DE102005059323A1 - Preparing metal-plated, extruded plastic, useful as e.g. decorative particle, comprises melt blending and extrusion of plastic mixture and contacting mixture with acid, neutral or basic metal salt solution by electrolessly/glavanically - Google Patents

Abstract

Preparation of metal-plated, extruded plastic comprises: melt blending and extrusion of a plastic mixture (comprising: thermoplastic polymer (A); metal powder (B) having an average particle diameter of 0.1-100 mu m and more negative normal potential in acid solution than silver; dispersant (C); and fibrous/particulate fillers or their mixture (D)); and contacting the extruded plastic object with an acid, neutral or basic metal salt solution through electrolessly or galvanically. Preparation of metal-plated, extruded plastic comprises: melt blending and extrusion of a plastic mixture (comprising 100 wt.% of the components related to the total weight: 5-50 wt.% of thermoplastic polymer (A); 50-95 wt.% of metal powder (B) having an average particle diameter of 0.1-100 mu m and more negative normal potential in acid solution than silver; 0-10 wt.% of dispersant (C); and 0-40 wt.% of fibrous/particulate fillers or their mixture (D)); and contacting extruded plastic object with an acid, neutral or basic metal salt solution through electrolessly or galvanically brought into contact , that metal having a more positive normal potential in a correspondingly acid, neutral or basic solution than component (B), where the plastic object is surface-activated in the non-molten state after the melt blending and extrusion step and before the contacting step. An independent claim is included for a metal-plated, extruded plastic object obtained by the process.

Description

• a 5 bis 50 Gew.-% eines thermoplastischen Polymers als Komponente A,
• b 50 bis 95 Gew.-% eines Metallpulvers mit einem mittleren Teilchendurchmesser von 0,01 bis 100 μm (bestimmt gemäß der in der Beschreibung genannten Methode), wobei das Metall ein negativeres Normalpotential in saurer Lösung aufweist als Silber, als Komponente B,
• c 0 bis 10 Gew.-% eines Dispergiermittels als Komponente C, und
• d 0 bis 40 Gew.-% faser- oder teilchenförmige Füllstoffe oder deren Gemische als Komponente D,

erfolgt, und in einem letzten Schritt der extrudierte Kunststoff-Gegenstand stromlos oder galvanisch mit einer sauren, neutralen oder basischen Metallsalzlösung in Kontakt gebracht wird, wobei dieses Metall ein positiveres Normalpotential in entsprechend saurer, neutraler oder basischer Lösung aufweist als Komponente B.The invention relates to processes for producing metallized, extruded plastic articles, wherein in a first step, the melt mixing and extrusion of a plastic mixture comprising, based on the total weight of components A, B, C, and D, which gives a total of 100 wt .-%,

• a 5 to 50% by weight of a thermoplastic polymer as component A,
• b 50 to 95% by weight of a metal powder having an average particle diameter of 0.01 to 100 μm (determined according to the method mentioned in the description), the metal having a more negative normal potential in acidic solution than silver, as component B,
• c 0 to 10 wt .-% of a dispersant as component C, and
• d from 0 to 40% by weight of fibrous or particulate fillers or mixtures thereof as component D,

takes place, and in a last step, the extruded plastic article is electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, this metal having a more positive normal potential in accordance with acidic, neutral or basic solution than component B.

Farther The invention relates to metallized extruded plastic articles which Use of these items as well as EMI shieldings such as absorbers, dampers or reflectors for electromagnetic Radiation, oxygen scavenger, comprising electrically conductive components, gas barriers and decorative parts these objects.

method for producing metallised plastic films or molded articles known and become diverse Application areas used.

