WO2008015167A1

WO2008015167A1 - Dispersion for applying a metal layer

Info

Publication number: WO2008015167A1
Application number: PCT/EP2007/057753
Authority: WO
Inventors: Rene Lochtman; Jürgen Kaczun; Norbert Schneider; Jürgen PFISTER; Norbert Wagner; Christoffer Kieburg; Ketan Joshi
Original assignee: Basf Se
Priority date: 2006-08-03
Filing date: 2007-07-27
Publication date: 2008-02-07
Also published as: TW200815545A

Abstract

The invention relates to a dispersion for applying a metal layer on to an electrically non-conducting substrate, comprising a) 0.1 to 99.8 wt. %, based on the total weight of components A, B, C and D, of an organic binder A; b) 0.1 to 30 wt. %, based on the total weight of components A, B, C and D, of carbon nanotubes as component B; c) 0.1 to 70 wt. %, based on the total weight of components A, B, C and D, of electrically conducting particles with an average particle diameter of 0.01 to 100 μm as C; d) 0 to 99.7 wt. %, based on the total weight of components A, B, C and D, of a solvent component D, a method for production of said dispersion, use of said dispersion, a method for production of a metal layer on the surface of an electrically non-conducting substrate and substrate surfaces and use thereof.

Description

Dispersion for applying a metal layer

description

The present invention relates to a dispersion for applying a metal layer, to processes for the production thereof and to processes for producing a metal layer on a substrate by means of the dispersion. The invention further relates to such coated substrate surfaces and their use.

For producing electrically conductive metallic layers on substrates which do not conduct the electric current, various techniques are known. Thus, electrically non-conductive substrates, such as plastics, can be vapor-deposited with metals in a high vacuum, such processes being complicated and expensive.

Usually, plastics are metallized by performing a series of process steps in succession. In this case, a surface activation step is initially carried out by strong acids or bases. In this case, substances that are of critical health, such as chromic acid, are often used. Subsequently, a coating of the plastic surface takes place by solutions with suitable transition-metal complexes. These allow a metallization of the activated plastic surface.

However, conductive coatings on non-electrically conductive surfaces can also be obtained by conductive inks or conductive pastes, which are applied to the plastic and yet have to have good adhesion to the material.

For example, DE-A 1 615 786 describes processes for the production of electrically conductive layers on electrically non-conductive surfaces with the aid of a lacquer layer which contains finely divided iron. The paint should also contain an organic solvent and certain amounts of binder.

However, it is known that such conductive inks have only relatively low conductivities, since the dispersed metallic particles do not form a coherent conductive layer due to the binder. Thus, the conductivities of these layers do not reach those of metal foils of comparable thickness. Although an increase in the proportion of metal pigment within the layer would also result in an increase in conductance, problems often arise here, for example too low an adhesion strength the conductive layer on the plastic surface or poor dispersibility of the relatively heavy metal particles in the paint.

DE-A 1 521 152 therefore proposes applying a conductive ink to the electrically nonconducting surface which contains a binder and finely divided iron and then applying a layer of silver or of copper to the conductive ink without current. Thereafter, another layer can be applied electrolessly or galvanically. Here, too, a high content of iron is advantageous for achieving sufficient electrical conductivities, which, however, likewise results in problems with the dispersibility of the relatively heavy metal particles in the conductive ink.

Another method of applying a conductive layer to electrically non-conductive surfaces are coatings based on conductive organic polymers. Thus, DE 198 41 804 describes the preparation of conductive structures of polyalkylenedioxythiophene on a support by means of inkjet printing. The disadvantage of the method, however, is the often insufficient adhesion of the conductive polymer on many substrates, as well as the low electrical conductivity over longer distances. Another disadvantage is the low chemical resistance of the resulting layers, which do not allow galvanic metal deposition.

Another well-known method of providing plastics that have electrical conductivity (which is a necessary prerequisite for electrodeposition) is the incorporation of carbon nanotubes, often referred to as "carbon nanotubes" or "carbon nanofibrils", in plastic. These electrically conductive carbon nanotubes also have the advantages, e.g. to have low weight over metal powders and to usually give plastics increased toughness (see, for example, US 2006/0025515 A1). A disadvantage of the production of carbon-nanotube-containing plastics, in which the complete plastic is filled with these particles, are the comparatively high costs, the usually poor incorporation of the carbon nanotubes and the usually reduced flowability of the plastic mixtures.

DE 102 59 498 A1 discloses electrically conductive thermoplastics containing both a particulate carbon compound such as carbon black or graphite, as well as carbon nanofibrils. The plastic mixtures described therein have, in addition to the electrical conductivity, good flowability, good surface quality and high toughness. They are particularly suitable for electrostatic painting. The disadvantage of such polymer mixtures is often very slow or not possible metal deposition in the galvanic metallization. In addition, flowability of conductive black and / or carbon nanotube based dispersions is not sufficient for many coating applications. (Further disadvantages of the processes known from the prior art are the poor adhesion as well as the lack of homogeneity and continuity of the metal layer deposited by electroless or galvanic metallization.) This is due, inter alia, to the fact that the electrically conductive particles are embedded in a matrix material and Because of this, only a small portion of them are free on the surface and thus only a small portion of these particles are available for electroless and / or galvanic metallization, which is particularly problematic when using very small particles (particles in the micrometer to nanometer range) The formation of a homogenous continuous metal coating is therefore very difficult or even impossible to realize at all, which means that process reliability does not exist, and an existing oxide layer on the electrically conductive particles even enhances this effect.

Another disadvantage of the already known methods is the slow electroless and / or galvanic metallization. By embedding the electrically conductive particles in the matrix material, the number of particles exposed on the surface, which are available as growth nuclei for electroless and / or galvanic metallization, is low. This is u.a. This is also due to the fact that when applying, for example, pressure dispersions, the heavy metal particles sink into the matrix material and thus only a few metal particles remain on the surface.

Object of the present invention is to provide optimized systems for homogeneous and continuous metallic coating of electrically non-conductive substrates, in particular using Leitlacken- or dispersions, compared to known systems an improved property combination of low weight, good adhesion, dispersibility, flowability and high have electrical conductivity, as well as faster metallization. Furthermore, the object of the invention to provide an alternative method by which electrically conductive, structured or full surface surfaces can be produced on a support, in which these surfaces are homogeneous and continuously electrically conductive.

