EP2288649A1

EP2288649A1 - Dispersion for applying a metal layer

Info

Publication number: EP2288649A1
Application number: EP09761679A
Authority: EP
Inventors: Rene Lochtman; Norbert Wagner; Jürgen Kaczun; Jürgen PFISTER
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2008-06-09
Filing date: 2009-06-08
Publication date: 2011-03-02
Also published as: WO2009150116A1; CN102089371A; KR20110027727A; TWI470041B; JP2011525034A; US20110086231A1; BRPI0914908A2; US8633270B2; CA2727215A1; TW201005049A; JP5456028B2; CN102089371B

Abstract

The invention relates to a dispersion for applying a metal layer to an electrically non-conductive substrate, said dispersion containing an organic binder component, a metal component and a solvent component. The invention further relates to methods for producing said dispersion, to methods for producing an optionally structured metal layer using said dispersion and to the substrate surfaces obtained in said manner and the 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 first carried out by strong acids or bases, such as, for example, chromosulfuric acid. Subsequently, a coating of the plastic surface by solutions with suitable transition metal complexes takes place. These allow a metallization of the activated plastic surface.

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

DE-A 1 615 786, for example, 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 coatings 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 occur due to insufficient adhesion of the conductive layer to the plastic surface. DE-A 1 521 152 therefore proposes applying a conductive ink to the electrically nonconductive surface which contains a binder and finely divided iron and then applying a layer of silver or of copper without current to the conductive ink. After that, another layer can be applied without current or galvanically.

EP-B 200 772 describes the coating of an electrically non-conductive article by means of a fluid organic dye binder to achieve electromagnetic shielding at a frequency greater than 10 kHz. Here, a primary layer is first applied with the fluid organic colorant in which active metal particles are dispersed, and then a second layer of copper is electrolessly deposited on the primary layer and finally a third layer of an electroplated metal is applied to the second layer.

DE-A 199 45 400 describes inter alia a magnetic dispersion which is intended to contain a special binder and a magnetic or magnetizable material.

DE-A-10 2005 043 242 A1 relates to a dispersion for applying a metal layer on a non-conductive substrate, comprising an organic binder component, a metal component with different metals and / or metal particles and a solvent component.

In view of increased requirements, there remains a need to optimize the systems for the metallic coating of electrically non-conductive substrates, in particular to improve the adhesion, to ensure in subsequent processing steps and the use of sufficient functionality.

It is therefore an object of the present invention to provide a dispersion which makes it possible to apply a metal layer to an electrically nonconducting substrate, wherein, in particular, increased adhesion strength and / or layer homogeneity of the metal layer can be achieved.

The present invention relates to a dispersion for depositing a metal layer on an electrically non-conductive substrate

an organic binder component A a metal component B a solvent component C, characterized in that the organic binder component A consists essentially of

A1 is a polyvinyl chloride copolymer having hydroxyl groups and A2 is a polyurethane having hydroxyl groups.

A preferred embodiment is characterized in that component A1 is obtainable by polymerization of vinyl chloride with at least one hydroxy acrylate or vinyl acetate and subsequent at least partial hydrolysis and that A2 is a hydroxyl-containing linear polyurethane. Component A1 in one embodiment contains vinyl acetate and vinyl alcohol recurring units. In another embodiment, A1 contains acrylate and vinyl alcohol units

A further preferred embodiment is characterized in that the components A1 and A2 make up at least 80% by weight of the binder component A.

A further preferred embodiment is characterized in that one part by weight of A2 accounts for about 0.25 to 4, in particular 1 to 2, parts by weight of component A1.

A further preferred embodiment is characterized in that the dispersion of the organic binder component A to 0.01 to 30 wt .-%, the metal component B to 30 to 89.99 wt .-%, the solvent component C to 10 to 69.99 wt .-%, in each case based on the total weight of the dispersion are included.

Another preferred embodiment is characterized in that component B contains

B1 0.01 to 99.99 wt .-% based on the total weight of the metal component B of a first metal having a first metal particle shape and

B2 99.99 to 0.01 wt .-% based on the total weight of the metal component B of a second metal having a second metal particle shape,

wherein in a particularly preferred embodiment at least one of the following conditions is fulfilled:

(1) The first and second metals are different

(2) The first and second particle shapes are different. The dispersion may further comprise at least one of the components

D) with 0.01 to 50 wt .-% based on the total weight of the dispersion of a

dispersant; and E) at 0.01 to 50 wt .-% based on the total weight of the dispersion of a filler component.