So can metal powder-containing plastic objects without current and / or galvanic be metallized. Such metallized plastic articles are due to the electrical conductivity used for example as electrical components. Farther you can find a lot of use and much more. in the decor area, as they look at same appearance as completely made of metal Items benefits have lower weight and cheaper production.

in the general is it in view of the mentioned fields of application and desirable for forming dense and adherent metal layers, one possible achieve high metal powder content in the plastic. With rising filling level but usually a deterioration of the mechanical properties the plastic mixtures are accompanied, so that at high degrees of filling for example, toughness, Bending strength and deformability are insufficient, creating a unacceptable deterioration of processing properties and a serious limitations freedom of design in forming processes can result. Plastic blends that still have good processability and design freedom in the shaping of the plastic semi-finished products produced from them such as films are therefore due to limited Metallpulverfüllgrade often only poorly or not metallizable.

It is therefore the object of the present invention, methods for Preparation of metallized plastic objects to provide the characterized by the fact that with comparably good processing properties and formal design freedom of plastic objects, for example in forming processes for the production of complex shaped components, across from known method for producing metallized plastic parts an improved electroless and galvanic metallization is possible. Another object of the present invention is to provide metallized Plastic items the opposite at metallized plastic bodies produced by known methods comparable good processing properties and formative Design freedom qualitatively improved, in particular more homogeneous and / or more adherent metal layers.

• a 5 bis 50 Gew.-% eines thermoplastischen Polymers als Komponente A,
• b 50 bis 95 Gew.-% eines Metallpulvers mit einem mittleren Teilchendurchmesser von 0,01 bis 100 μm (bestimmt gemäß der in der Beschreibung genannten Methode), wobei das Metall ein negativeres Normalpotential in saurer Lösung aufweist als Silber, als Komponente B,
• c 0 bis 10 Gew.-% eines Dispergiermittels als Komponente C, und
• d 0 bis 40 Gew.-% faser- oder teilchenförmige Füllstoffe oder deren Gemische als Komponente D,

erfolgt, und in einem letzten Schritt der extrudierte Kunststoff-Gegenstand stromlos oder galvanisch mit einer sauren, neutralen oder basischen Metallsalzlösung in Kontakt gebracht wird, wobei dieses Metall ein positiveres Normalpotential in entsprechend saurer, neutraler oder basischer Lösung aufweist als Komponente B,
wobei erfindungswesentlich ist, dass der Kunststoff-Gegenstand nach dem Schritt der Schmelzevermischung und Extrusion und vor dem Schritt des Kontaktierens mit der Metallsalzlösung im nicht-schmelzflüssigen Zustand (als nicht-schmelzflüssiger Zustand ist bei teilkristallinen Polymeren der Zustand innerhalb eines Temperaturbereichs von +/– 20 °C um den Schmelzpunkt Tm des teilkristallinen Polymeren zu verstehen; als nicht-schmelzflüssiger Zustand ist bei nicht-kristallinen Polymeren der Zustand im Temperaturbereich von 0 bis 70 °C oberhalb der höchsten anzutreffenden Glasstufe des nicht-kristallinen Polymeren zu verstehen) oberflächenaktiviert wird.Accordingly, the aforementioned methods for producing metallized, extruded plastic article were found, wherein in a first step, the melt mixing and extrusion of a plastic mixture comprising, based on the total weight of components A, B, C, and D, which is a total of 100 wt. % results,

• a 5 to 50% by weight of a thermoplastic polymer as component A,
• b 50 to 95% by weight of a metal powder having an average particle diameter of 0.01 to 100 μm (determined according to the method mentioned in the description), the metal having a more negative normal potential in acidic solution than silver, as component B,
• c 0 to 10 wt .-% of a dispersant as component C, and
• d from 0 to 40% by weight of fibrous or particulate fillers or mixtures thereof as component D,

takes place, and in a last step, the extruded plastic article is electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, said metal a more positive normal potential corresponding to acidic, neutral or basic solution than component B,
wherein it is essential to the invention that the plastic article after the step of melt mixing and extrusion and before the step of contacting with the metal salt solution in the non-molten state (as a non-molten state is the state within a temperature range of +/- 20 ° C to understand the melting point Tm of the semicrystalline polymer, non-molten state is understood to be surface-activated in non-crystalline polymers, the state in the temperature range of 0 to 70 ° C above the highest glass level of the non-crystalline polymer encountered).