Accordingly, a dispersion for depositing a metal layer on an electrically non-conductive substrate was found containing

a 0.1 to 99.8 wt .-% based on the total weight of components A, B, C and D of an organic binder component A;

b 0.1 to 30 wt .-% based on the total weight of components A, B, C and D carbon nanotubes as component B; c from 0.1 to 70% by weight, based on the total weight of components A, B, C and D, of electrically conductive particles having an average particle diameter of from 0.01 to 100 μm as component C;

d 0 to 99.7 wt .-% based on the total weight of components A, B, C and D of a solvent component D.

Furthermore, processes for producing this dispersion, the use of this dispersion, processes for producing a metal layer on the surface of a non-electrically conductive substrate and substrate surfaces and their use have been found.

The dispersions of the invention are essential for the provision of optimized systems for the metallic coating of electrically non-conductive substrates, in particular using Leitlacken- or dispersions, compared to known systems an improved property combination of low weight, good adhesion, dispersibility, flowability and high electrical conductivity have.

The dispersions according to the invention and the further articles, processes and uses according to the invention are described below.

The dispersion according to the invention for applying a metal layer to an electrically non-conductive substrate comprises, based on the total weight of the components A, B, C and D, which gives a total of 100% by weight,

a 0.1 to 99.8 wt .-%, preferably 2 to 87.5 wt .-%, particularly preferably 4 to

80 wt .-% of component A, b 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1 to 15 wt .-% of component B, c 0.1 to 70 Wt .-%, preferably 2 to 65 wt .-%, particularly preferably 4 to 55

Wt .-% of component C, and d 0 to 99.7 wt .-%, preferably 10 to 95.5 wt .-%, particularly preferably 15 bis

91% by weight of component D.

Apart from the abovementioned components A to D, the dispersion according to the invention may contain at least one of the components

e is from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, particularly preferably from 1 to 6% by weight, based on the total weight of components A - D of a dispersant component E; such as f 0.1 to 40 wt .-%, preferably 0.5 to 30 wt .-%, particularly preferably 1 to 10 wt .-%, based on the total weight of the components A - D contain at least one further additive F.

The individual components of the dispersion according to the invention are described below:

Component A

The organic binder component A is a binder or binder mixture. Possible binders are binders with pigment affinity anchor group, natural and synthetic polymers and their derivatives, natural resins and synthetic resins and their derivatives, natural rubber, synthetic rubber, proteins, cellulose derivatives, drying and non-drying oils and the like. These can - but need not - be chemically or physically curing, for example air-hardening, radiation-curing or temperature-curing.

Preferably, the binder component A is a polymer or polymer mixture.

Preferred polymers as component A are ABS (acrylonitrile-butadiene-styrene); ASA (acrylonitrile-styrene-acrylate); acrylated acrylates; alkyd resins; Alkylvinylacetate; Alkylenvi- nylacetat copolymers, in particular methylene vinyl acetate, ethylene vinyl acetate, butylene vinyl acetate; Alkylenvinylchlorid copolymers; amino resins; Aldehyde and ketone resins; Cellulose and cellulose derivatives, in particular alkylcellulose, cellulose esters, such as acetates, propionates, butyrates, cellulose ethers, carboxyalkylcelluloses, cellulose nitrate; epoxy acrylates; epoxy resins; modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, vinyl ethers, ethylene-acrylic acid copolymers; Hydrocarbon resins; MABS (containing transparent ABS with acrylate units); Melamine resins, maleic anhydride copolymers; Methacrylates, optionally amine-functionalized; Natural rubber; synthetic rubber; Chlorinated rubber; Natural resins; rosins; Shellac; Phenol resins; Polyester; Polyester resins such as phenylester resins; polysulfones; Polyether sulphones; polyamides; polyimides; polyanilines; polypyrroles; Polybutylene terephthalate (PBT); Polycarbonate (for example Makrolon ^® from Bayer MaterialScience AG); Polyester acrylate; polyether; polyethylene; Polyethylenthiophene; polyethylene naphthalates; Polyethylene terephthalate (PET); Polyethylene terephthalate glycol (PETG); polypropylene; Polymethyl methacrylate (PMMA); Polyphenylene oxide (PPO); Polystyrenes (PS), poly Tertrafluoroethylene (PTFE); polytetrahydrofuran; Polyethers (for example polyethylene glycol, polypropylene glycol), polyvinyl compounds, in particular polyvinyl chloride (PVC), PVC copolymers, PVdC, polyvinyl acetate and copolymers thereof, optionally partially hydrolyzed polyvinyl alcohol, polyvinyl acetals, polyvinyl acetates, polyvinyl pyrrolidone, polyvinyl ethers, polyvinyl acrylates and methacrylates in solution and as a dispersion and its copolymers, polyacrylic acid esters and polystyrene copolymers; Polystyrene (impact resistant or impact-resistant modified; polyurethanes, uncrosslinked or treated with isocyanates; polyurethane acrylates; Styrofoam-acrylic copolymers; styrene-butadiene block copolymers (for example, Styroflex ^® or Styrolux ^® of BASF Aktiengesellschaft, K-Resin ™ CPC) Proteins such as casein, SIS, SPS block copolymers, triazine resin, bismaleimide-triazine resin (BT), cyanate ester resin (CE), allylated polyphenylene ether (APPE) Furthermore, blends of two or more polymers can form the organic binder component A ) form.

Preferred polymers as component A are acrylates, acrylate resins, cellulose derivatives, methacrylates, methacrylate resins, melamine and amino resins, polyalkylenes, polyimides, epoxy resins, modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins , cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, vinyl ethers, and phenolic resins, polyurethanes, polyesters, polyvinyl acetals, polyvinyl acetates, polystyrenes, polystyrene copolymers, polystyrene acrylates, styrene-butadiene block copolymers, alkylene vinyl acetates and vinyl chloride copolymers, polyamides and their copolymers.

In the production of printed circuit boards, as component A for the dispersion, preference is given to thermal or radiation-curing resins, for example modified epoxy resins, such as bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, cyanate esters, vinyl ethers, phenolic resins, polyimides, melamine resins and amino resins, polyurethanes, polyesters and cellulose derivatives.

Component B

As component B, the dispersions according to the invention contain carbon nanotubes. Carbon nanotubes and their preparation are known in the art and described in the literature, for example in US 2005/0186378 A1. The synthesis of carbon nanotubes can be carried out, for example, in a reactor containing a carbon-containing gas and a metal catalyst (see, for example, US Pat. No. 5,643,502). Carbon nanotubes become commercial marketed, for example, by Bayer MaterialScience AG, the company Hyperion Catalysis or the company Applied Sciences Inc.