Component A

The binder component A essentially contains the polyvinyl chloride A1 and the polyurethane A2. In a preferred embodiment, the components A1 and A2 make up 80 to 100% of the binder component A.

Component A1

Preferred hydroxyl group-containing polyvinyl chlorides are for example those sold by Wacker Polymer Systems GmbH Burghausen, Germany Vinnol ^® E-types, which are prepared by emulsion polymerization. Suitable components A1 are, for example, vinyl chloride copolymers of vinyl chloride and hydroxy-functional comonomers, such as. B. allyl alcohol; Hydroxyacrylates, in particular 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl

(Meth) acrylate; Allyl esters of hydroxycarboxylic acids, in particular hydroxycaproic acid allyl esters. In a preferred embodiment, the copolymerized hydroxy-functional comonomers contain from 1 to 50, in particular from 5 to 30,% by weight in Al.

Also suitable are vinyl chloride copolymers of vinyl chloride and vinyl acetate, which are at least partially hydrolyzed after the polymerization to form recurring vinyl alcohol units, such as. For example, the UCAR ™ grades sold by the DOW Chemical Company. In a preferred embodiment, the repeating vinyl alcohol units are present at 1 to 25, in particular at 3 to 15 wt .-% in A1.

Particularly preferred components A1 have a molecular weight M _{w of} from 20,000 to 200,000 g / mol. Suitable components A1 are described, for example, in DD135620, pages 3 to 6; US-A-3036029, columns 1 to 3; US-A-2686172, columns 1 to 6 and WO 96/04135, pages 8 to 18. Polyurethane component A2

Suitable components A2 are in particular hydroxyl-containing polyurethanes having a molecular weight Mw of from 1,000 to 300,000, preferably from 5,000 to 300,000 (measured by GPC), prepared from diisocyanates and

a) hydroxyl-containing polyesters having a molecular weight Mw of 500 to 10,000 from alkanedicarboxylic acids and alkanediols or

b) polyesters having a molecular weight Mw of 500 to 10,000, which have been obtained by polycondensation of hydroxyalkane monocarboxylic acids or by polymerization of their lactones, or

c) hydroxyl-containing polyethers of the formula (I)

HO- (RX) _n -H (I), wherein:

R d-Cio-alkylene, C ₃ -C ₀ cycloalkylene or C ₅ -C ₄ arylene preferably

Phenylene means X is oxygen (O) and / or sulfur (S) and n is an integer from 10 to 100.

The number n in formula (I) is preferably selected so that the molecular weight Mw of the polyether is 500 to 10,000.

Examples of such polyethers are polyethylene oxide, polypropylene oxide, polybutylene oxide, polyhexamethylene glycol, etc.

Preference is given to polyurethanes of hydroxyl-containing polyesters of alkanedicarboxylic acids having at least six carbon atoms and alkanediols having at least four carbon atoms. Examples of suitable alkanedicarboxylic acids are adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc. Examples of suitable alkanediols are ethylene glycol, butanediol 1, 4, pentanediol 1, 5, hexanediol 1, 6, etc.

Particularly preferred are polyester polyurethanes prepared by the reaction of

aa) polyester diols having a molecular weight of more than 600 and, if appropriate, ab) diols having a molecular weight range of from 62 to 600 as a chain extender with ac) organic diisocyanates

with retention of an equivalent ratio of hydroxyl groups of components aa) and ab) to isocyanate groups of component ac) of 1: 0.9 to 1: 0.999, characterized in that component aa) contains at least 80% by weight of polyisocyanate. ester diols of the molecular weight range 4000 to 6000 on the basis of (i) adipic acid and (ii) mixtures of 1, 4-dihydroxybutane and 1, 6-dihydroxyhexane in the molar ratio of the diols of 4: 1 to 1: 4.

