EP2033501A1 - Method for producing electrically conductive surfaces on a carrier - Google Patents

Abstract

Method for producing electrically conductive, structured or whole-area surfaces on a carrier, in which a first step involves applying a structured or whole-area base layer to the carrier with a dispersion containing electrically conductive particles in a matrix material, a second step involves at least partly curing or drying the matrix material, a third step involves uncovering the electrically conductive particles by at least partly breaking up the matrix, and a fourth step involves forming a metal layer on the structured or whole-area base layer by means of electroless or electrolytic coating.

Description

Process for the production of electrically conductive surfaces on a support

The invention relates to a method for the production of electrically conductive, structured or full surface surfaces on a support.

The method according to the invention is suitable, for example, for producing printed conductors on printed circuit boards, RFID antennas, transponder antennas or other antenna structures, chip card modules, flat cables, seat heaters, film conductors, printed conductors in solar cells or in LCD or plasma picture screens or galvanically coated products in any desired form. Also, the method is useful for making decorative or functional surfaces on products that can be used, for example, to shield from electromagnetic radiation, to conduct heat, or to package. Finally, thin metal foils or one or two-sided metal-clad polymer carriers can also be produced by the process.

At present, structured metal layers are produced on a carrier body, for example, by first applying a structured adhesive layer to the carrier body. At this structured adhesive layer, a metal foil or a metal powder is fixed. Alternatively, it is also known to apply a metal foil or a metal layer over the entire surface of a carrier body made of a plastic material and to press with the aid of a structured, heated stamp against the carrier body and to fix it by its subsequent curing. The structuring of the metal layer takes place by mechanical removal of the regions of the metal foil or of the metal powder which are not connected to the adhesive layer or to the carrier body. Such a method is described for example in DE-A 101 45 749.

Another method for producing conductive structures on a support is known from WO-A 2004/049771. Here, first, a surface of the carrier is at least partially covered with conductive particles. Subsequently, a passivation layer is applied to the particle layer formed by the conductive particles. The passivation layer is formed as a negative image of the conductive structure. Finally, in the regions not covered by the passivation layer, the conductive structure is formed. The conductive structure acts, for example, by electroless and / or galvanic coating.

A disadvantage of this method known from the prior art is that the carrier is in each case initially covered over the full area with a metal foil or an electrically conductive powder. is covered. This requires a large amount of material and then a complex process to remove the metal again or only to continue to coat the areas that are to form the electrically conductive structure.

DE-A 1 490 061 relates to a method for producing printed circuits, in which an adhesive in the form of the structure of the conductor tracks is first applied to a carrier. The application of the adhesive takes place for example by screen printing. Subsequently, a metal powder is applied to the adhesive. The excess metal powder, d. H. the metal powder, which does not adhere to the adhesive layer, is then removed again. Finally, the electrically conductive tracks are produced by a galvanic coating.

A method in which a base support substrate is already provided with conductive particles and then the part of the base support substrate, which is not intended to contain an electrically conductive surface is passivated by a printing process, is known for example from DE-A 102 47 746. According to this document, after passivation, the part of the surface which has not been passivated is activated, for example, by a galvanic coating.

WO 83/02538 discloses a method for producing electrical conductor tracks on a carrier. For this purpose, a mixture of a metal powder and a polymer is first applied to the carrier in the form of the conductor tracks. Subsequently, the polymer is cured. In a next step, a part of the metal powder is replaced by a more noble metal by an electrochemical reaction. Finally, an additional metal layer is applied by galvanization.

Disadvantage of this method is that an oxide layer can form on the electrically conductive particles. This oxide layer increases the resistance. In order to be able to carry out a galvanic coating, it is necessary first to remove the oxide layer.

Further disadvantages of the processes known from the prior art are the poor adhesion and the lack of homogeneity and patency of the metal layer deposited by electroless or galvanic metallization. This is mostly due to the fact that the electrically conductive particles are embedded in a matrix material and therefore are only exposed to a small extent on the surface and thus only a small part of these particles for electroless and / or galvanic metallization Available. This is especially problematic when using very small particles (particles in the micrometer to nanometer range). The formation of a homogeneous continuous metal coating is therefore very difficult or even impossible to realize, so that the process reliability is not given. By an existing oxide layer on the electrically conductive particles, this effect is even enhanced.

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. also because 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.

The object of the invention is to provide an alternative method by which electrically conductive, structured or full-surface surfaces can be produced on a carrier, in which these surfaces are homogeneous and continuously electrically conductive.

The object is achieved by a method for the production of electrically conductive, structured or full surface surfaces on a support, which comprises the following steps:

a) applying a structured or full-surface base layer to the support with a dispersion containing electrically conductive particles in a matrix material,

b) at least partial curing and / or drying of the matrix material,

c) at least partially exposing the electrically conductive particles to the surface of the base layer by at least partially ablating the matrix,

d) forming a metal layer on the base layer by electroless and / or electroplating.

As a carrier to which the electrically conductive, structured or full-surface surface is applied, for example, rigid or flexible carrier are suitable. Preferably, the carrier is not electrically conductive. This means that the resistivity is more than 10 ⁹ Ohm x cm is. Suitable carriers are, for example, reinforced or unreinforced polymers, as are commonly used for printed circuit boards. 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 cristal 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, cyanate esters, bismaleimide-triazine resins, nylon, vinyl ester resins, polyesters, polyester resins, polyamides, polyanilines, phenolic resins, polypyrroles, polyethylene naphthalate (PEN), polymethylmethacrylate, polyethylenedioxythiophenes, phenolic resin-coated aramid paper, polytetrafluoroethylene (PTFE), melamine resins, silicone resins, fluororesins, Allylated polyphenylene ether (APPE), polyetherimide (PEI), polyph enylene 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), Styrolac- rylnitrile (SAN) and mixtures (blends) of two or more of the above polymers, which may be 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 below under the matrix material can also be used. Also suitable are other substrates which are likewise customary in the printed circuit board industry.

