerous fields of application. In particular, metallized textile surfaces can be used, for example, as heating jackets, furthermore as fashion articles, 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, one can use metallized textile surfaces for shielding electromagnetic radiation.

It is desirable to provide textiles with articles that require or generate electrical power, such as transistors or photocells. However, there is a problem in attempting to fix such articles on sheets so as to be in contact with electric current. If you try to incorporate electrically conductive wires in films, so special equipment is required.

However, previous methods for producing such metallized textile surfaces are still very complex 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. 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.

One can try to circumvent the above-described disadvantage by incorporating metal threads into a ready-made textile. However, such a procedure usually requires a lot of manual work and is expensive.

The use of electrically conductive polymer fibers has the additional disadvantage that many electrically conductive polymers such as, for example, oxidized polypyrrole are air- and / or moisture-sensitive.

It was therefore the object to provide a method for producing metallized textile surfaces, which are provided with articles that require or generate electrical power, the method avoids the disadvantages described above. A further object was to provide metallized textile surfaces which are provided with articles which require or generate electrical current. Another object was to provide uses for new metallized textile surfaces provided with articles that require or generate electrical power.

Accordingly, the method defined above was found.

The method defined at the outset starts from a textile surface, for example a knitted fabric, a knitted fabric or preferably a woven fabric or a nonwoven fabric (non-woven). Textile surfaces in the sense of the present invention may be stiff or preferably flexible. Preferably, these are textile surfaces which can be bent one or more times manually, for example, without it being possible to visually detect a difference between before bending and after recovery from the bent state.

Textile surfaces are preferably constituents of textile fabrics or three-dimensionally configured textile material. Textile surfaces in the sense 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. In another embodiment, glass fibers and carbon fibers are suitable.

In one embodiment of the present invention, textile surfaces are parts of a composite. Thus, for example, a textile material can be connected to another textile material, for example glued, laminated, sewn or needled. It is also possible that one textile material with another Material is connected, the textile surface, which is assumed to be laminated on a film, for example a polyester film, a polyolefin film, in particular a polyethylene film or a polypropylene film, further a polyamide film or a polyurethane film.

In one embodiment of the present invention, the textile surface may be a coated textile surface coated, for example, with binders such as polyurethane binder, polyacrylate binder or styrene-butadiene latex.

In one embodiment of the present invention, the textile surface may be a surface onto which a film is laminated or laminated, for example a polypropylene film, a polyester film, a polyethylene film or a polyurethane film, in particular a thermoplastic polyurethane film.

In particular, if one wishes to process textile surfaces selected from wide-meshed knits and loose weaves according to the invention, it may be advantageous to use the relevant wide-meshed knit fabric or the relevant wide-meshed fabric in coated form or to laminate it to a film.

To carry out the process according to the invention, in step (A) a formulation is applied to the textile surface which contains at least one metal powder (a). The application can be done, for example, by knife coating, spraying, roll coating, dipping and in particular by printing or printing.

The formulation containing at least one metal powder (a) may preferably be aqueous formulations, in particular aqueous liquors or, more preferably, a printing formulation.

In a preferred embodiment of the present invention, in step (A), a textile surface is printed with a printing formulation, preferably an aqueous printing formulation, containing at least one metal powder (a).

Examples of printing formulations are printing inks, e.g. As gravure inks, offset inks, flexographic inks, screen inks, printing inks such. As inks for the Valvolineverfahren and preferably printing pastes, preferably aqueous printing pastes.

Metal powder (a) is powdered metal, pure or as a mixture or alloy, excluding the alkali metals and the alkaline earth metals Be, Ca, Sr and Ba. Likewise, of course, the radioactive metals are excluded. Metal powder (a) may be selected, for example, from powdered Al, Zn, Ni, Cu, Ag, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi, for example, pure or as mixtures or in the form of powdered alloys of said metals with each other 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) are iron powder and / or copper powder, most preferably iron powder.

In a special variant, the metal powder selected is (a) carbon, in the modification as graphite in particulate form, carbon black or carbon nanotubes. This variant is particularly preferred when operating in step (C) described below with external voltage source. Carbon in the modification Graphite in particulate form, carbon black or carbon nanotubes is included in the scope of the present invention under the term metal powder (a).