Farther were metallized extruded plastic objects, the Use of these items as well as EMI shieldings such as absorbers, dampers or reflectors for electromagnetic radiation, Oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects found.

The inventive method for the production of metallized plastic objects characterized by that with comparably good processing properties and freedom of design freedom the plastic objects, For example, in forming processes for the production of complex shaped Components, opposite known method for producing metallized plastic parts an improved electroless and galvanic metallization is possible. The according to the inventive method producible metallized plastic objects have opposite to known Method produced metallized plastic bodies comparable good processing properties and formative Design freedom qualitatively improved, in particular more homogeneous and / or more adherent metal layers.

The inventive method as well as the other articles of the invention and Uses are described below.

Plastic mixture:

• a 5 bis 50 Gew.-%, bevorzugt 10 bis 40 Gew.-%, besonders bevorzugt 20 bis 30 Gew.-% der Komponente A,
• b 50 bis 95 Gew.-%, bevorzugt 60 bis 90 Gew.-%, besonders bevorzugt 70 bis 80 Gew.-% der Komponente B,
• c 0 bis 10 Gew.-%, bevorzugt 0 bis 8 Gew.-%, besonders bevorzugt 0 bis 5 Gew.-% der Komponente C, und
• d 0 bis 40 Gew.-%, bevorzugt 0 bis 30 Gew.-%, besonders bevorzugt 0 bis 10 Gew.-% der Komponente D.

The first step of the processes according to the invention comprises melt blending and extrusion of a plastics mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100% by weight,

• a from 5 to 50% by weight, preferably from 10 to 40% by weight, particularly preferably from 20 to 30% by weight, of component A,
• b 50 to 95 wt .-%, preferably 60 to 90 wt .-%, particularly preferably 70 to 80 wt .-% of component B,
• c 0 to 10 wt .-%, preferably 0 to 8 wt .-%, particularly preferably 0 to 5 wt .-% of component C, and
• d is 0 to 40% by weight, preferably 0 to 30% by weight, particularly preferably 0 to 10% by weight of component D.

• a 5 bis 49,9 Gew.-%, bevorzugt 10 bis 39,5 Gew.-%, besonders bevorzugt 20 bis 29 Gew.-% der Komponente A,
• b 50 bis 94,9 Gew.-%, bevorzugt 60 bis 89,5 Gew.-%, besonders bevorzugt 70 bis 79 Gew.-% der Komponente B,
• c 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 8 Gew.-%, besonders bevorzugt 1 bis 5 Gew.-% der Komponente C, und
• d 0 bis 40 Gew.-%, bevorzugt 0 bis 29,5 Gew.-%, besonders bevorzugt 0 bis 9 Gew.-% der Komponente D.

A preferred embodiment of the invention is based on a dispersant-containing plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100 wt .-%,

• a from 5 to 49.9% by weight, preferably from 10 to 39.5% by weight, particularly preferably from 20 to 29% by weight, of component A,
• b 50 to 94.9% by weight, preferably 60 to 89.5% by weight, particularly preferably 70 to 79% by weight of component B,
• c 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 5 wt .-% of the component C, and
• d 0 to 40 wt .-%, preferably 0 to 29.5 wt .-%, particularly preferably 0 to 9 wt .-% of component D.

In a particularly preferred embodiment of the invention, in addition to the metal powder fraction (component B) of the plastic mixture defined by said weight%, the elongation at break of component A is by a factor of 1.1 to 100, preferably by a factor of 1.2 to 50, more preferably by a factor of 1.3 to 10 greater than the elongation at break of the plastic mixture comprising the components A, B, and if present C and D, and also the tensile strength of component A by a factor of 0.5 to 4, preferably by the factor 1 to 3, more preferably by a factor of 1 to 2.5 is greater than the tensile strength of the plastic mixture comprising the components A, B, and if present C and D (a factor less than 1 means that the tensile strength of the component A is smaller as the tensile strength of the plastic mixture comprising the components A, B, and if present C and D);
These and all other elongations at break and tensile strengths mentioned in this application are determined in the tensile test according to ISO 527-2: 1996 on test specimens of type 1BA (Annex A of the cited standard: "small specimens").