Preferred carbon nanotubes typically have a mono- or multi-walled tubular structure. Single-walled carbon nanotubes ("SWCNs") are formed from a single graphitic carbon layer, multi-walled carbon nanotubes ("MWCNs") of multiple such graphitic carbon layers. The graphite layers are arranged in a concentric manner about the cylinder axis. Carbon nanotubes generally have a length to diameter ratio of at least 5, preferably at least 100, more preferably at least 1000. The diameter of the nanotubes is typically in the range of 0.002 to 0.5 .mu.m, preferably in the range of 0.005 to 0.08 microns, more preferably in the range of 0.006 to 0.05 microns. The length of the carbon nanotubes is typically 0.5 to 1000 μm, preferably 0.8 to 100 μm, particularly preferably 1 to 10 μm. The carbon nanotubes have a hollow, cylindrical core around which the graphite layers are formally wound. This cavity typically has a diameter of 0.001 to 0.1 μm, preferably a diameter of 0.008 to 0.015 μm. In a typical embodiment of the carbon nanotubes, the wall of the tube around the cavity consists, for example, of 8 graphite layers. The carbon nanotubes can be present as aggregates of up to 1000 μm in diameter, preferably up to 500 μm in diameter, of several nanotubes. The aggregates may take the form of bird nests, combed yarn or open mesh structures.

In one embodiment of the invention, the addition of the carbon nanotubes to the dispersion according to the invention can be carried out by first incorporating the carbon nanotubes into the binder component A; If component A is a polymer or a polymer mixture, this incorporation can take place during or after the polymerization of the monomers to form the binder component A. If the addition of the nanotubes takes place after the polymerization, it is preferably carried out by adding to the polymer melt in an extruder or in a kneader. The compounding process in the kneader or extruder allows aggregates of carbon nanotubes to be largely or even completely comminuted and the carbon nanotubes to be dispersed in the polymer matrix.

In a preferred embodiment of the previously performed incorporation of the carbon nanotubes into the binder component A, the carbon nanotubes can be metered in as highly concentrated masterbatches in polymers which are preferably selected from the group of polymers used as component A. The concentration of the carbon nanotubes in the masterbatches is usually in the range from 5 to 50, preferably 8 to 30, particularly preferably in the range from rich from 12 to 25 wt .-%. The preparation of masterbatches is described, for example, in US Pat. No. 5,643,502. Through the use of masterbatches, in particular the comminution of the aggregates can be improved.

The carbon nanotubes may have shorter length distributions than originally used due to the incorporation into the dispersion, or by the previous incorporation in component A, shorter length distributions.

Component C

As component C are all electrically conductive particles with any geometry of any electrically conductive material, mixtures of different electrically conductive materials or mixtures of electrically conductive and non-conductive materials suitable having an average particle diameter of 0.001 to 100 .mu.m, preferably from 0.005 to 50 microns, more preferably from 0.01 to 10 microns (determined by laser diffraction measurement on a device Microtrac X100). In the context of the present invention, "electrically conductive particles" are understood as meaning particles whose electrical resistance is less than 10 ⁹ ohms. Suitable electrically conductive materials are, for example, carbon (carbon black, graphite), electrically conductive metal complexes, conductive organic compounds or conductive polymers, for example polythiophenes or polypyrroles, or metals, preferably zinc, nickel, copper, tin, cobalt, manganese, iron, Magnesium, lead, chromium, bismuth, silver, gold, aluminum, titanium, palladium, platinum, tantalum and alloys thereof, or metal mixtures containing at least one of these metals. Examples of suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCo, NiPb, ZnFe, ZnNi, ZnCo and ZnMn. Particularly preferred are aluminum, iron, copper, nickel, silver, tin, zinc, and mixtures thereof. Particularly preferred is iron powder and copper powder.

The metal may also have a non-metallic content in addition to the metallic portion. Thus, the surface of the metal may at least partially be provided with a coating ("coating"). Suitable coatings may be inorganic (for example SiO 2, phosphates) or organic in nature. Of course, the metal may also be coated with another metal or metal oxide. Also, the metal may be in partially oxidized form.

The metal powder particles can in principle have any desired shape, for example, needle-shaped, plate-shaped or spherical metal particles can be used, preferably spherical and plate-shaped. Such metal powders are common commercial goods or can be easily prepared by known methods, such as by electrolytic deposition or chemical reduction from solutions of the metal salts 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. In the case of iron, preference is given to gas and water atomization and the reduction of iron oxides. Metal powders of the preferred grain size can also be made by grinding coarser metal powders. For this purpose, for example, a ball mill is suitable.

In a particularly preferred manner, metal powders with spherical particles, in particular carbonyl iron powder, are used.

The preparation of carbonyl iron powders by thermal decomposition of iron pentacarbonyl is known and is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599. The decomposition of the iron pentacarbonyl can be carried out, for example, at elevated temperatures in a heatable decomposer comprising a tube made of a heat-resistant material such as quartz glass or V2A steel in a preferably vertical position, that of a heating device, for example consisting of heating bands, heating wires or a surrounded by a heating medium flows through heating jacket.

The average particle diameters of the carbonyl iron powder which separates out can be controlled within a wide range by the process parameters and reaction behavior during the decomposition and are generally from 0.01 to 100 μm, preferably from 0.1 to 50 μm, particularly preferably from 0.5 to 10 μm.

If two different metals are to form component C, this can be done by mixing two metals. It is particularly preferred if the two metals are selected from the group consisting of aluminum, iron, copper, silver, zinc and tin.

However, component C may also include a first metal and a second metal in which the second metal is in the form of an alloy (with the first metal or one or more other metals), or component C contains two different alloys. Also for these two cases, the metal components are different from each other, so that their metal particle shape can be selected independently or different independently.

In addition to the choice of metals, the metal particle shape of the metals has an influence on the properties of the dispersion according to the invention after a coating. With regard to the shape, numerous variants known to the person skilled in the art are possible. The

Shape of the metal particle may, for example, acicular, cylindrical, plate-shaped or be spherical. These particle shapes represent idealized shapes, wherein the actual shape, for example due to production, may vary more or less strongly therefrom. For example, drop-shaped particles in the context of the present invention are a real deviation of the idealized spherical shape.

Metals with different particle shapes are commercially available.

If the metal components differ in their metal particle shape, it is preferred if the first is spherical and the second plate-shaped or needle-shaped.

In the case of different particle shapes, the metals aluminum, iron, copper, silver, zinc and tin are also preferred.