In a special variant, the metal powder (a) selected is a mixture of powdered Al, Zn, Ni, Cu, Ag, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi, in particular iron powder on the one hand
and carbon in the modification graphite in particulate form, carbon black or carbon nanotubes on the other hand.

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 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.

Metal powder (a) can be used in passivated form, for example in an at least partially coated ("coated") form. Suitable coatings include, for example, inorganic layers such as oxide of the metal in question, SiO ₂ or SiO ₂ .aq 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, cylindrical, plate-shaped or spherical particles can be used; spherical and plate-shaped particles are preferred. It can be the terms acicular, cylindrical, plate-shaped and spherical refer to idealized shapes, respectively.

In a particularly preferred manner, metal powders (a) with spherical particles are used, preferably predominantly with spherical (spherical) particles, very particularly preferably so-called carbonyl iron powders with spherical particles.

In another particularly preferred embodiment, metal powders (a) are used, which are a mixture of spherical (spherical) particles, most preferably so-called carbonyl iron powder with spherical particles, and platelet-shaped particles, in particular platelet-shaped copper particles.

Metal powder (a) can, in one embodiment of step (A), be applied and preferably printed so that the particles of metal powder are so close that they are already capable of conducting electrical current. In another embodiment of step (A), metal powder (a) may be applied, preferably by printing, that the particles of metal powder (a) are so far apart that they are not capable of conducting the electrical current.

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.

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.

The preparation of carbonyl iron powder by thermal decomposition of, in particular iron pentacarbonyl Fe (CO) ₅ is, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599 , described. 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 comprises a tube made of a heat-resistant material such as quartz glass or V2A steel in a preferably vertical position, which is surrounded by a heater, 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.

1. (a) mindestens ein Metallpulver, 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 formulation, preferably a printing formulation, containing:

1. (a) at least one metal powder, preferably carbonyl iron powder,
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.

Formulations used according to the invention, in particular printing formulations, may contain at least one binder (b), also called 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 other comonomers, for example styrene-butadiene binders. 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.

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.

As binder (b) suitable preferably anionic polyurethanes in the context of the present invention are obtainable, for example, by reacting one or more aromatic or preferably aliphatic or cycloaliphatic diisocyanate 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.

Ethylene (meth) acrylic acid copolymers 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 up to 2500 bar.

Ethylene (meth) acrylic acid copolymers which are particularly suitable as binders (b) may contain, for example, up to 90% by weight of ethylene in copolymerized form and have a kinematic melt viscosity 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.

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 one embodiment of the present invention, as binders (b), particularly suitable copolymers of at least one vinylaromatic copolymerized with at least one conjugated diene and optionally further comonomers are copolymerized: from 19.9 to 80% by weight of vinylaromatic,
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 one embodiment of the present invention, binder (b) has a dynamic viscosity at 23 ° C in the range of 10 to 100 dPa · s, preferably 20 to 30 dPa · s, determined, for example, by rotational viscometry, for example with a Haake viscometer.

As emulsifier (c) it is possible to use anionic, cationic or preferably nonionic surface-active substances.

Examples of suitable cationic emulsifiers (c) are, for example, C ₆ -C ₁₈ -alkyl-, 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.

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 are known in US 4,218,218 and homologues with y (from the formulas US 4,218,218 ) in the range of 10 to 37.

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.

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-mentioned emulsifiers, for example mixtures of nC ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) ₅ O -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 one embodiment of the present invention, formulations used in step (A), in particular printing formulations, may comprise at least one rheology modifier (d) selected from thickeners (d1), which may also be referred to as thickeners, and 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. 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.

Preference is given to the use of synthetic thickening agents 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 necessary for the fixation Lowering the pH can alternatively be done by adding non-volatile acids such as citric acid, succinic acid, glutaric acid or malic acid.

mit Molekulargewichten M_w 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.

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.

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.

Suitable viscosity lowering agents (d2) are, for example, organic solvents such as dimethylsulfoxide (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 -alkanol, preferably residual alcohol-free one to 10-fold, more 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 one embodiment of the present invention contains formulation used in step (A), in particular printing formulation
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 from 0 to 5 wt .-%, preferably 0.2 to 1 wt .-% rheology modifier (d), wherein in wt .-% are in each case based on the total used in step (A) formulation or printing formulation, and in which statements in% by weight of binder (b) relate to the solids content of the particular binder (b).