In the inventive method is a plastic mixture comprising the following components, used.

component A

In principle, all thermoplastic polymers are suitable as component A, in particular those having an elongation at break in the range of 10%. to 1000%, preferably in the range of 20 to 700, particularly preferably in the range of 50 to 500.

Suitable as component A are, for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene (impact-resistant or not impact-modified), ABS (acrylonitrile-butadiene-styrene), ASA (acrylonitrile-styrene-acrylate), MABS (transparent ABS, containing methacrylate units), styrene-butadiene block copolymer (for example, Styroflex ^® or Styrolux ^® of BASF Aktiengesellschaft, K-Resin ^TM CPC), polyamides, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polybutylene terephthalate (PBT), polycarbonate (such as Makrolon ^® of Bayer AG), polymethyl methacrylate (PMMA), poly (ether) sulfones and polyphenylene oxide (PPO).

Prefers as component A, one or more polymers are selected from impact-modified group vinylaromatic copolymers based on thermoplastic elastomers of styrene, polyolefins, polycarbonates and thermoplastic polyurethanes used.

When likewise preferred component A are polyamides can be used.

toughened vinylaromatic copolymers:

preferred impact modified vinylaromatic copolymers are impact-modified copolymers from vinylaromatic monomers and vinyl cyanides (SAN). Prefers be as impact modified SAN ASA polymers and / or ABS polymers used, and (meth) acrylate-acrylonitrile-butadiene-styrene polymers ("MABS", transparent ABS), but also blends of SAN, ABS, ASA and MABS with other thermoplastics such as polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, PVC, polyolefins.

The ASA and ABS usable as components A generally have breaking elongations from 10% to 300%, preferably 15 to 250%, particularly preferred 20% up to 200%.

Under ASA polymers are generally understood to be impact-modified SAN polymers, in which rubber-elastic graft copolymers of vinyl aromatic Compounds, in particular styrene, and vinyl cyanides, in particular Acrylonitrile, on polyalkylacrylate rubbers in a copolymer matrix in particular styrene and / or α-methylstyrene and acrylonitrile.

In a preferred embodiment, in which the plastic mixtures comprise ASA polymers, the rubber-elastic graft copolymer A ^{K of} the component A is composed of
a1 1-99% by weight, preferably 55-80% by weight, in particular 55-65% by weight, of a particulate grafting base A1 having a glass transition temperature below 0 ° C.,
a2 1-99 wt .-%, preferably 20-45 wt .-%, in particular 35-45 wt .-%, of a graft A2 from the monomers, based on A2,
a21 40-100 wt .-%, preferably 65-85 wt .-%, units of styrene, of a substituted styrene or of a (meth) acrylic acid ester or mixtures thereof, in particular of styrene and / or α-methylstyrene as component A21 and
a22 to 60 wt .-%, preferably 15-35 wt .-%, units of acrylonitrile or methacrylonitrile, in particular of the acrylonitrile as component A22.

The Graft A2 consists of at least one graft.

Component A1 consists of the monomers
a11 80-99.99% by weight, preferably 95-99.9% by weight, of at least one C _1-8 -alkyl ester of acrylic acid, preferably n-butyl acrylate and / or ethylhexyl acrylate as component A11,
a12 0.01-20 wt .-%, preferably 0.1-5.0 wt .-%, of at least one polyfunctional crosslinking monomer, preferably diallyl phthalate and / or DCPA as component A12.

According to one embodiment of the invention, the average particle size of the component A ^{K is} 50-1000 nm and is distributed monomodally.