Furthermore, suitable substrates composites, foam-like polymers, polystyrene ^®, styrodur ^®, polyurethanes (PU), ceramic surfaces, textiles, paperboard, cardboard, paper, polymer coated paper, wood, mineral materials, silicon, glass, plant tissue and animal tissue.

The carrier can be both rigid and flexible.

In a first step, the structured or full-surface base layer with a dispersion containing electrically conductive particles in a matrix material is applied to the support. The electrically conductive particles may be particles of any geometry made of any electrically conductive material, of mixtures of different electrically conductive materials or of mixtures of electrically conductive and non-conductive materials. Suitable electrically conductive materials are, for example Carbon, for example in the form of carbon black, graphite or carbon nanotubes, electrically conductive metal complexes, conductive organic compounds or conductive polymers 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, zinc, carbon and mixtures thereof.

The electrically conductive particles preferably have an average particle diameter of from 0.001 to 100 μm, preferably from 0.005 to 50 μm and particularly preferably from 0.01 to 10 μm. The average particle diameter can be determined by means of laser diffraction measurement, for example on a Microtrac X100 device. The distribution of the particle diameter depends on their production method. Typically, the diameter distribution has only one maximum, but several maxima are also possible.

The surface of the electrically conductive particle can be provided at least partially with a coating ("coating"). Suitable coatings may be inorganic (for example SiO ₂ , phosphates) or organic in nature. Of course, the electrically conductive particles may also be coated with a metal or metal oxide. Also, the metal may be in partially oxidized form.

If two or more different metals are to form the electrically conductive particles, this can be done by mixing these metals. It is particularly preferred if the metals are selected from the group consisting of aluminum, iron, copper, nickel and zinc.

However, the electrically conductive particles 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 the electrically conductive particles contain two different alloys.

In addition to the selection of the electrically conductive particles, the shape of the electrically conductive particles has an influence on the properties of the dispersion after a coating. With regard to the shape, numerous variants known to the person skilled in the art are possible. The shape of the electrically conductive particles may be, for example, acicular, cylindrical, plate-shaped or spherical. These particle shapes represent idealized forms, where when the actual shape, for example due to production, more or less strongly deviate from this. For example, drop-shaped particles in the context of the present invention are a real deviation of the idealized spherical shape.

Electrically conductive particles having various particle shapes are commercially available.

If mixtures of electrically conductive particles are used, the individual mixing partners can also have different particle shapes and / or particle sizes. It is also possible to use mixtures of only one type of electrically conductive particles having different particle sizes and / or particle shapes. In the case of different particle shapes and / or particle sizes, the metals aluminum, iron, copper, nickel and zinc and carbon are also preferred.

As already stated above, the electrically conductive particles in the form of their powders can be added to the dispersion. Such powders, for example metal powders, are common commercial products or can be easily prepared by known methods, such as by electrolytic deposition or chemical reduction from solutions of metal salts or by reduction of an oxidic powder, for example by hydrogen, by spraying or atomizing a molten metal, especially in cooling media , for example, gases or water. Preference is given to the gas and water atomization and the reduction of metal 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 the case of iron, in addition to gas and water atomization, the carbonyl iron powder process is preferred for the production of carbonyl iron powder. This is done by thermal decomposition of iron pentacarbonyl. This is described, for example, in Ullman's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A14, page 599. The decomposition of the iron pentacarbonyl can be carried out, for example, at elevated temperatures and elevated pressures in a heatable decomposer comprising a tube made of a refractory material such as quartz glass or V2A steel in a preferably vertical position, that of a heater, for example consisting of heating baths, heating wires or surrounded by a heating medium flows through the heating jacket.

Platelet-shaped electrically conductive particles can be controlled by optimized conditions in the production process or be obtained afterwards by mechanical treatment, for example by treatment in a stirred ball mill. Based on the total weight of the dried coating, the proportion of electrically conductive particles in the range of 20 to 98 wt .-%. A preferred range of the proportion of the electrically conductive particles is from 30 to 95% by weight, based on the total weight of the dried coating.

Suitable matrix materials are, for example, binders with pigment-affine anchoring 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 do not have to be, chemically or physically curing, for example air-hardening, radiation-curing or temperature-curing.

Preferably, the matrix material is a polymer or polymer mixture.

Preferred polymers as the matrix material are ABS (acrylonitrile-butadiene-styrene); ASA (acrylonitrile-styrene-acrylate); acrylated acrylates; alkyd resins; Alkylvinylacetate; Alkylene vinyl acetate copolymers, especially methylene vinyl acetate, ethylene vinyl acetate, butylene vinyl acetate; Alkylenvinylchlorid copolymers; amino resins; Aldehyde and ketone resins; Cellulose and cellulose derivatives, in particular hydroxyalkylcellulose, cellulose esters, such as acetates, propionates, butyrates, 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; 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 AG); polyester; polyether; polyethylene; Polyethylenthiophene; polyethylene naphthalates; Polyethylene terephthalate (PET); Polyethylene terephthalate glycol (PETG); polypropylene; Polymethyl methacrylate (PMMA); Polyphenylene oxide (PPO); Polystyrenes (PS), polytetrafluoroethylene (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 Solution and as dispersion and their copolymers, polyacrylates and polystyrene copolymers; Polystyrene (impact or not impact modified); Polyurethanes, non-crosslinked or crosslinked with isocyanates; polyurethane acrylates; Styrene-acrylic copolymers; Styrene-butadiene block copolymers (for example, Styroflex ^® or Styrolux ^® from BASF AG, K-Resin ™ CPC); Proteins, such as casein; SIS; Triazine resin, bismaleimide-triazine resin (BT), cyanate ester resin (CE), allied polyphenylene ether (AP-PE). Furthermore, mixtures of two or more polymers can form the matrix material.