In one embodiment of the present invention, in step (A) of the process according to the invention can be printed with a formulation, in particular printing formulation, in addition to metal powder (a) and optionally binder (b), emulsifier (c) and optionally rheology modifier (d) at least one Aid (s) contains. Auxiliaries (e) which may be mentioned by way of example are handle improvers, defoamers, wetting agents, leveling agents, urea, corrosion inhibitors, 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.

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.

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.

Suitable biocides are, for example, commercially available as Proxel brands. Examples include: 1,2-Benzisothiazolin-3-one ("BIT") (commercially available as Proxel® 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 one embodiment of the present invention, formulation used in step (A), in particular printing formulation, comprises auxiliaries (e) up to 30% by weight, based on the sum of metal powder (a), binder (b), emulsifier (c) and optionally Rheology modifier (d).

In step (A) it is possible to apply a formulation containing metal powder (a), for example by spraying, knife coating or dipping. It is preferred to carry out the application as printing or printing.

In one embodiment of the present invention, in step (A), such patterns are applied, in particular by printing, in which metal powders (a) are arranged in the form of straight or preferably curved stripe patterns or line patterns on textile, said lines having, for example, a width and Thickness in each case in the range of 0.1 .mu.m to 5 mm and said strips can have a width in the range of 5.1 mm to, for example, 10 cm or optionally more and a thickness of 0.1 .mu.m to 5 mm.

In a specific embodiment of the present invention, in step (A), such stripe patterns or line patterns of metal powder (a) are applied, in particular by printing, in which the stripes do not touch or intersect.

In another specific embodiment of the present invention, in step (A), such stripe patterns or line patterns of metal powder (a) are applied, in particular by printing, in which the stripes branch or unite, for example, when printed Wants to produce circuits.

In one embodiment of the present invention, in step (A), various methods are known which are known per se. In one embodiment of the present invention, a stencil is used by means of which the formulation, in particular printing 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).

Formulations used in the process according to the invention, in particular printing formulations, particularly preferably printing pastes, comprise in one embodiment of the present invention
in the range from 10 to 90% by weight, preferably from 50 to 80% by weight, of metal powder (a), in particular carbonyl iron powder,
in the range of 5 to 30% by weight, preferably 10 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% by weight, preferably 0.2 to 1% by weight of rheology modifier (d),
wherein in wt .-% are in each case based on the entire formulation used in step (A) or printing formulation.

In one embodiment of the present invention, formulation used in the process according to the invention, in particular printing formulation contains up to 30% by weight of auxiliary agent (s), based on the sum of metal powder (a), binder (b), emulsifier (c) and rheology modifier (i.e. ).

1. (a) mindestens ein Metallpulver, besonders bevorzugt ist Carbonyleisenpulver,
2. (b) mindestens ein Bindemittel,
3. (c) mindestens einen Emulgator und
4. (d) gegebenenfalls mindestens einen Rheologiemodifizierer,

sowie gegebenenfalls ein oder mehrere Hilfsmittel (e) in beliebiger Reihenfolge miteinander vermischt.For the preparation of formulations used in the process according to the invention, in particular printing formulations can proceed as follows

1. (a) at least one metal powder, particularly preferred is carbonyl iron powder,
2. (b) at least one binder,
3. (c) at least one emulsifier and
4. (d) optionally at least one rheology modifier,

and optionally one or more adjuvants (e) mixed together in any order.

For the preparation of the formulation used in the process according to the invention, in particular pressure formulation, it is possible, for example, to agitate water and optionally one or more auxiliaries, for example a defoamer, for example a silicone-based defoamer. Then you can add one or more emulsifiers.

Next, one or more handle enhancers may be added, for example, one or more silicone emulsions.

Then you can add one or more emulsifiers (c) and the one or more metal powder (a).

Subsequently, one or more binders (b) and finally optionally one or more rheology modifiers (d) can be added and homogenized with further mixing, for example stirring. It usually comes with relatively short stirring times, for example, 5 seconds to 5 minutes, preferably 20 seconds to 1 minute at stirring speeds in the range of 1000 to 3000 U / min.