According to a further embodiment of the invention, the particle size distribution of the component A ^{K is} bimodal, wherein 60-90 wt .-% have an average particle size of 50-200 nm and 10-40 wt .-% have an average particle size of 50-400 nm, based on the total weight of the component A ^K.

The mean particle size or particle size distribution are the sizes determined from the integral mass distribution. The mean particle sizes according to the invention are in all cases the weight average particle size as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z. Polymers 250 (1972), pages 782-796. Ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size. The mean particle diameter, which is also referred to as the d ₅₀ value of the integral mass distribution, is defined as the particle diameter at which the 50th Wt .-% of the particles have a smaller diameter than the diameter corresponding to the d ₅₀ value. Likewise, then 50 wt .-% of the particles have a larger diameter than the d ₅₀ value. To characterize the width of the particle size distribution of the rubber particles, in addition to the d ₅₀ value (average particle diameter), the d ₁₀ and d ₉₀ values resulting from the integral mass distribution are used. The d ₁₀ or d ₉₀ value of the integral mass distribution is defined in accordance with the d ₅₀ value, with the difference that they are based on 10 or 90% by weight of the particles. The quotient (d 90 - d 10 ) / D 50 = Q represents a measure of the distribution width of the particle size. Rubber-elastic graft copolymers A ^K preferably have Q values of less than 0.5, in particular less than 0.35.

The acrylate rubbers A1 are preferably alkyl acrylate rubbers of one or more C _1-8 -alkyl acrylates, preferably C _4-8 -alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n Butyl and 2-ethylhexyl acrylate is used. These alkyl acrylate rubbers may contain up to 30% by weight of polymers which form hard polymers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate, vinyl ethers.

The Acrylate rubbers also contain 0.01-20 wt .-%, preferably 0.1-5 wt .-%, on crosslinking, polyfunctional monomers (crosslinking monomers). Examples of this are monomers which have 2 or more double bonds capable of copolymerizing which are preferably not conjugated in the 1,3-positions are.

suitable Crosslinking monomers are, for example, divinylbenzene, diallyl maleate, Diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, Tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, Allyl acrylate, allyl methacrylate. As a particularly favorable crosslinking monomer dicyclopentadienyl acrylate (DCPA) has been found (see DE-PC 12 60 135).

The component A ^K is a graft copolymer. The graft copolymers A ^K have an average particle size d ₅₀ of 50-1000 nm, preferably of 50-800 nm and particularly preferably of 50-600 nm. These particle sizes can be achieved if, as the grafting base A1, particle sizes of 50-800 nm, preferably used of 50-500 nm and more preferably of 50-250 nm. The graft copolymer A ^K is generally one or more stages, ie a polymer composed of a core and one or more shells. The polymer consists of a base (graft) A1 and one or - preferably - more grafted on steps A2 (graft), the so-called grafting or grafting.

By simple grafting or multiple stepwise grafting can one or more grafts be applied to the rubber particles, each graft a other composition may have. In addition to the grafting monomers can polyfunctional crosslinking or reactive group-containing monomers with grafted on (see, for example, EP-A 230 282, DE-AS 36 01 419, EP-A 269 861).

In a preferred embodiment, component A ^K consists of a multistage graft copolymer, wherein the grafting steps are generally prepared from resin-forming monomers and have a glass transition temperature T _g above 30 ° C., preferably above 50 ° C. The multi-stage structure serves inter alia to achieve (partial) compatibility of the rubber particles A ^K with the thermoplastic matrix.

Graft copolymers A ^K are prepared, for example, by grafting at least one of the monomers A2 listed below onto at least one of the grafting bases or grafted core materials A1 listed above.

According to one embodiment the invention, the graft A1 is 15-99 wt .-% acrylate rubber, 0.1-5 % By weight of crosslinker and 0-49.9 Wt .-% of one of the stated further monomers or rubbers composed.

suitable Monomers for forming the graft A2 are styrene, α-methylstyrene, (meth) acrylic acid ester, Acrylonitrile and methacrylonitrile, in particular acrylonitrile.