Particularly preferred polymers as matrix material 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 novolaks. 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, the matrix material for the dispersion is preferably thermally 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.

Based on the total weight of the dry coating, the proportion of the organic binder component is from 0.01 to 60% by weight. Preferably, the proportion is 0.1 to 45 wt .-%, more preferably 0.5 to 35 wt .-%.

In order to be able to apply the dispersion containing the electrically conductive particles and the matrix material to the support, the dispersion may furthermore be admixed with a solvent or a solvent mixture in order to adjust the viscosity of the dispersion which is suitable for the respective application method. 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 alcohol). acetate, isobutyl acetate, isopropyl acetate, 3-methylbutanol), alkoxy alcohols (for example methoxypropanol, methoxybutanol, ethoxypropanol), alkylbenzenes (for example ethylbenzene, isopropylbenzene), butylglycol, butyldiglycol, alkylglycolacetates (for example butylglycol acetate, butyldiglycolacetate), 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 ethers, DBE (dibasic esters), 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, 2-butanone, cyclohexanone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK)), methyl diglycol, methylene chloride, methylene glycol, methyl glycol acetate, methylphenol (ortho -, meta-, para-cresol), pyrrolidone (zum Example, N-methyl-2-pyrrolidone), propylene glycol, propylene carbonate, carbon tetrachloride, toluene, trimethylolpropane (TMP), aromatic hydrocarbons and mixtures, aliphatic hydrocarbons and mixtures, alcoholic 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 (cf. Ethyl acetate, butyl acetate, butyl glycol acetate, butyl diglycol acetate, diglycol alkyl ether acetates, dipropylene glycol alkyl 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 solvent are particularly preferred.

In the case of liquid matrix materials (eg liquid epoxy resins, acrylate esters), the respective viscosity can alternatively also be adjusted via the temperature during the application, or via a combination of solvent and temperature The dispersion may further contain a dispersant component. 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.

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 in the

Generally referred to as soaps. Usually they are called sodium, potassium or

Ammonium salts used. 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 sulfates, for example sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali metal salts of C ₂ -C ₆ -

Paraffin sulfonic acids. Furthermore, sodium dodecylbenzenesulfonate and sodium dioctylsulfonosuccinate are suitable.

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

In particular, according to the invention, nonionic surfactants can be used as the dispersant component. 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 are, for example, polyethylene oxide or polypropylene oxide-based substances, such as Pluronic® or 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 1000 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 alkoxides, such as sodium methoxide, 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 antimony pentachloride, boron fluoride etherate or bleaching earth, as catalysts of one or more alkylenoxides 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. Possible starter molecules are, for example: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid or terephthalic acid, aliphatic or a- romantic, optionally N-mono-, N ₁ 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.

Also suitable as starter molecules are: alkanolamines, for example ethanolamine, N-methyl- and N-ethylethanolamine, dialkanolamines, for example diethanolamine, N-methyl- and N-ethyldiethanolamine, and trialkanolamines, for example triethanolamine, and ammonia. Preference is given to using polyhydric, in particular dihydric, trihydric or higher 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 the dispersant component are esterified polyalkylene glycols, for example the mono-, di-, tri- or polyesters of the stated polyalkylene glycols obtained by reaction of the terminal OH groups of said polyalkylene glycols with organic acids, preferably adipic acid or terephthalic acid, in a manner known per se can be produced. 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 alkylglycosides obtained by reaction of fatty alcohols with sugars. Sugar esters are obtained by reacting sugars with fatty acids. The sugar, fatty alcohols and fatty acids necessary for the preparation 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 the sorbitan 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 dilaurate, sorbitan trilaurate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan monopalmitate, sorbitan palmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate and sorbitan sesquioleate, a mixture of sorbitan mono - and diesters of oleic acid. Possible dispersants 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, tri-stearate, oleate, trioleate, in particular polyethoxysorbitan, which for example as Tween ^® 60, the ICI Amer- rica Inc. (described for example in CD Römpp Chemie Lexikon - Version 1.0 , Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Tween ^® ").

The use of polymers as dispersants is also possible.

The dispersant may be used in the range of 0.01 to 50% by weight based on the total weight of the dispersion. The proportion is preferably 0.1 to 25% by weight, more preferably 0.2 to 10% by weight.

Furthermore, the dispersion of the invention may contain a filler component. This can consist of one or more fillers. Thus, the filler component of the metallizable composition may contain fibrous, layered or particulate fillers or mixtures thereof. These are preferably commercially available products, such as carbon and mineral fillers.

Furthermore, fillers or reinforcing materials such as glass powder, mineral fibers, whiskers, aluminum hydroxide, metal oxides such as alumina or iron oxide, mica, quartz powder, calcium carbonate, barium sulfate, titanium dioxide or wollastonite can be used.