Component D

Furthermore, the dispersion of the invention contains a solvent component D. This consists of a solvent or a solvent mixture.

Suitable solvents are, for example, aliphatic and aromatic hydrocarbons (for example n-octane, cyclohexane, toluene, xylene), alcohols (for example methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, amyl alcohol), polyhydric alcohols, such as glycerol, ethylene glycol, propylene glycol, neopentyl glycol, alkyl esters (for example methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, 3-methylbutanol), alkoxy alcohols (for example methoxypropanol, methoxybutanol, ethoxypropanol), alkylbenzenes (cf. Ethylbenzene, isopropylbenzene), butyl glycol, butyl diglycol, alkyl glycol acetates (for example butylglycol acetate, butyldiglycol acetate), carbonates (for example ethylene carbonate and propylene carbonate), chloroform, diacetone alcohol, diglycol dialkyl ethers, diglycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, diglycol alkyl ether acetates, dipropylene glycol alkyl ether acetates, Dioxane, dipropylene glycol and ethers , Diethylene glycol and ether, DBE (dibasic ester), ethers (for example diethyl ether, tetrahydrofuran), ethylene chloride, ethylene glycol, ethylene glycol acetate, ethylene glycol dimethyl ester, cresol, lactones (for example butyrolactone), ketones (for example acetone, Butanone, cyclohexanone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl diglycol, methylene chloride, methylene glycol, methyl glycol acetate, methylphenol (ortho-, meta-, para-cresol), pyrrolidones (for example N-methyl-2-pyrrolidone), Propylene glycol, propylene carbonate, carbon tetrachloride, toluene, trimethylolpropane (TMP), aromatic hydrocarbons and mixtures, aliphatic hydrocarbons and mixtures, alco- Holotic monoterpenes (such as terpineol), water and mixtures of two or more of these solvents.

Preferred solvents are alcohols (for example ethanol, 1-propanol, 2-propanol, butanol), alkoxyalcohols (for example methoxypropanol, ethoxypropanol, butylglycol, butyldiglycol), butyrolactone, diglycol dialkyl ethers, diglycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, esters (for example ethyl acetate , Butyl acetate, butyl glycol acetate, butyl diglycol acetate, diglycol alkyl ether acetates, dipropylene glycol alkyl ether acetates, DBE), ethers (for example tetrahydrofuran), polyhydric alcohols such as glycerol, ethylene glycol, propylene glycol, neopentyl glycol, ketones (for example acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), hydrocarbons (for Example cyclohexane, ethylbenzene, toluene, xylene), N-methyl-2-pyrrolidone, water and mixtures thereof.

When the dispersion is applied to the support by an inkjet method, alkoxy alcohols (for example ethoxypropanol, butylglycol, butyldiglycol) and polyhydric alcohols, such as glycerol, esters (for example butyldiglycol acetate, butylglycol acetate, dipropylene glycol methyl ether acetates), water, cyclohexanone, butyrolactone, N- Methyl-pyrrolidone, DBE and mixtures thereof as a solvent particularly preferred.

Component E

The dispersion according to the invention may further comprise a dispersant component E. This consists of one or more dispersants.

In principle, all dispersants known to the person skilled in the art for use in dispersions and described in the prior art are suitable. Preferred dispersants are surfactants or surfactant mixtures, for example anionic, cationic, amphoteric or nonionic surfactants.

Further preferred are the commercially available, oligomeric and polymeric dispersants known to the person skilled in the art, as described in CD Römpp Chemie Lexikon - Version 3.0, Stuttgart / New York: Georg Thieme Verlag 2006, keyword "dispersing aid".

Examples are polycarboxylic acids, polyamines, salts of long-chain polyamines and polycarboxylic acids, amine / amide functional polyesters and polyacrylates, soya lecithins, polyphosphates, modified caseins. The polymeric dispersants may be present as block copolymers, comb polymers or random copolymers Cationic and anionic surfactants are described, for example, in "Encyclopedia of Polymer Science and Technology", J. Wiley & Sons (1966), Vol. 5, pp. 816-818, and in "Emulsion Polymerization and Emulsion Polymers", editors P. Lovell and M. El-Asser, published by Wiley & Sons (1997), pages 224-226.

Examples of anionic surfactants are alkali metal salts of organic carboxylic acids having chain lengths of 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms. These are commonly referred to as soaps. They are usually used as sodium, potassium or ammonium salts. In addition, alkyl sulfates and alkyl or alkylaryl sulfonates having 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms, can be used as anionic surfactants. Particularly suitable compounds are alkali dodecyl sulphates, e.g. Sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali salts of C12-C16 paraffin sulfonic acids. Furthermore, sodium dodecylbenzenesulfonate and sodium dioctylsulfone succinate are suitable.

Examples of suitable cationic surfactants are salts of amines or diamines, quaternary ammonium salts, e.g. Hexadecyltrimethylammoniumbromid and salts of long-chain substituted cyclic amines, such as pyridine, morpholine, piperidine. In particular, quaternary ammonium salts, e.g. Hexadecyltrimethylammoniumbromid of trialkylamines used. The alkyl radicals preferably have 1 to 20 carbon atoms therein.

In particular, according to the invention nonionic surfactants can be used in component E. Nonionic surfactants are described, for example, in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "nonionic surfactants".

Suitable nonionic surfactants include for example polyethylene oxide or polypropylene oxide-based substances such as Pluronic ^® and Tetronic ^® from BASF Aktiengesellschaft.

Polyalkylene glycols suitable as nonionic surfactants generally have a number average molecular weight M _n in the range from 1000 to 15000 g / mol, preferably 2000 to 13000 g / mol, particularly preferably 4000 to 11000 g / mol. Preferred nonionic surfactants are polyethylene glycols.

The polyalkylene glycols are known per se or can be prepared by processes known per se, for example by anionic polymerization with alkali metal hydroxides, such as sodium or potassium hydroxide or alkali metal, such as sodium, sodium or potassium or potassium isopropoxide, as catalysts and with the addition of at least one starter molecule, the 2 to 8, preferably 2 to 6, bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as monpentachlorid, borofluoride etherate or bleaching earth, are prepared as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.

Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 2 or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and / or 1, 2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures. Suitable starter molecules are, for example: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid or terephthalic acid, aliphatic or aromatic, optionally N-mono-, N, N- or N, N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 3-propylenediamine, 1, 3 or 1, 4-butylenediamine, 1, 2, 1, 3, 1, 4, 1, 5 or 1, 6-hexamethylenediamine.