According to one embodiment The invention serves as the grafting base A1 crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. The crosslinked acrylic acid ester polymers should preferably have a glass transition temperature below -20 ° C, in particular below -30 ° C, own.

In a preferred embodiment the graft A2 consists of at least one graft and the outermost graft shell of it has a glass transition temperature of more than 30 ° C, where a polymer formed from the monomers of the graft A2 Glass transition temperature of more than 80 ° C would have.

Suitable preparation processes for graft copolymers A ^K are the emulsion, solution mass or suspension polymerization. The graft copolymers A ^K are preferably prepared by free-radical emulsion polymerization in the presence of latexes of component A1 at temperatures of 20 ° C.-90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.

suitable Emulsion polymerization processes are described in DE-A 28 26 925, 31 49 358 and in DE-C 12 60 135.

Of the Structure of the graft sheaths is preferably carried out in the emulsion polymerization process as described is in DE-A 32 27 555, 31 49 357, 31 49 358, 34 14 118. The defined Adjustment of the particle sizes of 50-1000 nm is preferably carried out according to the methods described in DE-C 12 60 135 and DE-A 28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929. The use of polymers with different Particle sizes for example, known from DE-A 28 26 925 and US-A 5,196,480.

According to the in DE-C 12 60 135 described method is first the Grafting A1 prepared by the or the according to a embodiment acrylic acid esters used in the invention and the polyfunctional, the networking effecting monomers, if necessary together with the other comonomers, in aqueous emulsion in known per se Way at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, be polymerized. It can the usual Emulsifiers, such as, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, Fatty alcohol sulfonates, higher salts fatty acids with 10 to 30 carbon atoms or resin soaps. Preferably, the sodium salts of alkyl sulfonates are used or fatty acids with 10 to 18 carbon atoms. According to one embodiment are the emulsifiers in amounts of 0.5-5 wt .-%, in particular of 1-2% by weight, based on the monomers used in the preparation of the grafting base A1, used. In general, at a weight ratio of Water to monomers from 2: 1 to 0.7: 1 worked. As polymerization initiators In particular, the customary persulfates, such as potassium persulfate. However, redox systems can also be used to be used. The initiators are generally in amounts from 0.1-1 Wt .-%, based on that in the preparation of the graft A1 used monomers used. As further polymerization auxiliaries can the usual Buffer substances, by which adjusted pH values of preferably 6-9 such as sodium bicarbonate and sodium pyrophosphate, as well as 0-3% by weight a molecular weight regulator, such as mercaptans, terpinols or dimers a-methylstyrene, to be used in the polymerization.

The exact polymerization conditions, in particular the type, dosage and amount of the emulsifier are determined in detail within the ranges given above such that the resulting latex of the crosslinked acrylic ester polymer has a d ₅₀ value in the range of about 50-800 nm, preferably 50-500 nm , more preferably in the range of 80-250 nm. The particle size distribution of the latex should preferably be narrow.

For the preparation of the graft polymer A ^K , a monomer mixture of styrene and acrylonitrile is then polymerized in a next step in the presence of the thus obtained latex of the crosslinked acrylic acid ester polymer, wherein the weight ratio of styrene to acrylonitrile in the monomer mixture according to an embodiment of the Invention in the range of 100: 0 to 40: 60, preferably in the range of 65: 35 to 85: 15, should lie. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylate polymer used as the grafting base again in aqueous emulsion under the customary conditions described above. The graft copolymerization may suitably be carried out in the same system as the emulsion polymerization for the preparation of the graft A1, wherein, if necessary, further emulsifier and initiator may be added. The monomer mixture of styrene and acrylonitrile to be grafted on in accordance with one embodiment of the invention can be added to the reaction mixture at once, batchwise in several stages or preferably continuously during the polymerization. The graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out so that a grafting degree of 1-99 wt .-%, preferably 20-45 wt .-%, in particular 35-45 wt .-%, based on the Total weight of the component A ^K , resulting in the graft copolymer A ^K. Since the graft yield in the graft copolymerization is not 100%, a slightly larger amount of the monomer mixture of styrene and acrylonitrile must be used in the graft copolymerization, as it corresponds to the desired degree of grafting. The control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A ^K is familiar to the skilled worker and can be done, for example, by the metering rate of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 et seq. ). In the emulsion graft copolymerization arise in general NEN about 5-15 wt .-%, based on the graft copolymer, of free, ungrafted styrene / acrylonitrile copolymer. The proportion of the graft copolymer A ^K in the polymerization product obtained in the graft copolymerization is determined by the method indicated above.