Component aa) preferably comprises at least 80% by weight of polyester diols of a molecular weight from 4000 to 6000 which can be calculated from the hydroxyl number, based on (i) adipic acid and (ii) mixtures of 1,4-dihydroxybutane and 1,6-diene. Dihydroxyhexane in the molar ratio of the diols of 4: 1 to 1: 4, preferably 7: 3 to 1: 2. The preparation of these polyester diols is carried out in known manner by the reaction of adipic acid with one, corresponding to the molecular weight of said excess of the diol mixture at 100 to 220 ⁰ C until the acid number of the reaction mixture has fallen below the second

In addition to these polyester diols, component aa) may contain up to 20% by weight of other polyester diols having a molecular weight of more than 600 and being of molecular weight which can be calculated from the hydroxyl number. In general, these polyester diols, which may be used, have a molecular weight between 1000 and 4000. These polyester diols are those which are obtainable in a manner known per se by reacting alkanedicarboxylic acid having preferably at least 6 carbon atoms and alkanediols having preferably at least 4 carbon atoms. Examples of suitable diols are 1,4-dihydroxybutane, 1,5-dihydroxypentane or 1,6-dihydroxyhexane.

In the preparation of the polyester-ester polyurethanes, it is optionally possible to use as starting component ab) the low-molecular-weight chain extenders which have two terminal hydroxyl groups and are known per se. These are generally dihydric alcohols in the molecular weight range from 62 to 600, preferably 62 to 18.

These chain extenders are preferably alkanediols having 2 to 8, preferably 2 to 8, preferably 2 to 8, preferably 4 to 6 carbon atoms, such as terminal hydroxyl groups. B. 1, 2-dihydroxyethane, 1, 3-dihydroxypropane, 1, 4-dihydroxybutane, 1, 5-dihydroxypentane, 1, 6-dihydroxyhexane or any mixtures of such diols. The component ab) is used, if at all, in an amount of up to 200, preferably up to 100 and preferably up to 70 hydroxyl equivalent percent, based on the component aa), with. In particular, when using mixtures of alkanediols of the type mentioned as component ab) the chain extenders can be used in total in an amount of 100 to 200 hydroxy equivalent percent, based on the component aa), with. When using only one chain extender of the type exemplified, the amount of the component is in general from a maximum of 100 hydroxyl equivalent percent, based on the component aa). Particularly preferred is the use of the component ab) in an amount of 30 to 70 hydroxyl equivalent percent, based on the component aa).

Aliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates of any kind are suitable for the preparation of the hydroxyl-polyurethane component (A) to be used according to the invention, especially those of the formula

Q (NCO) ₂

in which

Q is an aliphatic hydrocarbon radical having in particular 4 to 10, preferably 6 carbon atoms, a cycloaliphatic hydrocarbon radical having in particular 5 to 15 carbon atoms, preferably 6 to 13 carbon atoms, an aromatic hydrocarbon radical having in particular 6 to 15, preferably 7 to 13 carbon atoms or an araliphatic Koh - Hydrocarbon radical having in particular 1 to 13 carbon atoms.

Examples of preferred diisocyanates are 1,4-butane diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexylene diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, 2,4- and 2, respectively. 6-diisocyanatotoluene and mixtures thereof, 4,4'-diphenylmethane diisocyanate, etc.

The reaction of the diisocyanates with the hydroxyl polyesters and ethers a) -c) is preferably carried out in a manner known per se by heating the components together at temperatures between 70 and 160 ^° C.

Suitable examples are the Desmocoll® grades from Bayer AG / Bayer Material Science AG, Leverkusen, in particular types 140, 500 and 530. Further constituents of the binder component A

The binder component A may additionally contain other binders, for example natural and synthetic polymers and their derivatives, natural resins and synthetic resins and their derivatives, natural rubber, synthetic rubber, proteins, cellulose derivatives, such as. As cellulose nitrate, alkylcelluloses, cellulose esters, drying and non-drying oils and the like, in particular polyalkylenes, polyimides, epoxy and phenolic resins, styrene-butadiene block copolymers, styrene-isoprene block copolymers, Alkylenvinylacetate and copolymers, copolymers of vinyl chloride and vinyl ethers, polyamides and their copolymers, poly (meth) acrylates or polyvinyl nyl ethers, polyvinyl acetals and their copolymers.

Based on the total weight of the dispersion, the proportion of the organic binder component A), in particular 0.01 to 30 wt .-%; Preferably, the proportion is 0.1 to 20 wt .-%, more preferably 0.5 to 10 wt .-%.

Component B

The metal component B preferably contains a first metal having a first metal particle shape and a second metal having a second metal particle shape.

The first metal may be a metal that is the same or different than the second metal. Also, the first metal particle shape may be the same as or different from the second metal particle shape. However, it is preferred that at least the metals or the particle shapes differ. However, it is also possible that both the first and the second metal and the first and second particle form are different from each other.