Further suitable starter molecules are: alkanolamines, e.g. Ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, e.g. Diethanolamine, N-methyl and N-ethyldiethanolamine, and trialkanolamines, e.g. Triethanolamine, and ammonia. Preference is given to using polyhydric, in particular dihydric, trihydric or polyhydric alcohols, such as ethanediol, propanediol 1, 2 and 1, 3, diethylene glycol, dipropylene glycol, butanediol 1, 4, hexanediol 1, 6, glycerol, Trimethylolpropane, pentaerythritol, and sucrose, sorbitol and sorbitol.

Also suitable for component E are esterified polyalkylene glycols, for example the mono-, di-, tri- or polyesters of the polyalkylene glycols mentioned, which are obtained by reaction of the terminal OH groups of said polyalkylene glycols with organic acids, preferably adipic acid or terephthalic acid can be produced in a known manner.

Nonionic surfactants are substances produced by alkoxylation of compounds with active hydrogen atoms, for example addition products of alkylene oxide onto fatty alcohols, oxo alcohols or alkylphenols. Thus, for example, ethylene oxide or 1,2-propylene oxide can be used for the alkoxylation.

Further possible nonionic surfactants are alkoxylated or non-alkoxylated sugar esters or sugar ethers.

Sugar ethers are alkyl glycosides obtained by reaction of fatty alcohols with sugars. Sugar esters are obtained by reacting sugars with fatty acids. The sugars, fatty alcohols and fatty acids necessary for the production of the substances mentioned are known to the person skilled in the art. Suitable sugars are described for example in Beyer / Walter, textbook of organic chemistry, S. Hirzel Verlag Stuttgart, 19th edition, 1981, pages 392 to 425. Possible sugars are D-sorbitol and sorbitans obtained by dehydration of D-sorbitol.

Suitable fatty acids are saturated or mono- or polyunsaturated unbranched or branched carboxylic acids having 6 to 26, preferably 8 to 22, particularly preferably 10 to 20 C atoms, as described, for example, in CD Römpp Chemie Lexikon, Version 1.0, Stuttgart / New York : Georg Thieme Verlag 1995, keyword "fatty acids" are called. Conceivable are fatty acids such as lauric acid, palmitic acid, stearic acid and oleic acid.

Suitable fatty alcohols have the same carbon skeleton as the compounds described as suitable fatty acids.

Sugar ethers, sugar esters and the processes for their preparation are known in the art. Preferred sugar ethers are prepared by known processes by reacting the said sugars with the stated fatty alcohols. Preferred sugar esters are prepared by known processes by reacting the said sugars with said fatty acids. Suitable sugar esters are mono-, di- and triesters of sorbitans with fatty acids, in particular sorbitan monolaurate, sorbitan diethylate, sorbitan trilaurate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate and sorbitan sesquioleate, of a mixture of sorbitan mono- and diesters of oleic acid.

Possible for the component E are thus alkoxylated sugar ethers and sugar esters, which are obtained by alkoxylation of said sugar ethers and sugar esters. Preferred alkoxylating agents are ethylene oxide and 1,2-propylene oxide. The degree of alkoxylation is generally between 1 and 20, preferably 2 and 10, more preferably 2 and 6. Examples of these are polysorbates which are obtained by ethoxylation of the sorbitan esters described above, for example described in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Polysorbate". Suitable polysorbates are polyethoxysorbitan, stearate, - palmitate, tristearate, oleate, trioleate, especially polyethoxysorbitan which Tween ^® 60 from ICI America Inc., for example, as available (for example, described in CD Rompp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Tween ^®").

The use of polymers as dispersants is also possible. Component F

Furthermore, the dispersion of the invention may contain at least one further additive F, which is different from the components A, B, C, D and E. This can consist of one or more additives. Thus, component F may contain soluble, fibrous or particulate additives or mixtures thereof. These are preferably commercially available products.

Furthermore, fillers or reinforcing materials, such as glass powder, glass cloth, glass fleece, mineral fibers, whiskers, alumina fibers, mica, quartz powder or WoIlastonit can be used. Furthermore, silicic acid, silicates, such as aerosols or phyllosilicates, dyes, fatty acids, amides, plasticizers, wetting agents, drying agents, complexing agents, calcium carbonate, barium sulfate, titanium dioxide, waxes, Woelastonit, pigments or aramid fibers can be used.

Furthermore, further additives, such as thixotropic agents, for example silica, silicates, such as aerosils or benthonites or organic thixotropic agents and thickeners, such as polyacrylic acid, polyurethanes, hydrogenated castor oil, dyes, fatty acids, fatty acid amides, plasticizers, wetting agents, defoamers, lubricants, Dry substances, crosslinkers, photoinitiators, complexing agents, waxes, pigments can be used.

Furthermore, the dispersions of the invention as component F, for example, processing aids and stabilizers such as UV stabilizers, lubricants, corrosion inhibitors and flame retardants.

Another object of the present invention is a process for preparing the dispersion of the invention comprising the steps

a ^' ) mixing the components A to C and at least part of the component D, and optionally E, F and further components and

b ^' ) dispersing the mixture

c ') optionally adding the proportion of component D not used in step a ^' ) to

Adjustment of the viscosity for the respective application method. The dispersion preparation can be carried out by intensive mixing and dispersing with aggregates known in the art. This involves mixing the components in an intensely dispersing aggregate, such as kneaders, ball mills, bead mills, dissolvers, three-roll mills or rotor-stator mixers

It is possible to mix all the desired components of the dispersion in one process step. However, it is also possible to premix two or more components, for example components A and B as described above, and to add the remaining components only in a subsequent separate method step.

A further subject of the present invention is a method for producing a metal layer on at least part of the surface of a non-electrically conductive substrate, comprising the steps:

a) at least partially applying a dispersion of the invention on the substrate;

b) at least partially drying and / or curing of the applied dispersion on the substrate layer; and

c) electroless and / or galvanic deposition of a metal on the at least partially dried and / or cured dispersion layer to form a metal layer.

When applying the dispersion and adjusting the viscosity in step a), it is preferred if the dispersion is stirred and tempered.

Optionally, an activation step can be inserted between steps b) and c). This consists of the at least partial exposure of the electrically conductive particles by at least partial chemical and / or mechanical disruption of the dried and / or cured dispersion layer.