Furthermore, further additives, such as thixotropic agents, for example silica, silicates, such as aerosils or bentonites 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, conductive polymer particles, can be used. The proportion of the filler component based on the total weight of the dry coating is preferably 0.01 to 50 wt .-%. Further preferred are 0.1 to 30 wt .-%, particularly preferably 0.3 to 20 wt .-%.

Furthermore, processing aids and stabilizers such as UV stabilizers, lubricants, corrosion inhibitors and flame retardants can be present in the dispersion according to the invention. Usually, their proportion based on the total weight of the dispersion 0.01 to 5 wt .-%. Preferably, the proportion is 0.05 to 3 wt .-%.

After the application of the structured or full-surface base layer on the support with the dispersion containing the electrically conductive particles in the matrix material, and the drying or hardening of the matrix material, the particles are for the most part within the matrix, so that no continuous electrical conductive surface was generated. To produce the continuous electrically conductive surface, it is necessary to coat the structured or full-surface base layer applied to the carrier with an electrically conductive material. This coating is generally carried out by electroless and / or galvanic metallization.

In order to be able to electrolessly and / or electrolytically coat the structured or full-surface base layer, it is first necessary to at least partially dry or cure the structured or full-surface base layer applied with the dispersion. The drying or hardening of the structured or full-surface area is carried out by customary methods. For example, the matrix material can be cured chemically, for example by polymerization, polyaddition or polycondensation of the matrix material, for example by UV radiation, electron radiation, microwave radiation, IR radiation or temperature, or by purely physical means by evaporation of the solvent are dried. A combination of drying by physical and chemical means is possible. After at least partial drying or hardening, according to the invention, the electrically conductive particles contained in the dispersion are at least partially exposed in order to obtain already electrically conductive nuclei at which the metal ions form during the subsequent electroless and / or galvanic metallization to form a metal layer can separate. If the particles consist of materials which oxidize easily, it may additionally be necessary to at least partially remove the oxide layer beforehand. Depending on the implementation of the method, for example when using acidic electrolyte solutions, the removal of the oxide layer can already take place simultaneously with the onset of metallization without the need for an additional process step. An advantage of exposing the particles prior to the electroless and / or galvanic metallization is that, by exposing the particles, an approximately 5 to 10% by weight lower proportion of electrically conductive particles must be present in the coating in order to produce a continuous electrically conductive layer Surface as it does when the particles are not exposed. Further advantages are the homogeneity and consistency of the coatings produced and the high process reliability.

The exposure of the electrically conductive particles can be done either mechanically, for example by brushing, grinding, milling, sand blasting or irradiation with supercritical carbon dioxide, physically, for example by heating, laser, UV light, corona or plasma discharge, or chemically. In the case of a chemical exposure, a suitable chemical or chemical mixture is preferably used for the matrix material. In the case of a chemical exposure, either the matrix material can be at least partially dissolved and washed down by a solvent on the surface or can be at least partially destroyed by means of suitable reagents, the chemical structure of the matrix material, whereby the electrically conductive particles are exposed. Reagents that swell the matrix material are also suitable for exposing the electrically conductive particles. The swelling results in cavities in which the metal ions to be deposited can penetrate from the electrolyte solution, as a result of which a larger number of electrically conductive particles can be metallized. The adhesion, the homogeneity and the continuity of the subsequently electrolessly and / or electrodeposited metal layer are significantly better than in the methods described in the prior art. Due to the higher number of exposed electrically conductive particles, the process speed during metallization is also considerably higher, which allows additional cost advantages to be achieved.

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 exposure of the electroconductive particles is preferably carried out 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 manganate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen, oxygen in the presence of catalysts such as, 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 ferrate, dichromate / sulfuric acid, chromic acid in sulfuric acid. or in acetic acid or in acetic anhydride 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, such as, for example, chlorates or bromates or iodates, salts of halogenated acids, for example sodium periodate or sodium perchlorate, sodium perborate, dichromates, for example sodium dichromate, salts of persulphuric acid, such as potassium peroxodisulphate, Potassium peroxymonosulfate, pyridinium chlorochromate, salts of hypohalogenic acids, for example sodium hypochlorite, dimethyl sulfoxide in the presence of electrophilic reagents, tert-butyl hydroperoxide, 3-chloroperbenzoic acid, 2,2-dimethylpropanal, des-Martin periodinane, oxalyl chloride, urea-hydrogen peroxide adduct , Urea peroxide, 2-iodoxybenzoic acid, potash peroxymonosulphate, 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, trifluoroacetic 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-methylmorpholine N-oxide, percarbonates, for example sodium or potassium percarbonate, perborates, for example sodium or potassium perborate; Persulfates, for example sodium or potassium persulfate; sodium, potassium and ammonium peroxodi- and monosulfates, sodium hypochlorite, urea-hydrogen peroxide adducts, salts of oxohalogenic acids, such as chlorates or bromates or iodates, salts of haloperacids, such as Sodium periodate or sodium perchlorate, tetrabutylammonium peroxydisulfate, 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 electrically conductive particles in a matrix material containing, for example, ester structures, such as polyester resins, polyester acrylates, polyether acrylates, polyester urethanes, it is preferred 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 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 electrically conductive 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. 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.

Furthermore, it is also possible to expose the electrically conductive particles by a mechanical method. Suitable mechanical methods include, for example, brushing, grinding, abrasive polishing, or jet blasting, blasting, or supercritical carbon dioxide blasting. By such a mechanical process, in each case the uppermost layer of the cured printed structured base layer is removed. As a result, the electrically conductive particles contained in the matrix material are exposed.