In addition to the metal components B1 and B2, the dispersion may comprise further metals different from the first and second metals, different from the first or second metals, or equal to the first and second metals. The same applies to the metal particle form of another metal. However, in the present invention, it is preferable that at least a first and second metal and a first metal particle shape and a second metal particle shape are present under the condition that the first and second metals are different and / or that the first and second particle shapes are different from each other

In the context of the present invention, the metals have the oxidation state 0 and can be supplied as metal powder to the dispersion. Preferably, the metals have an average particle diameter of 0.001 to 100 microns, preferably from 0.002 to 50 microns and more preferably from 0.005 to 10 microns. The average particle diameter can be determined by means of laser diffraction measurement, for example on a Microtrac X100 device. The distribution of particle diameters depends on their production process. Typically, the diameter distribution has only one maximum, but several maxima are also possible.

So it is z. B. possible to mix particles with a mean particle diameter <100nm with particles> 1 micron, as a denser particle packing can be achieved.

Examples of suitable metals are zinc, nickel, copper, tin, cobalt, manganese, iron, magnesium, lead, chromium, bismuth, silver, gold, aluminum, titanium, palladium, platinum, tantalum and alloys thereof. Examples of suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCo, NiPb, ZnFe, ZnNi, ZnCo and ZnMn. Particularly preferred are iron, zinc, aluminum, copper and silver.

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.

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

However, the metal component B 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 metal component B contains two different alloys. Also for these two cases, the metal components B1 and B2 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 be, for example, acicular, cylindrical, plate-shaped or 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 component B1 and B2 differ in their metal particle shape, it is preferred that the first is spherical and the second plate-shaped or needle-shaped.

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

As already stated above, the metals in the form of their powders can be added to the dispersion. 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 metal salts or by reduction of an oxide powder, for example by means of hydrogen, by spraying or atomizing a molten metal, especially in cooling media, such as gases or water , Preference is given to gas and water atomization.

In the case of iron, besides the gas and water atomization, the carbonyl iron powder process (CEP process) is preferred for the preparation 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 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 baths, heating wires or is surrounded by a heating medium flowed through by a heating jacket.

Platelet-shaped metals can be obtained by optimized conditions in the production process or afterwards by mechanical treatment, for example by treatment in a stirred ball mill.

Based on the total weight of the dispersion, the metal component B is in a proportion of 30 to 89.99 wt .-%. The metal component B1 has a share from 99.99 to 0.01 wt .-% based on the total weight of component B on. The metal component B2 has a content of 0.01 to 99.99 wt .-%. If no further metals are present, B1 and B2 give 100% of the metal component B.

A preferred range of B is from 50 to 85% by weight, based on the total weight of the dispersion.

The weight ratio of components B1 and B2 is preferably in the range of 1000: 1 to 1: 1, more preferably 100: 1 to 1: 1, most preferably in the range of 20: 1 to 1: 1.

Component C

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

Suitable solvents are acetone, alkyl acetates, butyl diglycol, alkyl glycol acetates, such as butyl glycol acetate, butylglycol, benzyl acetate, butyl acetate, gamma-butyrolactone, benzyl alcohol, chloroform, cyclohexanone, diacetone alcohol, diglycol dimethyl ether, dioxane, ethyl acetate, ethylene chloride, ethylene glycol acetate, ethyl glycol, ethoxypropyl acetate, ethylene glycol. glycol di- methyl ether, isophorone, isobutyl acetate, isopropyl acetate, methyl acetate, methyl glycol, methylene chloride, methylene glycol, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl glycol acetate, propyl acetate, propylene glycol monoalkyl ethers, such as. As methoxypropyl acetate, carbon tetrachloride, tetrahydrofuran, and mixtures of two or more of these solvents.

Preferred solvents are acetone, alkyl acetates, alkyl glycol acetates, such as butyl glycol acetate, gamma-butyrolactone, benzyl alcohol, benzyl acetate, cyclohexanone, diacetone alcohol, dioxane, ethyl acetate, ethylene glycol acetate, ethoxypropyl acetate, isopropyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl glycol acetate, propyl acetate, Propylene glycol monoalkyl ethers such as. B. methoxypropyl acetate, tetrahydrofuran and mixtures thereof.

The solvent component C has a proportion based on the total weight of the dispersion of 10 to 69.99 wt .-%. Preferably, the proportion is 15 to 50 wt .-%. Component D

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.