The finished formulation according to the invention, in particular printing formulation can, if it is to be used as a printing paste, 30 to 70 wt .-% white oil. Aqueous synthetic thickeners (d1) preferably contain up to 25% by weight of synthetic polymer suitable as thickener (d1). If it is desired to use thickeners (d1) in aqueous formulations, this is generally done aqueous ammonia too. The use of granular, solid formulations thickener (c) are applicable to produce emissions-free prints.

In order to carry out the process according to the invention, in step (B) at least two points are fixed where in step (A) formulation containing metal powder (a) has at least one article which requires or generates electrical current. Such articles are referred to in the context of the present invention as article (B).

For the purposes of the present invention, "at least two sites" are to be understood as meaning those sites of the pattern from step (A) which have metal powders (a).

In one embodiment of the present invention, two of the printed areas in step (A) on which one fixes in step (B) at least one article which requires or generates electric current belong to different parts, for example, strips of the material prepared in step (A). printed pattern.

Preferably, in each case two of the points mentioned in step (B) are close to one another, for example in the range from 0.1 to 5 mm, preferably to 2 mm.

In one embodiment of the present invention, the articles that require or generate electrical power in step (B) are relatively small, for example, with a mean diameter in the range of 1 to 5 mm or smaller.

In one embodiment of the present invention, article (B) has at least two electrical connections, one of which is fixed at the above-mentioned location.

Article (B) may be different or similar.

In one embodiment of the present invention, articles (B) are selected from light emitting diodes, liquid crystal display elements, Peltier elements, transistors, electrochromic dyes, chips (integrated electronic components), resistive elements, capacitive elements, inductive elements, diodes, transistors, actuators, electromechanical Elements and solar cells.

Light emitting diodes, liquid crystal display elements, Peltier elements, transistors, electrochromic dyes, chips (integrated electronic components), resistive elements, capacitive elements, inductive elements, diodes, transistors, actuators, electromechanical elements and solar cells are known as such and commercially available.

In one embodiment of the present invention, the fixing of articles (B) is carried out in known assembly processes and installations. Examples of assembly methods and equipment are known, for example, from printed circuit board manufacturing (surface mount technology). Pick and place machines place, for example, one or more articles (B) at the respective desired location of the textile surface processed after step (A).

In one embodiment of the present invention, in which sufficiently small articles (B) are to be fixed, the starting point is articles (B) wrapped in cardboard or plastic straps. In the straps there are pockets containing the articles (B). The top of the bag is closed, for example, by a film which can be pulled off to remove article (B). The straps themselves are wound up on a roll. On at least one side of the role at regular intervals holes, over which the belt can be moved from the placement machine. These rolls are fed to the placement machine by means of feed modules, so-called feeders. The articles (B) are removed, for example, with vacuum tweezers or grippers and then placed on the target position of the textile substrate. This process is repeated for all articles (B) to be fixed.

In step (C) of the process according to the invention, a further metal is deposited on the textile surface. In this case, it is possible in step (C) to deposit one or more further metals, preferably one deposits only one further metal.

To carry out the process according to the invention, a further metal is deposited on the textile surface in step (C). By "the textile surface" is meant the textile surfaces which have previously been processed according to steps (A) to (C) and optionally further steps such as (D).

It is possible to deposit a plurality of further metals in step (C), but it is preferred to deposit only one more metal.

In one embodiment of the present invention, as metal powder (a) in step (A) carbonyl iron powder is selected and as further metal in step (C) silver, gold or in particular copper.

In one embodiment of the present invention, hereinafter also referred to as step (C1), the procedure is to operate in step (C1) without an external voltage source and that the additional metal in step (C1) 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.

This can be done, for example, that treated in step (A) and in step (B) thermally treated textile surface 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 one embodiment of the present invention, in step (C1), in the range of 0.5 minutes, up to 12 hours, preferably up to 30 minutes, are treated.

In another embodiment of the present invention, in step (C1), it is treated in the range of 10 seconds to 30 seconds.

In one embodiment of the present invention, in step (C1), 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.