In the preparation of the graft copolymers A ^K by the emulsion process, reproducible particle size changes are possible in addition to the given procedural advantages, for example by at least partial agglomeration of the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A ^K. In particular, the component A ^K of the graft base and the graft shell (s) can be optimally adapted for the respective intended use, in particular with regard to the particle size.

The graft copolymers A ^K generally contain 1-99 wt .-%, preferably 55-80 and particularly preferably 55-65 wt .-% of the graft A1 and 1-99 wt .-%, preferably 20-45, particularly preferably 35-45 Wt .-% of the graft A2, each based on the total graft copolymer.

Under ABS polymers are generally understood to be impact-modified SAN polymers, in which diene polymers, in particular 1,3-polybutadiene, in a copolymer matrix in particular styrene and / or α-methylstyrene and acrylonitrile available.

In a preferred embodiment, in which the plastic mixtures comprise ABS polymers, the rubber-elastic graft copolymer A ^K 'of component A is composed of
a1 'from 10 to 90% by weight of at least one rubber-elastic graft base having a glass transition temperature below 0 ° C., obtainable by polymerization of, based on A1',
a11 'from 60 to 100, preferably from 70 to 100,% by weight of at least one conjugated diene and / or C ₁ - to C ₁₀ -alkyl acrylate, in particular butadiene, isoprene, n-butyl acrylate and / or 2-ethylhexyl acrylate,
a12'0 to 30, preferably 0 to 25 wt .-% of at least one further monoethylenic unsaturated monomer, in particular styrene, α-methylstyrene, n-butyl acrylate, methyl methacrylate or mixtures thereof, among the latter in particular butadiene / styrene and n-butyl acrylate / styrene -Copolymers, and
a13'0 to 10, preferably 0 to 6 wt .-% of at least one crosslinking monomer, preferably divinylbenzene, diallyl maleate, allyl esters of (meth) acrylic acid, Dihydrodicyclopentadienylacrylat, dinvinyl esters of dicarboxylic acids such as succinic and adipic and diallyl and divinyl ether bifunctional alcohols such as ethylene glycol or butane-1,4-diol,
a2 'from 10 to 60, preferably 15 to 55 wt .-% of a graft A2' from, based on A2 ',
a21 'from 50 to 100, preferably from 55 to 90,% by weight of at least one vinylaromatic monomer, preferably styrene and / or α-methylstyrene,
a22 'from 5 to 35, preferably from 10 to 30,% by weight of acrylonitrile and / or methacrylonitrile, preferably acrylonitrile,
a23 '0 to 50, preferably 0 to 30 wt .-% of at least one further monoethylenically unsaturated monomer, preferably methyl methacrylate and n-butyl acrylate.