Also fatty acids such. As oleic acid or stearic acid are suitable as a dispersant component

However, it is also possible to use polymers known to the person skilled in the art with pigment-affine anchor groups as dispersants.

The dispersant component D can be used in the range of 0.01 to 50 wt .-% based on the total weight of the dispersion. Preferably, the proportion is 0.1 to 25 wt .-%, particularly preferably 0.3 to 10 wt .-%.

Component E

Furthermore, the dispersion according to the invention may contain a filler component E. This may consist of one or more fillers. Thus, the component E may contain the metallizable mass of fibrous or particulate fillers or mixtures thereof. These are preferably commercially available products, such as carbon modifications z. For example, carbon blacks, graphenes, carbon nanotubes and glass fibers.

Furthermore, fillers or reinforcing materials, such as glass powder, mineral fibers, whiskers, alumina, mica, quartz powder or wollastonite can be used. Furthermore, carbon, silica, silicates, such as aerosils or phyllosilicates, dyes, fatty acids, amides, plasticizers, wetting agents, driers, catalysts, complexing agents, calcium carbonate, barium sulfate, waxes, pigments, adhesion promoters or conductive polymer particles can be used. The proportion of component E based on the total weight of the dispersion is preferably 0.01 to 50 wt .-%. Further preferred are 0.1 to 10 wt .-%, particularly preferably 0.3 to 5 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 .-%.

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

A mixing of components A to C and optionally D, E and further components and

B dispersing the mixture.

The dispersion preparation can be carried out by intensive mixing and dispersing with aggregates known in the art. This involves mixing the components in a dissolver or a comparable intensively dispersing aggregate, dispersing in a stirred ball mill or a large-capacity powder fluidizer.

Another object of the present invention is a method for producing a metal layer on at least a part of the surface of a non-electrically conductive substrate

a) applying a dispersion of the invention on the substrate;

b) drying the coated layer on the substrate; and

c) optionally electroless and / or electrodeposition of a metal on the dried dispersion layer.

Suitable substrates are electrically non-conductive materials such as polymers. Suitable polymers are epoxy resins, for example bifunctional or polyfunctional, aramid-reinforced or glass-fiber reinforced or paper-reinforced epoxy resins (for example FR4), glass-reinforced plastics, polyphenylene sulfides (PPS), polyoxymethylenes (POM), polyaryletherketones (PAEK), polyetheretherketones (PEEK), polyamides ( PA) Polycarbonates (PC), polybutylene terephthalates (PBT), polyethylene terephthalates (PET), polyethylene naphthenates (PEN), polyimides (PI), phenolic resin coated aramid paper dielectrics, APPE, polyetherimides (PEI), polyphenylene oxides (PPO), polypropylenes (PP), polyethylenes (PE), polysulfones (PSU), polyethersulfones (PES), polyarylamides (PAA), polyvinyl chlorides (PVC), polystyrenes (PS), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylates (ASA), styrene acrylonitriles (SAN) and mixtures (blends) two or more of the above polymers, which may be in various forms. The substrates may comprise additives known to the person skilled in the art, for example lubricants, stabilizers or flame retardants.

Particularly preferred substrates are polyethylene terephthalate (PET), polyethylene naphthenate (PEN), polyamide (PA), polycarbonate (PC), polyvinyl chloride (PVC).

Further suitable substrates are composite materials, foam-like polymers, Styropor® ^®, ^® styrodur, ceramic surfaces, textiles, paperboard, cardboard, paper, polymer coated paper, wood, mineral materials, glass.

In the context of the present invention, the term "non-electrically conductive" is preferably understood to mean that the specific resistance 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.

Likewise, the drying of the applied layer by conventional methods. Alternatively, the binder can also be cured by chemical or physical means, for example by temperature.

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

The dispersion according to the invention can be structured or applied in a planar manner in step a). It is preferred if the steps of application (step a), drying (step b) and optionally the deposition of a further metal (step c) are carried out in a continuous mode of operation. This is possible by simply carrying out steps a), b) and optionally c). However, of course, a batchwise or semi-continuous process is possible. The coating can be carried out using the customary and generally known coating methods (casting, brushing, knife coating, printing (gravure printing, screen printing, flexographic printing, pad printing, inkjet, offset, etc.), spraying, dipping, powdering, fluidized bed, etc.) , The layer thickness preferably varies between 0.01 and 100 μm, more preferably between 0.1 and 50 μm, particularly preferably between 1 and 25 μm. The layers can be applied both over the entire surface as well as structured.