In addition, one can add one or more reducing agents in step (C1). 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 another embodiment, hereinafter also referred to as step (C2), the present invention is carried out by operating in step (C2) with external voltage source and that the additional metal in step (C2) 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 (C2) 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 (2). C1) is deposited.

To carry out step (C2), 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.

For performing step (C2), it is possible to operate, for example, over a period of 1 to 160 hours using an external power source.

In one embodiment of the present invention, step (C1) and step (C2) are combined by operating first with and without external voltage source and the further metal in step (C) in the electrochemical series of the elements being more positive Normal potential may have as a metal, the metal powder (a) is based.

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.

Particularly suitable buffers are acetic acid / acetate buffer.

Particularly suitable surfactants are selected from cationic, anionic and in particular nonionic surfactants.

Examples of cationic surfactants are: primary, secondary, tertiary or quaternary ammonium salts containing C ₆ -C ₁₈ -alkyl, aralkyl or heterocyclic, 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.

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 are known in US 4,218,218 and homologues with y (from the formulas US 4,218,218 ) in the range of 10 to 37.

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.

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 Diethylenpentaaminpentaessigsäure and the corresponding alkali metal salts mentioned.

In one embodiment of the present invention, metal is deposited so much further that a layer thickness in the range from 100 nm to 500 μm, preferably from 1 μm to 100 μm, particularly preferably 2 μm to 50 μm, is produced.

In carrying out step (C), metal powder (a) is in most cases partially or completely replaced by further metal, wherein the morphology of further deposited metal need not be identical to the morphology of metal powder (a).

After completion of the deposition of further metal (C), metallized textile surfaces according to the invention are obtained. Metallized textile surfaces according to the invention can be rinsed one or more times, for example with water.

For the production of, for example, such metallized textile surfaces according to the invention, which are to be used for the production of display devices, it is still possible to fasten, for example solder, power cables to the ends in a manner known per se.

In one embodiment of the present invention, one or more thermal treatment steps (D) may be performed following step (A), step (B), or step (C). In the context of the present invention, thermal treatment steps carried out immediately after step (A) are also referred to as thermal treatment steps (D1), thermal treatment steps carried out immediately after step (B) also as thermal treatment steps (D2) and thermal treatment steps carried out after step (C) also as thermal treatment steps (D3).

If one wishes to carry out several thermal treatment steps, one can carry out the various thermal treatment steps at the same or preferably at different temperatures.

In step (D) or each individual step (D) can be treated, for example, at temperatures in the range of 50 to 200 ° C. Care must be taken to ensure that the thermal treatment according to step (D) does not allow the material from which the textile surface used as starting material softens or even melts. It remains in any case with the temperature below the softening or melting point of the textile material in question, or one chooses the duration of the thermal treatment so short that a softening or even melting does not take place.

In step (D) or each individual step (D) can be treated, for example, over a period of 10 seconds to 15 minutes, preferably 30 seconds to 10 minutes.

Particular preference is given in a first step (D1) at temperatures in the range of, for example, 50 to 110 ° C over a period of 30 seconds to 3 minutes and in a second step (D2) then at temperatures in the range of 130 ° C to 200 ° C over a period of 30 seconds to 15 minutes.

It is possible to carry out step (D) or each individual step (D) in devices known per se, for example in drying cabinets, tenter frames or vacuum drying cabinets.

In a preferred embodiment of the present invention, a further step (E) is carried out before step (B). In order to carry out step (E), at some points on the textile surface provided with metal powder (a) after step (A), a mixture which likewise contains a metal in preferably powder form, which may be different from metal powder (a), is deposited is preferably the same.

In one embodiment of the process according to the invention, a mixture which also contains metal powder (a) is precipitated in step (E) at at least two printed areas. In this case, the mixture, which likewise contains metal powder (a), can be a further printing formulation and in particular printing paste, as used in step (A), or else a mixture which contains further constituents. In a third embodiment of step (E) is at the mixture, which also contains metal powder (a), to a preparation containing solder.

In one embodiment of the present invention, in step (E), so much mixture containing metal is deposited that the layer thickness of metal is in the range of 2 to 200 times as thick as the layer thickness of metal powder (a) of step (A). ,

In one embodiment of the present invention, in step (E), there is deposited so much mixture containing metal powder (a) that the layer thickness of metal powder (a) on the textile surface is in the range of 0.1 to 5 mm.