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 cured dispersion by the pressure jetting with the water jet, the water jet preferably contains small solid particles, for example pumice flour (Al 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.

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

Suitable mechanical methods for removing the oxide layer from the electrically conductive particles are generally the same as the mechanical methods of exposing the particles.

In order that the dispersion which is applied to the support adheres firmly to the support, in a preferred embodiment it is cleaned before the application of the structured or full-surface base layer by a dry process, a wet-chemical process and / or a mechanical process. In particular, it is also possible by means of the wet-chemical and the mechanical method to roughen the surface of the carrier so that the dispersion adheres better to it. As a wet-chemical method is particularly suitable rinsing the carrier with acidic or alkaline reagents or with suitable solvents. Also water in conjunction with ultrasound can be used. Suitable acidic or alkaline reagents are, for example, hydrochloric acid, sulfuric acid or nitric acid, phosphoric acid or sodium hydroxide solution, potassium hydroxide solution or carbonates, such as potassium carbonate. Suitable solvents are the same as they may be included in the dispersion for applying the base layer. Preferred solvents are alcohols, ketones and hydrocarbons, which are to be selected depending on the carrier material. Also, the oxidizing agents that have already been mentioned in the activation, can be used.

Mechanical methods of cleaning the substrate prior to applying the patterned or full-surface base layer are generally the same as they can be used to expose the electrically conductive particles and remove the oxide layer of the particles.

To remove dust and other particles that may affect the adhesion of the dispersion on the support, as well as for roughening the surface are particularly dry cleaning methods. These are, for example, dedusting by means of brushing and / or deionized air, corona discharge or low-pressure plasma and particle removal by means of rollers and / or rolls provided with an adhesive layer. By corona discharge and low-pressure plasma, the surface tension of the substrate is selectively increased, the substrate surface is cleaned of organic residues and thus improves both the wetting with the dispersion and the adhesion of the dispersion.

Preferably, the structured or full-surface base layer is printed with the dispersion by any printing method on the support. The printing process used to print the patterned surface is, for example, a web or sheet fed printing process, such as screen printing, gravure, flexo, letterpress, pad printing, ink jet printing, the Lasersonic® process as described in DE10051850, or offset printing. However, it is also possible to use any further printing method known to the person skilled in the art. It is also possible to apply the surface by another common and well-known coating method. Such coating methods are, for example, casting, brushing, knife coating, brushing, spraying, dipping, rolling, tumbling, fluidized bed or the like. The layer thickness of the structured or full surface area produced by the printing or the coating method preferably varies between 0.01 and 50 μm, more preferably between 0.05 and 25 μm and particularly preferably between 0.1 and 15 μm. The layers can be applied both over the entire surface as well as structured.

Depending on the printing process, different fine structures can be imprinted.

Preferably, the dispersion is stirred or pumped in a storage container prior to application to the carrier. By stirring and / or pumping a possible sedimentation of the particles contained in the dispersion is prevented. Furthermore, it is also advantageous if the dispersion is heated in the reservoir. This makes it possible to achieve an improved printed image of the base layer on the carrier, since a constant viscosity can be set by the tempering. The temperature control is particularly necessary when the dispersion is heated, for example, by the stirring and / or pumping due to the energy input of the stirrer or the pump and thereby changes the viscosity thereof.

To increase the flexibility and cost reasons, digital printing processes, for example inkjet printing, LaserSonic® are particularly suitable in the case of a print application. These processes generally eliminate the cost of producing printing stencils, such as printing rolls or screens, as well as their constant change when several different structures need to be printed one behind the other. In the digital The new printing process can be converted to a new design without any need for retooling or downtime.

In the case of application of the dispersion by means of the inkjet process, it is preferred to use electrically conductive particles having a maximum size of 15 μm, more preferably 10 μm, in order to prevent clogging of the inkjet nozzles. To avoid sedimentation in the inkjet head, the dispersion can be pumped by means of a pumped circulation, so that the particles do not settle. Furthermore, it is advantageous if the system can be heated to adjust the viscosity of the dispersion verdruckbar.

In addition to the one-sided application of the dispersion to the carrier, it is also possible with the method according to the invention to provide the carrier at its top and bottom with an electrically conductive structured or full-surface base layer. With the aid of plated-through holes, the structured or full-surface electrically conductive base layers on the top side and the underside of the carrier can be electrically connected to one another. For the via, for example, a wall of a bore in the carrier is provided with an electrically conductive surface. In order to produce the plated-through hole, it is possible, for example, to form bores in the support, on the wall of which the dispersion which contains the electrically conductive particles is applied during the printing of the structured or full-surface base layer. In a sufficiently thin carrier, it is not necessary to coat the wall of the bore with the dispersion, as in the electroless and / or electroplating with a sufficiently long coating time also within the hole forms a metal layer by the top and Grow together underside of the carrier into the hole growing metal layers, whereby the electrical connection of the electrically conductive structured or full-surface surfaces of the top and bottom of the carrier is formed. In addition to the method according to the invention, it is also possible to use other methods known from the prior art for metallizing bores and / or blind holes.