In a particularly preferred embodiment, the dispersion according to the invention is applied to the substrate by means of a printing device which emits energy in the form of electromagnetic waves, the dispersion undergoes a change in volume and / or position and thereby the transmission the dispersion is carried out on the substrate. Such methods are known, for example, from WO 03/074278 A1, WO 01/72518 A1 and DE-A-1 00 51 850. Such a method is offered by Aurentum Innovationstechnologien GmbH under the name LaserSonic® Technology.

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. One or more metal layers may be electroless and / or galvanic, i. under application of external voltage and current flow. In principle, all metals, the noble or the same noble as the most noble metal of the dispersion for electroless and / or galvanic deposition in question. Preferably, copper, chromium, silver, gold and / or nickel layers are electrodeposited. The electrodeposition of layers of aluminum is also preferred. The thicknesses of the one or more deposited layers in step c) are in the usual range known to the person skilled in the art and are not essential to the invention.

In a preferred embodiment of the invention, the substrate is treated with a primer before the application of the dispersion according to the invention. In a preferred embodiment, the primer corresponds to the dispersion according to the invention with the proviso that the metal component B is not included. Thus, in one embodiment, the primer contains essentially an organic binder component A, a solvent component C, optionally a dispersant component D and optionally a filler component E. In a further preferred embodiment, the filler component E contains fillers which can act as spacers and thus prevent sticking of coated substrate when rolling up. Another object of the present invention is a substrate having a 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 according to the invention can be used in particular for various applications listed below.

For example, the production of printed conductor structures, for example for the production of antennas, such as RFI D antennas, transponder antennas, printed circuit boards (multilayer internal and external layers, micro-via, chip-on-board, flexible and rigid Printed circuit boards, paper and composites, etc.), flat cables, seat heaters, contactless chip cards, capacitors, resistors, connectors, foil conductors, electrical fuses.

Furthermore, it is possible to produce antennas with contacts for organic electronic components as well as coatings on surfaces consisting of electrically nonconductive material for electromagnetic shielding.

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 according to the invention and the substrate surface according to the invention allows cost-effective production of metallized, even non-conductive substrates, especially for use as switches, sensors and MIDs (Molded Interconnect devices), absorber for electromagnetic radiation or decorative parts, in particular decorative parts for the motor vehicle, sanitary, toy, household and office sector and packaging, and films. 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 RFID) Transponder antennas, sensors, heating elements, antistatic (also for plastics), shielding, etc.).

Examples of such applications are housings such as computer cases, display cases, cell phones, audio, video, DVD, camera, electronic component housings, military and non-military shields, shower and washbasin faucets, showerheads, shower rods and holders, metalized 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, the production of contact points or contact pads or wiring on an integrated electrical component is possible.

The dispersion according to the invention can likewise be used for the metallization of holes, vias, blind holes etc. in printed circuit boards and RFID antennas with the aim of contacting the upper and lower printed circuit board side. This also applies if other substrates are used.

Furthermore, the metallized articles 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 thus produced serves as a printed circuit board, RFID antenna, transponder antenna, seat heating, flat cable or contactless chip cards.

Examples

example 1

In a solution of 3.5 g Vinnol ^® 15 / 40A (OH-functionalized PVC copolymer Fa. Wacker) and 1, 7g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31, 8g of methyl ethyl ketone, 50.5 g of a spherical iron powder and 12.5 g of a platelet-shaped copper powder were stirred with a dissolver stirrer. The resulting dispersion was applied with a doctor blade to a PET film in a layer thickness of about 4 microns. After drying, an approximately 20 μm thick copper layer was deposited on this metal layer with a commercially available acidic copper sulfate bath. After storage for 5 days at room temperature, the adhesion of the deposited metal layer was determined by means of a tensile elongation tester (Zwick).

Example 2

A solution of 3.5 g Vinnol ^® 15 / 40A (OH-functionalized PVC copolymer Fa. Wacker) and 1, 7 g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31, 5 g of methyl ethyl ketone was by means of a Doctor blade applied to a PET film in a layer thickness of about 1, 5 microns and dried. Thereafter, the dispersion of Example 1 was applied to the thus primed PET film. After drying, an approximately 20 μm thick copper layer was deposited on this metal layer with a commercially available acidic copper sulfate bath. After storage for 5 days at room temperature, the adhesion of the deposited metal layer was determined by means of a tensile elongation tester (Zwick).