In one embodiment of the present invention, metal powder (a) differs from step (A) of metal powder (a) from step (E), preferably by the mean particle diameter.

In a preferred embodiment of the present invention, metal powders (a) from step (A) and step (E) are the same.

In one embodiment of the present invention, a so-called "dot printing" is performed.

After performing step (E), step (D) can be repeated. However, it is preferable to dispense with a thermal treatment (D) immediately after performing step (E) and immediately perform step (B).

• (F) Aufbringen einer korrosionsinhibierenden Schicht oder
• (G) Aufbringen einer flexiblen Schicht,

wobei die korrosionsinhibierende Schicht starr, beispielsweise nicht biegsam, oder flexibel sein kann.In a specific embodiment of the present invention, after step (C), at least one further step, selected from

• (F) applying a corrosion inhibiting layer or
• (G) applying a flexible layer,

wherein the corrosion inhibiting layer may be rigid, for example, non-flexible, or flexible.

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 ,

As flexible layers, 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 under polyethylene and polypropylene in each case also copolymers of ethylene or propylene are to be understood.

In another embodiment of the present invention, a flexible layer is a binder (b2) which may be the same or different from optionally printed binder (b1) from step (A).

The application can be carried out in each case by lamination, gluing, welding, doctoring, printing, spraying or pouring.

If a binder has been applied in step (G), it is then possible to re-treat it thermally according to step (D).

• von Textilien, die Strom in Wärme umwandeln,
• von Textilien, die elektrische Felder abschirmen können,
• von Textil-integrierter Elektronik,
• von Anzeigeeinrichtungen,
• von Dachhimmeln von Fahrzeugen, insbesondere von Automobilen, und
• von Textilien, die durch Photovoltaik Strom erzeugen können.

Another object of the present invention are metallized textile surfaces, obtainable by the method described above. Not only can metallized textile surfaces according to the invention be produced in a good and targeted manner, the flexibility and 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 textile surfaces according to the invention can be used in many ways, for example as a component or for production

• of textiles that convert electricity into heat,
• of textiles that can shield electrical fields,
• of textile-integrated electronics,
• of display devices,
• of headliners of vehicles, especially automobiles, and
• of textiles that can generate electricity through photovoltaic.

In one embodiment of the present invention, metallized textile surfaces 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 one embodiment of the present invention, metallized textile surfaces 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 surfaces according to the invention as textiles that convert electricity into heat, as textiles that can shield electrical fields, as textile integrated Electronics, as display devices, as a headliner of vehicles and as textiles that can generate electricity, for example by photovoltaics.

Another object of the present invention is the use of metallised textile surfaces as described above for producing textiles that convert electricity into heat, textiles that can shield electrical fields, textile-integrated electronics, display devices, vehicle headliners and vehicles Textiles that can generate electricity, for example through photovoltaics.

Another object of the present invention are textiles that convert electricity to heat, textiles that can shield electrical fields, textile-integrated electronics, displays, headliners of vehicles, and textiles that can generate electricity, such as photovoltaics, manufactured using articles with inventive metallized surface.

Examples of textile-integrated electronics are textile-integrated sensors, transistors, chips, LEDs (light-emitting diodes), solar modules, solar cells and Peltier elements. For example, textiles such as in particular textile-integrated sensors are suitable for monitoring the bodily functions of babies or older people. Suitable applications are still warning clothing such. B. safety vests. Further applications include antennas for example in transponders that can be incorporated in RFID tags, textile-integrated chip card modules, use as flat cables, seat heaters, foil conductors, for the production of LCD or plasma screens or for the production of single- or double-sided metal-clad textiles, floor , Wall or ceiling lighting or as decorative applications of all kinds (eg in the textile or packaging sector, but also for the decoration of eg fabric bags or shoes.

The present invention furthermore relates to processes for the production of such textiles which convert electricity into heat, and furthermore to such textile-integrated electronics using metallized textile surfaces according to the invention. Processes according to the invention for the production of such textiles which convert electricity into heat using metallized textile surfaces according to the invention can be carried out, for example, by fabricating textiles having surfaces metallized according to the invention.