If the electrically conductive particles contain a material which can easily oxidize, in a variant of the method, before forming the metal layer on the structured or full-surface dried and / or hardened dispersion layer, the oxide layer of the electrically conductive particles can be at least partially removed. The removal of the oxide layer can take place, for example, chemically and / or mechanically. Suitable substances with which the dried and / or cured dispersion layer can be treated in order to chemically remove an oxide layer from the electrically conductive particles are, for example, acids, such as te or dilute sulfuric acid or concentrated or dilute hydrochloric acid, citric acid, phosphoric acid, sulfamic acid, formic acid, acetic acid.

The at least partial removal of the oxide layer as well as the at least partial release of the electrically conductive particles on the surface can also take place in the same work step.

As electrically non-conductive substrates on which the dispersion according to the invention is applied, for example, rigid or flexible carrier are suitable. Suitable carriers are, for example, reinforced or unreinforced polymers. Suitable polymers are epoxy resins, or modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, aramid-reinforced or glass-fiber-reinforced or paper-reinforced epoxy resins (for example FR4), glass fiber reinforced plastics, liquid crystal Polymers (LCP), polyphenylene sulfides (PPS), polyoxymethylenes (POM), polyaryletherketones (PAEK), polyetheretherketones (PEEK), polyamides (PA), polycarbonates (PC), polybutylene terephthalates (PBT), polyethylene terephthalates (PET), polyimides (PI ), Polyimide resins, cyanoester, bismaleimide-triazine resins, nylon, vinyl ester resins, polyesters, polyester resins, polyamides, polyanilines, phenol resins, polypyrroles, polynaphthalene terephthalates (PEN), polymethyl methacrylate, phosphorus-modified epoxy resins, polyethylene dioxythiophenes, phenolic resin coated aramid paper, polytetrafluoroethylene ( PTFE), melamine resins, silicone resins, fluororesins, dielectrics, APPE, poly etherimides (PEI), polyphenylene oxides (PPO), polypropylenes (PP), polyethylenes (PE), polysulfones (PSU), polyethersulfones (PES), polyarylamides (PAA), polyvinyl chlorides (PVC), polystyrenes (PS), acrylonitrile butadiene styrenes (ABS ), Acrylonitrile-styrene-acrylates (ASA), styrene-acrylonitriles (SAN) and mixtures (blends) of two or more of the abovementioned polymers, which can be present in various forms. The substrates may have additives known to the person skilled in the art, for example flame retardants.

In principle, all polymers listed under component A can also be used.

Furthermore, suitable substrates composites, foam-like polymers, Styropor® ^®, styrodur ^®, polyurethanes (PU), ceramic surfaces, textiles, cardboard, KAR ton, paper, polymer-coated paper, wood, mineral materials, silicon, glass, plant tissue and animal tissue , or resin-impregnated fabrics pressed into sheets or rolls.

In the context of the present invention, a "non-electrically conductive substrate" is preferably understood to mean that the surface resistance of the substrate is more than 10 ⁹ ohm / cm. The dispersion can be applied by methods known to the person skilled in the art. The application to the substrate surface can take place on one or more sides and extend to one, two or three dimensions. In general, the substrate can have any desired geometry adapted to the intended use.

The application of the dispersion can be carried out by the customary and generally known coating methods (casting, brushing, knife coating, printing (gravure printing, screen printing, flexographic printing, pad printing, inkjet, offset, Lasersonic® process as described in DE10051850, etc.) The layer thickness varies preferably between 0.01 and 100 μm, more preferably between 0.1 and 50 μm, in particular preferably between 1 and 25 μm The layers can be both full-surface and structured be applied.

The drying or curing of the structured or fully applied dispersion is carried out by conventional methods. Thus, for example, the dispersion can be cured chemically, for example by polymerization, polyaddition or polycondensation of the binder, for example by UV radiation, electron radiation, microwave radiation, IR radiation or temperature, or by purely physical means by evaporation of the solvent be dried. A combination of drying by physical and chemical means is possible.

The layer obtained after application of the dispersion and drying and / or curing enables a subsequent electroless and / or galvanic deposition of a metal on the at least partially dried and / or cured dispersion layer.

The dispersion according to the invention can be structured or applied in a planar manner in step a). It is preferable if the steps of applying [step a)], drying and / or curing [step b)] and depositing another metal [step c)] are carried out in a continuous mode. This is possible by simply carrying out steps a), b) and c). However, it goes without saying that a batchwise or semi-continuous process is possible.

The currentless and / or galvanic deposition of a metal carried out in step c) can be carried out according to the method known to the person skilled in the art and described in the literature. It is possible for one or more metal layers to be applied without current and / or galvanically, ie by applying external voltage and current flow. In principle, all metals are nobler than component C. the dispersion, for the electroless deposition in question. In principle, all metals are suitable for the electrodeposition. Preferably, copper, chromium, silver, gold and / or nickel layers are electrodeposited. The thickness of the one or more deposited layers in step c) is in the usual range known to the person skilled in the art and is not essential to the invention.

Although a special pretreatment of the surface of the metallizable substrates is not necessary prior to the electroless and / or galvanic metallization, in principle a surface activation can be carried out by processes known to the person skilled in the art. A surface activation can be used to improve the adhesion or to accelerate the metal deposition by the surface is roughened targeted, or exposed to carbon nanotubes and, for example, metal particles on the surface. Exposing the nanotubes and metal particles also has the advantage that a lesser amount is needed in the polymer matrix to achieve metallization.

Surface activation can be accomplished, for example, by mechanical abrasion, in particular by brushing, grinding, abrasive polishing or jet blasting, sandblasting or supercritical carbon dioxide (dry ice) blasting, physically, for example by heating, laser, UV light, corona or plasma discharge and / or chemical abrasion, in particular by etching and / or oxidation. Methods for carrying out the mechanical abrasion and / or chemical abrasion are known to the person skilled in the art and described in the prior art.

As abrasives for polishing, it is possible to use all abrasives known to the person skilled in the art. A suitable abrasive is, for example, pumice. In order to remove the uppermost layer of the hardened dispersion by pressure blasting with the water jet, the water jet preferably contains small solid particles, for example pumice flour (AI 2 O 3) having an average particle size distribution of 40 to 120 μm, preferably 60 to 80 μm, and quartz flour ( SiO 2) with a particle size> 3 μm.