Example 3

To a solution of 3g Vinnol ^® 15 / 48A (OH-functionalized PVC copolymer Fa. Wacker) and 3 g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31 g Metyhlethyl- were ketone 50,5g of a spherical iron powder and 12 , 5 g of a platelet-shaped copper powder stirred with a Dissolverrührer. The resulting dispersion was applied with a doctor blade to a PET film in a layer thickness of about 4 microns. After drying, an approximately 20 μm thick copper layer was deposited on this metal layer with a commercially available acidic copper sulfate bath. After storage for 5 days at room temperature, the adhesion of the deposited metal layer was determined by means of a tensile elongation measuring device (Zwick)

Example 4

A solution of 3 g Vinnol ^® 15 / 48A (OH-functionalized PVC copolymer Fa. Wacker) and 3g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31, 5 g of methylene was lethylketon by means of a doctor blade on a PET Applied film in a layer thickness of about 1, 5 microns and dried. Thereafter, the dispersion of Example 3 was applied to the thus primed PET film. After drying, an approximately 20 μm thick copper layer was applied to this metal layer using a commercially available acid copper oxide. deposited sulfate bath. After storage for 5 days at room temperature, the adhesion to the metal layer was determined by means of a tensile elongation measuring device (Zwick)

Example 5

A solution of 3.5 g Vinnol ^® 15 / 40A (OH-functionalized PVC copolymer Fa. Wacker) and 1, 7g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31, 5 g of methyl ethyl ketone was on by means of a doctor blade a PET film in a layer thickness of about 1, 5 microns applied and dried.

Thereafter, the following dispersion was applied to the so-primed PET film:

To a solution of 3 g Vinnol ^® 15 / 40A (OH-functionalized PVC copolymer Fa. Cker Wa) and 3 g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31 g Metyhlethyl- ketone were 50.5 g of a spherical iron powder and 12.5 g of a platelet-shaped copper powder stirred with a Dissolverrührer. The resulting dispersion was applied with a doctor blade to a PET film in a layer thickness of about 4 microns. After drying, an approximately 20 μm thick copper layer was deposited on this metal layer with a commercially available acidic copper sulfate bath. After storage for 5 days at room temperature, the adhesion of the deposited metal layer was determined by means of a tensile elongation tester (Zwick).

Example 6

A solution of 3.5 g Vinnol ^® 15 / 40A (OH-functionalized PVC copolymer Fa. Wacker) and 1, 7 g Desmocoll ^® 140 (OH-functionalized polyurethane polymer) in 31, 5 g of methyl ethyl ketone was by means of a Doctor blade applied to a PET film in a layer thickness of about 1, 5 microns and dried.

Thereafter, the following dispersion was applied to the so-primed PET film:

To a solution of 1, 7g Vinnol ^® 15 / 40A (OH-functionalized PVC copolymer Fa. Wacker) and 3.5 g of Desmocoll ^® 1 40 (OH-functionalized polyurethane polymer) in 31, 5 g of methyl ethyl ketone 50.5 g of a spherical iron powder and 12.5 g of a platelet-shaped copper powder stirred with a dissolver stirrer. The resulting dispersion was applied with a doctor blade to a PET film in a layer thickness of about 4 microns. After drying, an approximately 20 μm thick copper layer was deposited on this metal layer with a commercially available acidic copper sulfate bath. After storage for 5 days at room temperature, the adhesion of the deposited metal layer was determined by means of a tensile elongation tester (Zwick).

Comparative Example 1

Example 1 of DE-A-102005043242 was reproduced exactly:

8.4 g of an ethylene-vinyl acetate copolymer were dissolved in 126 g of n-butyl acetate. In this solution, 378 g of spherical iron powder and 42.0 g of platelet-shaped copper powder were dispersed by means of a dissolver stirrer. The obtained dispersion was applied to a primed PET film in a thickness of 4 μm. After drying, a copper layer of 9 μm thickness was applied in an acidic copper sulfate bath.

Comparative Example 2

Example 2 of DE-A-102005043242 was reproduced exactly:

8.4 g of an ethylene-vinyl acetate copolymer were dissolved in 96.6 g of n-butyl acetate. In this solution, 378 g of spherical iron powder and 42.0 g of platelet-shaped copper powder were dispersed by means of a dissolver stirrer. The obtained dispersion was applied to a primed PET film in a thickness of 4 μm. After drying, a copper layer of 9 μm thickness was applied in an acidic copper sulfate bath.