The invention will be explained by working examples.

I. Preparation of a printing paste

• 54 g Wasser
• 750 g Carbonyleisenpulver, d₁₀ 3 µ, d₅₀ 4,5 µm, d₉₀ 9 µm, passiviert mit einer mikroskopisch dünnen Eisenoxidschicht.
• 125 g einer wässrigen Dispersion, pH-Wert 6,6, Feststoffgehalt 39,3 Gew.-%, eines statistischen Emulsionscopolymerisats von
• 1 Gew.-Teil N-Methylolacrylamid, 1 Gew.-Teil Acrylsäure, 28,3 Gew.-Teile Styrol, 69,7 Gew.-Teilen n-Butylacrylat, Angaben in Gew.-Teilen sind jeweils bezogen auf gesamten Feststoff, mittlerer Partikeldurchmesser (Gewichtsmittel) 172 nm, bestimmt durch Coulter Counter, Tg: - 19°C (Bindemittel b.1)
  dynamische Viskosität (23°C) 70 mPa·s,
• 20 g Verbindung der Formel
  
• 20 g einer 51 Gew.-% Lösung eines Umsetzungsprodukts von Hexamethylendiisocyanat mit n-C₁₈H₃₇(OCH₂CH₂)₁₅OH in Isopropanol/Wasser (Volumenanteile 2:3)

One mingled with each other:

• 54 g of water
• 750 g of carbonyl iron powder, d ₁₀ 3 μ, d ₅₀ 4.5 μm, d ₉₀ 9 μm, passivated with a microscopically thin iron oxide layer.
• 125 g of an aqueous dispersion, pH 6.6, solids content 39.3 wt .-%, of a random emulsion of
• 1 part by weight of N-methylolacrylamide, 1 part by weight of acrylic acid, 28.3 parts by weight of styrene, 69.7 parts by weight of n-butyl acrylate, parts in parts by weight are in each case based on total solids, average Particle diameter (weight average) 172 nm, determined by Coulter Counter, Tg: - 19 ° C. (binder b.1)
  dynamic viscosity (23 ° C) 70 mPa · s,
• 20 g of the compound of the formula
  
• 20 g of a 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)

The mixture was stirred at 5000 rpm for a period of 20 minutes (Ultra-Thurrax). A printing paste having a dynamic viscosity of 30 dPa.s at 23 ° C., measured with a Haake rotary viscometer, was obtained.

II. Printing Textile, Step (A), and Thermal Treatment, Step (D1)

I printed with printing paste of I. a polyester fleece, basis weight 90 g / m ² - with a sieve, mesh 80 with a stripe pattern. The pattern is shown in Fig. 1 as a schematic illustration.

It was then dried in a drying oven over a period of 10 minutes at 100 ° C. This gave printed and thermally treated polyester fleece.

III. Provided with a mixture containing metal powder (a1), step (E), and fixing articles requiring electric power, step (B)

I again printed printing paste from I., in the form of small circles with a diameter of 2 mm on the under II printed pattern.

Subsequently, light-emitting diodes of the type Everlight model 67-22SURSYGC S530-A2 / TR8 device number: DSE-672-025 from Everlight Electronics Co., Ltd. in red and green were distributed by hand (SUR type AlGalnP for red Light-emitting diodes, SYR type AlGalnP for yellow light-emitting diodes), format: 3.2 mm, 2.7 mm.

IV. Separation of Another Metal, Step (C) IV.1 Separation of copper without external voltage source

• 1,47 kg CuSO₄·5 H₂O
• 382 g H₂SO₄
• 5,1 I 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 fleece from III. was treated for 10 minutes in a bath (room temperature) composed as follows:

• 1.47 kg of CuSO ₄ .5H 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)

The polyester fleece was removed, rinsed twice under running water and dried at 90 ° C. over a period of one hour.

Inventive metallized polyester nonwoven PES-1 was obtained.