In the case of chemical abrasion, it is preferable to use a suitable chemical or chemical mixture for the polymer. In the case of a chemical abrasion, either the polymer can be at least partially dissolved and washed down by a solvent on the surface, for example, or at least partially destroyed by means of suitable reagents, the chemical structure of the matrix material, whereby the carbon nanotubes are exposed. Reagents that cause the matrix material to swell are also used for the release. suitable for the carbon nanotubes. The swelling creates cavities in which the metal ions to be deposited can penetrate from the electrolyte solution, whereby a larger number of carbon nanotubes can be metallized. Due to the higher number of exposed carbon nanotubes, the process speed during metallization is higher.

For example, when the matrix material is an epoxy resin, a modified epoxy resin, an epoxy novolac, a polyacrylic acid ester, ABS, a styrene-butadiene copolymer or a polyether, the carbon nanotubes and, for example, the metal particles are exposed with an oxidizing agent. The oxidizing agent breaks up bonds in the matrix material, which allows the binder to be peeled off and thereby expose the particles. Suitable oxidizing agents are, for example, manganates, for example potassium permanganate, potassium manganeseate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen, oxygen in the presence of catalysts, for example manganese, molybdenum, bismuth, tungsten and cobalt salts, ozone, Vanadium pentoxide, selenium dioxide, ammonium polysulfide solution, sulfur in the presence of ammonia or amines, manganese dioxide, potassium ferrite, dichromate / sulfuric acid, chromic acid in sulfuric acid or in acetic acid or in acetic anhydride, nitric acid, hydroiodic acid, hydrobromic acid, pyridinium dichromate, chromic acid-pyridine Complex, chromic anhydride,

Chromium (VI) oxide, periodic acid, lead tetraacetate, quinone, methylquinone, anthraquinone, bromine, chlorine, fluorine, iron (III) salt solutions, disulphate solutions, sodium percarbonate, salts of oxohalogenic acids, for example chlorates or bromates or iodates, salts of halogenated acids, such as sodium periodate or sodium perchlorate, sodium perborate, dichromates such as sodium dichromate, salts of persulfuric acid such as potassium peroxodisulfate, potassium peroxomonosulfate, pyridinium chlorochromate, salts of hypohalogenic acids, for example sodium hypochlorite, dimethyl sulfoxide in the presence of electrophilic reagents, tert-butyl hydroperoxide , 3-chlorobenzobenzoic acid, 2,2-dimethylpropanal, des-Martin periodinane, oxalyl chloride, urea-hydrogen peroxide adduct, urea peroxide, 2-iodoxybenzoic acid, potassium peroxomonosulfate, m-chloroperbenzoic acid, N-methylmorpholine N-oxide, 2-methylprop-2 -yl hydroperoxide, peracetic acid, pivaldehyde, osmium tetraoxide, oxones, ruthenium (III) - and (IV) Salts, oxygen in the presence of 2,2,6,6-tetramethylpiperidinyl-N-oxide, triacetoxiperiodinane, trifluoroperacetic acid, trimethylacetaldehyde, ammonium nitrate. Optionally, to improve the exposure process, the temperature may be increased during the process.

Preference is given to manganates, for example potassium permanganate, potassium manganate,

sodium permanganate; Sodium manganate, hydrogen peroxide, N-methyl-morpholine N-oxide, percarbonates, for example sodium or potassium percarbonate, perborates, for

Example, sodium or potassium perborate; Persulfates, for example sodium or potassium persulphates, sodium, potassium and ammonium peroxodis and monosulphates, sodium hypochlorite, urea-hydrogen peroxide adducts, salts of oxohalogenic acids, such as, for example, chlorates or bromates or iodates, salts of halogenated acids, for example sodium periodate or sodium perchlorate, tetrabutylammonium peroxidi sulfate, quinones, iron (III) salt solutions, vanadium pentoxide, pyridinium dichromate, hydrochloric acid, bromine, chlorine, dichromates.

Particularly preferred are potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide and its adducts, perborates, percarbonates, persulfates, peroxodisulfates, sodium hypochlorite and perchlorates.

In order to expose the carbon nanotubes and, for example, the metal particles in a matrix material containing, for example, ester structures such as polyester resins, polyester acrylates, polyether acrylates, polyester urethanes, it is preferable to use, for example, acidic or alkaline chemicals and / or chemical mixtures. Preferred acidic chemicals and / or chemical mixtures are, for example, concentrated or dilute acids, such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid. Also organic acids, such as formic acid or acetic acid, may be suitable depending on the matrix material. Suitable alkaline chemicals and / or chemical mixtures are, for example, bases, such as sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or carbonates, for example sodium carbonate or potassium carbonate. Optionally, to improve the exposure process, the temperature may be increased during the process.

Solvents can also be used to expose the carbon nanotubes and, for example, the metal particles in the matrix material. The solvent must be matched to the matrix material as the matrix material must dissolve in the solvent or swell through the solvent. If a solvent is used in which the matrix material dissolves, the base layer is only brought into contact with the solvent for a short time, so that the upper layer of the matrix material is dissolved and thereby becomes detached. In principle, all abovementioned solvents can be used. Preferred solvents are xylene, toluene, halogenated hydrocarbons, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diethylene glycol monobutyl ether. Optionally, to improve the dissolution behavior, the temperature during the dissolution process can be increased.

Another object of the present invention is a substrate surface with at least partially having electrically conductive metal layer, which is obtainable by the above-described method according to the invention for producing a metal layer. Such a substrate surface may be used to conduct electricity or heat, shield electromagnetic radiation, and magnetize.

Another object of the present invention is the use of a dispersion according to the invention for applying a metal layer.

The substrate surface according to the invention and the method according to the invention can be used in particular for various applications listed below.

The substrate surface according to the invention and / or the method according to the invention is suitable, for example, for producing printed conductors on printed circuit boards. Such printed circuit boards are, for example, those with multilayer inner and outer layers, microvias, chip-on-board, flexible and rigid printed circuit boards, and are incorporated, for example, in products such as computers, telephones, televisions, automotive electrical components, keyboards, Radios, video, CD, CD-ROM and DVD players, game consoles, measuring and control devices, sensors, electrical kitchen appliances, electric toys, etc.

Also, with the method according to the invention, electrically conductive structures can be coated on flexible circuit carriers. Such flexible circuit carriers are, for example, plastic films made of the materials mentioned above for the carrier, on which electrically conductive structures are printed. Furthermore, the method according to the invention is suitable for the production of RFI D antennas, transponder antennas or other antenna structures, chip card modules, flat cables, seat heaters, foil conductors, conductor tracks in solar cells or in LCD or plasma picture screens, capacitors, foil capacitors, resistors, convectors, e dielectric fuses or for the production of electroplated products in any desired form, for example single- or double-sided metal-clad polymer supports with defined layer thickness, 3D-Molded Interconnect Devices or also for the production of decorative or functional surfaces on products, for example for shielding of electromagnetic radiation, for heat conduction or as packaging.