The results given in the following table were obtained.

table

Claims

Patent claims

1. Containing a dispersion for applying a metal layer to an electrically non-conductive substrate

an organic binder component A, a metal component B, a solvent component C, characterized in that the organic binder component A essentially consists of

A1 is a polyvinyl chloride copolymer with hydroxyl groups and A2 is a polyurethane with hydroxyl groups.

2. Dispersion according to claim 1, characterized in that component A1 is obtainable by polymerizing vinyl chloride with allyl alcohol and / or a hydroxyacrylate and / or an allyl ester of a hydroxycarboxylic acid and that

A2 is a linear polyurethane containing hydroxyl groups.

3. Dispersion according to at least one of the preceding claims, characterized in that component A1 is obtainable by polymerization of vinyl chloride and vinyl acetate, the polymer obtained can be further hydrolyzed to form recurring vinyl alcohol units and that A2 is a linear polyurethane containing hydroxyl groups.

4. Dispersion according to at least one of the preceding claims, characterized in that the components A1 and A2 make up at least 80% by weight of the binder component A.

5. Dispersion according to at least one of the preceding claims, characterized in that one part by weight of A2 contains approximately 0.25 to 4, in particular 1 to 2 parts by weight of component A1.

6. Dispersion according to at least one of the preceding claims, characterized in that

The organic binder component A is contained in 0.01 to 30% by weight, the metal component B in 30 to 89.99% by weight, and the solvent component C in 10 to 69.99% by weight, each based on the total weight of the dispersion.

7. Dispersion according to at least one of the preceding claims, characterized in that the metal component contains B

B1 0.01 to 99.99% by weight based on the total weight of the metal component B of a first metal with a first metal particle shape and

B2 99.99 to 0.01% by weight, based on the total weight of the metal component B, of a second metal with a second metal particle shape;

wherein at least one of the following conditions is met: (1) the first and second metals are different

(2) the first and second particle shapes are different.

8. Dispersion according to at least one of the preceding claims, characterized in that it further contains at least one of the components

D 0.01 to 50% by weight based on the total weight of the dispersion of a dispersant component; as well as

E contains 0.01 to 50% by weight based on the total weight of the dispersion of a carbon-based filler component.

9. Dispersion according to at least one of the preceding claims, characterized in that the metal component B is optionally coated and independently selected from the group consisting of zinc, nickel, copper, tin, cobalt, manganese, iron, magnesium, lead, chromium , bismuth, silver, gold, aluminum, titanium, palladium, platinum, tantalum and alloys thereof.

10. Dispersion according to at least one of the preceding claims, characterized in that the metal component B contains at least two different metals.

1 1. Dispersion according to at least one of the preceding claims, that the metal component B is present in at least two different particle shapes.

12. Dispersion according to at least one of the preceding claims, characterized in that the average particle diameter of the metal of the metal component B is in the range from 0.001 to 100 μm.

13. A process for producing a dispersion according to at least one of the preceding claims

1. Mixing components A to C and, if necessary, D, E and other components and

2. Disperse the mixture.

14. Method for producing a metal layer on at least part of the surface of a non-electrically conductive substrate

a) applying a dispersion according to at least one of the preceding claims to the substrate;

b) drying the applied layer on the substrate; and

c) optionally electroless and/or galvanic deposition of a metal on the dried dispersion layer.

15. The method according to claim 14, characterized in that a primer is first applied to the support before applying the dispersion.

16. The method according to claim 15, characterized in that the binder component of the primer contains the components A1 + A2, as well as optionally a dispersant component D and a filler component E.

17. The method according to at least one of the preceding claims 14 to 16, characterized in that the substrate is a PET, PVC, PEN, PC or PA film.

18. The method according to at least one of claims 14 to 17, characterized in that the dispersion is applied to the substrate using a printing process, in which the dispersion has a volume with the aid of an energy-emitting device which emits energy in the form of electromagnetic waves -and/or changes in position and this results in the transfer of the dispersion to the substrate.

19. Coated substrate with a surface available according to at least one of claims 14 to 18.

20. Use of a substrate surface according to claim 19 for conducting electrical current, heat, as a decorative metal surface, for shielding from electromagnetic radiation and for magnetization.