V. Coating with a flexible layer

• 260 g Wasser
• 700 g einer wässrigen Dispersion, pH-Wert 7,0, Feststoffgehalt 55 Gew.-%, eines statistischen Emulsionscopolymerisats von
• 1 Gew.-Teil N-Methylolacrylamid, 1 Gew.-Teil Acrylsäure, 28,3 Gew.-Teile Styrol, 69,7 Gew.-Teile n-Butylacrylat, Angaben in Gew.-Teilen sind jeweils bezogen auf gesamten Feststoff, mittlerer Partikeldurchmesser (Gewichtsmittel) 172 nm, bestimmt durch Coulter Counter, T_g: - 19°C (Bindemittel b.2)
  dynamische Viskosität (23°C) 70 mPa·s,
• 20 g Verbindung der Formel
  
• 20 g einer 51 Gew.-% Lösung eines Umsetzungsprodukts von Hexamethylendiisocyanat mit n-C₁₈H₃₇(OCH₂CH₂)₁₅OH in Isopropanol/Wasser (Volumenanteile 2:3)

One mingled with each other:

• 260 g of water
• 700 g of an aqueous dispersion, pH 7.0, solids content 55 wt .-%, of a random emulsion copolymer of
• 1 part by weight of N-methylolacrylamide, 1 part by weight of acrylic acid, 28.3 parts by weight of styrene, 69.7 parts by weight of n-butyl acrylate, in parts by weight are in each case based on the total solid, medium Particle diameter (weight average) 172 nm, determined by Coulter Counter, T _g : - 19 ° C. (binder b.2)
  dynamic viscosity (23 ° C) 70 mPa · s,
• 20 g of the compound of the formula
  
• 20 g of a 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)

The mixture was stirred at 5000 rpm for a period of 20 minutes (Ultra-Thurrax). A printing paste having a dynamic viscosity of 30 dPa.s at 23 ° C., measured with a Haake rotary viscometer, was obtained.

The metallized textile surfaces of IV. Was coated using an air knife, application speed 20 m / min, with a recording of 300 g / m ² .

Claims (13)

1. A process for producing a metallized textile surface comprising one or more articles needing or generating electric current, which comprises

   (A) applying a formulation comprising at least one metal powder (a) as a component atop a textile surface patternedly or uniformly,

   (B) fixing at least one article needing or generating electric current in at least two locations where formulation was applied in step (A),

   (C) depositing a further metal on the textile surface.
2. The process according to claim 1 wherein the formulation used in step (A) comprises:

   (a) at least one metal powder,

   (b) at least one binder,

   (c) at least one emulsifier,

   (d) if appropriate at least one rheology modifier.
3. The process according to claim 1 or claim 2 wherein 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 the claims 1 to 3 wherein one or more thermal treatment steps (D) are carried out following step (A), (B) or (C).
5. The process according to any one of the claims 1 to 4 wherein said metal powder (a) is obtained by thermal decomposition of iron pentacarbonyl.
6. The process according to any one of the claims 1 to 5 wherein no external source of voltage is used in step (C) and the further metal in step (C) has a more strongly positive standard potential in the electrochemical series of the elements than the metal underlying metal powder (a).
7. The process according to any one of the claims 1 to 5 wherein an external source of voltage is used in step (C) and the further metal in step (C) has a more strongly or more weakly positive standard potential in the electrochemical series of the elements than the metal underlying metal powder (a).
8. The process according to any one of the claims 1 to 7 wherein articles needing or generating electric current are selected from light-emitting diodes, liquid-crystalline display elements, Peltier elements, transistors, electrochromic dyes, electromechanical elements and solar cells.
9. The process according to any one of the claims 1 to 8 wherein emulsifier (c) is selected from nonionic emulsifiers.
10. The process according to any one of the claims 1 to 9 wherein step (C) is followed by at least one further step selected from

    (F) applying a corrosion-inhibiting layer,

    (G) applying a flexible layer,

    the corrosion-inhibiting layer being flexible or rigid.
11. A metallized textile surface obtainable by a process according to any one of the claims 1 to 10.
12. The use of a metallized textile surface according to claim 11 as or for producing a textile that converts current into heat, a textile able to screen off an electric field, a textile-integrated electronic system, a display means, a roof liner of vehicles and a textile able to generate current.
13. A textile that converts current into heat, a textile able to screen off an electric field, a textile-integrated electronic system, a display means, a roof liner of vehicles and a textile able to generate current, produced using a metallized textile surface according to claim 11.