In order to obtain a mechanically stable structured or full-surface base layer on the support, it is preferred that the dispersion with which the structured or full-surface base layer is applied to the support, at least partially cures after application. Depending on the matrix material, hardening takes place as described above, for example by the action of heat, light (UVA / is) and / or radiation, for example infrared radiation, electron radiation, gamma radiation, X-radiation, microwaves. To initiate the curing reaction, it may be necessary to use a suitable be added. Curing can also be achieved by combining various methods, for example by combining UV radiation and heat. The combination of the curing processes can be carried out simultaneously or sequentially. For example, UV radiation can only be used to first harden the layer so that the formed structures no longer flow apart. Thereafter, the layer can be cured by exposure to heat. The heat can be done directly after the UV-curing and / or after the galvanic metallization. After at least partial curing - as already described above - in a preferred variant, the electrically conductive particles are at least partially exposed. In order to produce the continuous electrically conductive surface, after exposing the electrically conductive particles, at least one metal layer is formed on the structured or full-surface base layer by electroless and / or galvanic coating. The coating can be carried out by any method known to those skilled in the art. Also, any conventional metal coating can be applied by the coating method. In this case, the composition of the electrolyte solution used for the coating depends on which metal the electrically conductive structures are to be coated on the substrate. In principle, all metals which are nobler or equally noble as the most noble metal of the dispersion can be used for electroless and / or electroplating. Typical metals which are deposited by electroplating on electrically conductive surfaces are, for example, gold, nickel, palladium, platinum, silver, tin, copper or chromium. The thicknesses of the one or more deposited layers are within the usual range known to the person skilled in the art and are not essential to the invention.

Suitable electrolyte solutions which can be used to coat electrically conductive structures are those skilled in the art, for example, Werner Jillek, Gustl Keller, Manual of printed circuit board technology. Eugen G. Leuze Verlag, 2003, Volume 4, pages 332-352 known.

For coating the electrically conductive structured or full surface on the carrier, the carrier is first supplied to the bath with the electrolyte solution. The carrier is then conveyed through the bath, wherein the electrically conductive particles contained in the previously applied structured or full-surface base layer are contacted with at least one cathode. In this case, any customary, known in the art, suitable cathode can be used. As long as the cathode contacts the structured or solid surface, metal ions are deposited from the electrolyte solution to form a metal layer on the surface. A suitable device, in which the structured or full-surface electrically conductive base layer is galvanically coated, generally comprises at least one bath, one anode and one cathode, wherein the bath contains an electrolyte solution containing at least one metal salt. From the electrolyte solution, metal ions are deposited on electrically conductive surfaces of the substrate to form a metal layer. The at least one cathode is for this purpose brought into contact with the base layer of the substrate to be coated, while the substrate is conveyed through the bath.

For galvanic coating, all electroplating processes known to those skilled in the art are suitable. Such electroplating processes are, for example, those in which the cathode is formed by one or more rollers which contact the material to be coated. The cathodes can also be designed in the form of segmented rolls, in which in each case at least the segment of the roll, which is in communication with the substrate to be coated, is connected cathodically. In the case of segmented rolls, in order to remove metal deposited on the roll, it is possible to anodically switch the segments which do not contact the base layer to be coated, whereby the metal deposited thereon is deposited again into the electrolytic solution.

In one embodiment, the at least one cathode comprises at least one band with at least one electrically conductive portion, which is guided around at least two rotatable shafts. The waves are carried out with a suitable, matched to the respective substrate cross-section. Preferably, the waves are cylindrically shaped and may for example be provided with grooves in which the at least one band runs. For electrically contacting the band, at least one of the shafts is preferably connected in a cathodic manner, wherein the shaft is designed in such a way that the current is transmitted from the surface of the shaft to the band. If the shafts are provided with grooves in which the at least one belt runs, the substrate can be contacted simultaneously via the shafts and the belt. However, only the grooves can be electrically conductive and the regions of the waves between the grooves can be made of an insulating material in order to avoid that the substrate is also electrically contacted via the waves. The power supply of the waves takes place for example via slip rings, but it can also be used any other suitable device with which power can be transmitted to rotating shafts.

Because the cathode comprises at least one band with at least one electrically conductive section, substrates with short electrically conductive structures, especially in the transport direction of the substrate, can also be provided with a sufficiently thick layer. Layering be provided. This is possible because, as a result of the design of the cathode as a band, even short electrically conductive structures are in contact with the cathode for a longer time.

In order to coat also the regions of the electrically conductive structure on which the band designed as a cathode rests for contacting, preferably at least two bands are arranged offset one behind the other. The arrangement is generally such that the second band, which is arranged offset behind the first band, contacts the electrically conductive structure in the region on which the metal was deposited during the contacting with the first band. A greater thickness of the coating can be achieved by designing more than two bands in succession.

A shorter construction, viewed in the direction of transport, can be achieved in that successive, staggered bands are guided over at least one common shaft.

The at least one band can, for example, also have a network structure so that only small areas of the electrically conductive structures to be coated on the substrate are covered by the band. The coating takes place in each case in the brackets of the net. In order to coat the electrically conductive structures in the areas in which rests the network, it is also advantageous in the case that the bands are formed in the form of a network structure, at least two bands arranged one behind the other.

It is also possible that the at least one band comprises alternating conductive and non-conductive sections. In this case, it is possible to additionally guide the band around at least one anodically connected wave, wherein care should be taken that the length of the conductive portions is smaller than the portion between a cathodic and an adjacent anodically connected wave. In this way, the regions of the ribbon which are in contact with the coated substrate are switched cathodically, and the regions of the ribbon which are not in contact with the substrate become anodic. The advantage of this circuit is that metal which deposits on the tape during the cathodic circuit of the tape is removed during the anodic circuit. In order to remove all the metal deposited on the tape while it was cathodically connected, the anodized region is preferably longer or at least as long as the cathodically connected region. On the one hand, this can be achieved in that the anodically connected shaft has a larger one On the other hand, it is also possible, with the same or smaller diameter of the anodically connected waves, to provide thereof at least as many as cathodically connected waves, wherein the distance of the cathodically connected waves and the distance of the anodischgeschalteten WeI- len preferably the same size.