Furthermore, the production of antennas with contacts for organic electronic components as well as coatings on surfaces consisting of electrically non-conductive material for electromagnetic shielding (EMI) is possible.

Furthermore, the production of a metallic inner coating for the realization of waveguides for high-frequency signals with a mechanically supporting structure is made electrically non-conductive material possible. Likewise, the substrate surface may be part of film capacitors.

A further use is possible in the field of flowfields of bipolar plates for use in fuel cells.

Furthermore, it is possible to produce a full-surface or structured electrically conductive layer for the subsequent decorative metallization of molded parts from the abovementioned electrically non-conductive substrate.

The scope of the inventive method for producing a metal layer using the dispersion of the invention and the substrate surface according to the invention enables a cost-effective production of metallized, even non-conductive substrates, in particular for use as switches and sensors, absorbers for electromagnetic radiation or gas barriers or decorative parts, in particular decorative parts for motor vehicle, sanitary, toy, household and office sectors and packaging as well as foils. Also in the field of security printing for bills, credit cards, identity papers, etc., the invention may find application. Textiles can be electrically and magnetically functionalized by means of the method according to the invention (antennas, transmitters, RFID and transponder antennas, sensors, heating elements, antistatic (also for plastics), shielding, etc.).

Examples of such applications are housings, such as computer housings, housing for screens, mobile phone, audio, video, DVD, camera, housing for electronic components, military and non-military shielding devices, shower and washbasin faucets, showerheads, shower rods and holders, metallized door handles and door knobs, toilet paper roll holders, bath tub handles, metallised trim strips on furniture and mirrors, shower enclosure frames, packaging materials.

Also to be mentioned are: metallized plastic surfaces in the automotive sector such as trim strips, exterior mirrors, radiator grills, front-end metallization, wind deflectors, body exterior and interior parts, door sill, tread plate replacement, wheel covers.

Furthermore, such parts of non-conductive material can be produced, which were previously made partially or entirely of metals. Examples include downpipes, gutters, doors and window frames.

Furthermore, it is possible to produce contact points or contact pads or wirings on an integrated electrical component. Furthermore, the production of thin metal foils or one or two-sided laminated polymer supports, metallized plastic surfaces, such as trim strips or exterior mirrors, is possible.

The dispersion according to the invention and / or the method can also be used for the metallization of holes, vias, blind holes, etc., for example in printed circuit boards, RFID antennas or transponder antennas, flat cables, foil conductors with the aim of a through contact of the top and bottom. This also applies if other substrates are used.

Furthermore, the metallized objects produced according to the invention - insofar as they comprise magnetizable metals - are used in areas of magnetizable functional parts such as magnetic boards, magnetic games, magnetic surfaces in, for example, refrigerator doors. In addition, they find application in areas where a good thermal conductivity is advantageous, for example in films for seat heaters, underfloor heating and insulation materials.

Preferred uses of the substrate surface metallized according to the invention are those in which the substrate produced in this way is used as a printed circuit board, RFI D antenna, transponder antenna, seat heating, flat cable, contactless chip cards, thin metal foils or polymer backing coated on one or two sides, foil conductors, conductor tracks in solar cells or in LCD or plasma screens or as a decorative application such as for packaging materials.

The novel dispersions and processes are essential for the provision of optimized systems for the metallic coating of electrically non-conductive substrates, in particular using Leitlacken- or dispersions, compared to known systems an improved combination of properties of low weight, good adhesion, dispersibility, flowability and high have electrical conductivity. With the dispersion according to the invention and the method, it is also possible to produce homogeneous and continuous metal layers on electrically non-conductive materials.

After the electroless and / or galvanic coating, the substrate can be further processed according to all steps known to those skilled in the art. For example, existing electrolyte residues can be removed from the substrate by rinsing and / or the substrate can be dried.

Claims

claims

1. dispersion for applying a metal layer on an electrically non-conductive substrate containing

b 0.1 to 30 wt .-% based on the total weight of components A, B, C and D carbon nanotubes as component B;

c from 0.1 to 70% by weight, based on the total weight of components A, B, C and D, of electrically conductive particles having an average particle diameter of from 0.01 to 100 μm as component C;

2. Dispersion according to claim 1, characterized in that it further comprises at least one of the components

e is from 0.1 to 20% by weight, based on the total weight of components A, B, C and D, of a dispersant component E; such as

f 0.1 to 40% by weight, based on the total weight of components A,

B, C and D of an additive F contains.

3. Dispersion according to claim 1 or 2, characterized in that the binder component A consists of a polymer or polymer mixture.

4. Dispersion according to one of claims 1 to 3, characterized in that the component B of single or multi-walled carbon nanotubes with a length in the range of 0.5 to 1000 microns and a diameter in the range of 0.002 to 0.5 microns consists.

5. Dispersion according to one of claims 1 to 4, characterized in that metal powder is used as component C.

6. A process for preparing a dispersion according to any one of claims 1 to 5 comprising the steps a ^' ) mixing the components A to C and at least part of the component D, and optionally E, F and further components and

b ^' ) dispersing the mixture.

7. A method for producing a metal layer on at least part of the surface of a non-electrically conductive substrate comprising the steps

a) at least partially applying a dispersion according to any one of claims 1 to 5 on the substrate;

b) at least partial drying and / or partial curing of the applied dispersion layer on the substrate; and

c) electroless and / or electrodeposition of a metal on the at least partially dried and / or at least partially cured dispersion layer to form a metal layer.

8. The method according to claim 7, characterized in that between the steps b) and c) a surface activation of the at least partially dried and / or cured dispersion layer is carried out.

9. The method according to claims 7 to 8, characterized in that in step a) the dispersion is structured or applied flat.

10. Substrate surface with at least partially having electrically conductive metal layer obtainable from the method according to one of claims 7 to 9.

1 1. Use of a substrate surface according to claim 10 for conducting electrical power, heat, as Dekormetalloberfläche, for shielding electromagnetic radiation and for magnetization.

12. Use according to claim 11 as a printed circuit board, RFID antenna, Transponderan- antenna or other antenna structure, seat heating, flat cable, foil conductor, contactless chip card, printed conductors in solar cells or in LCD or plasma screens or for the production of electroplated products in any Shape.

13. Use of a dispersion according to one of claims 1 to 5 for applying a metal layer.