Alternatively, it is also possible for the cathode to comprise at least two disks rotatably mounted on one shaft in each case instead of the belts, the disks meshing with one another. This also makes it possible that short electrically conductive structures, especially in the transport direction of the substrate, can be provided with a sufficiently thick and homogeneous coating. The disks are generally designed in a cross-section adapted to the respective substrate. The disks preferably have a circular cross section. The waves can have any cross section. Preferably, however, the shafts are cylindrical.

In order to be able to coat structures that are wider than two adjacent disks, several disks are arranged next to one another on each shaft, depending on the width of the substrate. In each case, a sufficient distance is provided between the individual disks, in which the disks of the following shaft can engage. In a preferred embodiment, the distance between two disks on a shaft corresponds at least to the width of a disk. This makes it possible that in the distance between two discs on a shaft, a disc can engage another shaft.

The power supply of the discs takes place for example via the shaft. This makes it possible, for example, to connect the shaft outside the bath with a voltage source. This connection is generally made via a slip ring. However, any other connection is possible with which a voltage transfer from a stationary voltage source is transmitted to a rotating element. In addition to the power supply via the source, it is also possible to supply the contact disks with electricity over their outer circumference. For example, sliding contacts, such as brushes, may be in contact with the contact disks on the side facing away from the substrate.

In order to supply the disks, for example, with electricity via the shafts, the shafts and the disks are preferably made at least in part from an electrically conductive material. In addition, however, it is also possible to manufacture the shafts from an electrically insulating material and the power supply to the individual disks, for example by electrical conductors, such as wires to realize. In this case, then the individual wires are each connected to the contact discs, so that the contact discs are supplied with voltage.

In a preferred embodiment, the discs distributed over the circumference individual, electrically isolated from each other sections. The sections which are electrically insulated from one another are preferably switchable both cathodically and anodically. This makes it possible that a portion which is in contact with the substrate, is switched cathodically, and as soon as it is no longer in contact with the substrate is switched a nodal. As a result, deposited metal is removed during the cathodic circuit on the portion during the anodic circuit. The voltage supply of the individual segments generally takes place via the shaft.

In addition to the removal of the deposited on the shaft and the discs, or the bands, metal by reversing the waves or bands other cleaning variants, for example, a chemical or mechanical cleaning, possible.

The material from which the electrically conductive parts of the discs or bands are made, is preferably an electrically conductive material, which does not pass into the electrolyte solution during operation of the device. Suitable materials include metals, graphite, conductive polymers such as polythiophenes or metal / plastic composites. Preferred materials are stainless steel and / or titanium.

It is also possible to connect several baths with different electrolyte solutions in succession in order to deposit a plurality of different metals on the base layer to be coated in this way. Furthermore, it is also possible first to deposit electrolessly metal and then electrolessly on the base layer. In this case, different metals or even the same metal can be deposited by the electroless and the electrolytic deposition.

The galvanic coating apparatus may further be provided with a device with which the substrate can be rotated. The axis of rotation of the device, with which the substrate can be rotated, is arranged perpendicular to the surface of the substrate to be coated. By rotating electrically conductive structures, which are initially seen in the transport direction of the substrate, wide and short, aligned so that they are seen after turning in the transport direction narrow and long. The layer thickness of the metal layer deposited on the electrically conductive structure by the method according to the invention depends on the contact time, which results from the passage speed of the substrate through the device and the number of cathodes positioned behind one another, and the current intensity with which the device is operated. A higher contact time can be achieved, for example, by connecting several devices according to the invention in at least one bath in succession.

For example, in order to allow simultaneous coating of the top and bottom base layers, two rollers or two shafts with the disks or two belts mounted thereon may be arranged so that the substrate to be coated can be passed between them.

If flexible films are to be coated whose length exceeds the length of the bath - so-called endless films, which are initially unwound from a roll, passed through the device for electroplating and then wound up again - this can also be zigzag-shaped, for example or in the form of a meander to several devices for electroplating, which can then be arranged, for example, one above the other or next to each other, are passed through the bath.

The galvanic coating device may be equipped with any additional device known to those skilled in the art as needed. Such ancillary devices include, for example, pumps, filters, chemical feeders, roll-up and roll-down devices, etc.

To shorten the maintenance intervals, all methods of care of the electrolyte solution known to those skilled in the art can be used. Such care methods are, for example, systems in which the electrolyte solution regenerates itself.

The device according to the invention can also be operated, for example, in the pulse method known from Werner Jillek, Gustl Keller, Handbuch der Leiterplattentechnik, Eugen G. Leuze Verlag, Vol. 4, pages 192, 260, 349, 351, 352, 359.

The process according to the invention for the production of electrically conductive, structured or full surface surfaces on a support can be operated in a continuous, partially continuous or discontinuous manner. Also, it is possible that only individual Steps of the process are carried out continuously while other steps are carried out batchwise.

The method according to the invention is suitable, for example, for the production of printed conductors on printed circuit boards. Such circuit boards are, for example, those with multilayer

Internal and external layers, micro-via, chip-on-board, flexible and rigid 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 RFID antennas, transponder antennas or other antenna structures, chip card modules, flat cables, seat heaters, film conductors, printed conductors in solar cells or in LCD or plasma picture screens, capacitors, film capacitors, resistors, convectors, electrical fuses or for Her - Positioning of electroplated products in any form, such as one or two-sided metal-clad polymer carrier with a defined layer thickness, 3D molded interconnect devices or for the production of decorative or functional surfaces on products that, for example, to shield electromagnetic radiation, for Heat conduction or used as packaging. Furthermore, it is also possible to produce contact pads or contact pads or wirings on an integrated electronic component.

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, possible.

A use is further 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 application of the method according to the invention enables cost-effective production of metallized, even non-conductive substrates, in particular for use as switches and sensors, gas barriers or decorative parts, in particular decorative parts for motor vehicles, plumbing, toys, household and office use and packaging as well as slides. 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 using the method according to the invention (antennas, transmitters, RFID and transponder antennas, sensors, heating elements, anti-static (also for plastics), shielding, etc.).

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 method according to the invention can likewise 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 through-connection of the top and bottom side. This also applies if other substrates are used.

Furthermore, find the metallized articles according to the invention provided that they comprise magnetizable metals - application 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 in which a good thermal conductivity is advantageous, for example in films for seat heaters, floor heating and insulation materials.

Preferred uses of the surfaces metallized according to the invention are those in which the products thus produced are printed circuit boards, RFID antennas, transponder antennas, seat heaters, flat cables, 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.

After the galvanic coating, the substrate can be processed further in accordance with all steps known to the person skilled in the art. For example, existing electrolyte residues can be removed from the substrate by rinsing and / or the substrate can be dried. An advantage of the method according to the invention is that sufficient coating is possible even when using materials for the electrically conductive particles which oxidize easily.

Claims

claims

1. A process for the production of electrically conductive, structured or full surface surfaces on a support, comprising the following steps:

a) applying a structured or full-surface base layer to the support with a dispersion containing electrically conductive particles in a matrix material,

b) at least partial curing and / or drying of the matrix material,

c) at least partially exposing the electrically conductive particles by at least partially rupturing the cured or dried matrix,

d) forming a metal layer on the structured or full-surface base layer by electroless and / or electroplating.

2. The method according to claim 1, characterized in that the exposure of the electrically conductive particles in step c) takes place chemically, physically or mechanically.

3. The method according to claim 1 or 2, characterized in that the exposure of the electrically conductive particles in step c) is carried out with an oxidizing agent.

4. The method according to claim 3, characterized in that the oxidizing agent potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide or its adducts, a perborate, a percarbonate, a persulfate, a

Peroxodisulfate, sodium hypochlorite or a perchlorate.

5. The method according to claim 1, characterized in that the exposure of the electrically conductive particles in step c) by the action of substances that dissolve the matrix rixmaterial, attach and / or swell, takes place.

6. The method according to claim 5, characterized in that the substance which dissolve, causticize and / or swell the matrix material is an acidic or alkaline chemical or a chemical mixture or a solvent.

7. The method according to any one of claims 1 to 6, characterized in that before the electroless and / or galvanic coating of the structured or full-surface Base layer, an optional oxide layer is removed from the electrically conductive particles.

8. The method according to any one of claims 1 to 7, characterized in that the carrier before applying the structured or full-surface coating with the

Dispersion is purified by a dry process, a wet chemical process and / or a mechanical process.

9. The method according to claim 8, characterized in that the dry process is a dedusting by brushing and / or deionized air, low-pressure plasma, Corona discharge or particle removal by provided with an adhesive layer rolls or rollers, the wet-chemical process rinsing with an acidic or alkaline chemical or chemical mixture or a solvent, and the mechanical method is brushing, grinding, polishing or pressure blasting with an air or water jet possibly containing particles.

10. The method according to any one of claims 1 to 9, characterized in that the structured or full-surface base layer is applied by a coating method.

1 1. A method according to claim 10, characterized in that the coating method is a printing, casting rolling dipping or spraying.

12. The method according to any one of claims 1 to 1 1, characterized in that the dispersion is stirred or recirculated in a storage container prior to application.

13. The method according to any one of claims 1 to 12, characterized in that a structured or full-surface base layer is applied to the top and bottom of the carrier.

14. The method according to claim 13, characterized in that the structured and / or full-surface base layers are connected to each other on the top and bottom of the carrier by at least one via.

15. The method according to claim 14, characterized in that for Durchkontaktie- tion a wall of the at least one bore in the carrier is provided with an electrically conductive surface.

16. The method according to any one of claims 1 to 15, characterized in that the structured or full-surface base layer after application of the dispersion at least partially hardens or dries.

17. The method according to claim 16, characterized in that the curing or drying depending on the matrix material on chemical or physical

Paths or combinations of these ways.

18. The method according to any one of claims 1 to 17, characterized in that the electrically non-conductive material from which the carrier is made, a resin-impregnated tissue which is pressed into plates or rolls, or an unreinforced plastic film.

19. The method according to any one of claims 1 to 18 for the production of printed conductors on printed circuit boards, RFID antennas, transponder antennas or other Antennenstruktu- ren, smart card modules, flat cables, seat heaters, foil conductors, conductor tracks in

Solar cells or in LCD or plasma screens or for the production of electroplated products in any form.

20. The method according to any one of claims 1 to 18 for the production of decorative or functional surfaces on products that are used to shield electromagnetic radiation, for heat conduction or as packaging.

21. The method according to any one of claims 1 to 18 for the production of thin metal foils or one or two-sided metal-clad polymer supports.