In a further preferred embodiment, in which the plastic mixtures contain ABS, component A ^K 'is a graft rubber with a bimodal particle size distribution, based on A ^K ',
a1 '' 40 to 90, preferably 45 to 85 wt .-% of a rubbery elastic particulate grafting base A1 '', obtainable by polymerization of, based on A1 '',
a11 '' 70 to 100, preferably 75 to 100 wt .-% of at least one conjugated diene, in particular butadiene and / or isoprene,
a12 '' 0 to 30, preferably 0 to 25 wt .-% of at least one further monoethylenic unsaturated monomer, in particular styrene, α-methyl styrene, n-butyl acrylate or mixtures thereof,
a2 '' from 10 to 60, preferably 15 to 55 wt .-% of a graft A2 '' from, based on A2 '',
a21 '' from 65 to 95, preferably from 70 to 90,% by weight of at least one vinylaromatic monomer, preferably styrene,
a22 '' from 5 to 35, preferably from 10 to 30% by weight of acrylonitrile,
a23 '' 0 to 30, preferably 0 to 20 wt .-% of at least one further monoethylenically unsaturated monomer, preferably methyl methacrylate and n-butyl acrylate.

In a preferred embodiment, in which the plastic mixtures comprise ASA polymers as component A, the hard matrix A ^M of component A is at least one hard copolymer containing units derived from vinyl aromatic monomers, and wherein, based on the total weight of vinylaromatic monomers of dissipative units, 0-100 wt .-%, preferably 40-100 wt .-%, particularly preferably 60 to 100 wt .-% of α-methyl styrene and 0-100 wt .-%, preferably 0-60 wt %, more preferably 0-40% by weight of units deriving from styrene, from, based on A ^M ,
a ^M 1 40-100% by weight, preferably 60-85% by weight, of vinylaromatic units as component A ^M 1,
a ^M 2 to 60 wt .-%, preferably 15-40 wt .-%, units of acrylonitrile or methacrylonitrile, in particular of the acrylonitrile as component A ^M 2.

In a preferred embodiment, in which the plastic mixtures ABS polymers as Component A, the hard matrix A ^M 'of component A is at least one hard copolymer containing units derived from vinyl aromatic monomers, and wherein, based on the total weight of vinyl aromatic monomers derived units, 0-100 wt .-% , preferably 40-100 wt .-%, particularly preferably 60 to 100 wt .-% of α-methyl styrene and 0-100 wt .-%, preferably 0-60 wt .-%, particularly preferably 0-40 wt. % of styrene-derived units are taken from, based on A ^M ',
a ^M 1 'from 50 to 100, preferably from 55 to 90% by weight of vinylaromatic monomers,
a ^M 2 '0 to 50 wt .-% of acrylonitrile or methacrylonitrile or mixtures thereof,
a ^M 3 '0 to 50 wt .-% of at least one further monoethylenically unsaturated monomers, for example methyl methacrylate and N-alkyl or N-Arylmaleinimide such as N-phenylmaleimide.

In a further, preferred embodiment in which the plastic mixtures contain ABS as component A, component A ^M 'is at least one hard copolymer having a viscosity number VZ (determined according to DIN 53726 at 25 ° C. in 0.5% strength by weight solution in Dimethylformamide) of 50 to 120 ml / g, which contains units derived from vinyl aromatic monomers, and wherein, based on the total weight of vinyl aromatic monomers dissipative units, 0-100 wt .-%, preferably 40-100 wt. %, particularly preferably 60 to 100 wt .-% of α-methyl styrene and 0-100 wt .-%, preferably 0-60 wt .-%, particularly preferably 0-40 wt .-% of styrene-derived units are included , from, relative to A ^M '
a _M 1 '' from 69 to 81, preferably from 70 to 78% by weight of vinylaromatic monomers,
a _M 2 "19 to 31, preferably 22 to 30 wt .-% acrylonitrile,
a _M 3 '' 0 to 30, preferably 0 to 28 wt .-% of at least one further, monoethylenically unsaturated monomers, for example methyl methacrylate or N-alkyl or N-Arylmaleinimide such as N-phenylmaleimide.

In one embodiment, components A ^M 'are present side by side in the ABS polymers which differ in their viscosity numbers VZ by at least five units (ml / g) and / or in their acrylonitrile contents by five units (% by weight) , Finally, in addition to the component A ^M 'and the other embodiments, copolymers of (α-methyl) styrene and maleic anhydride or maleimides, from (α-methyl) styrene, maleimides and methyl methacrylate or acrylonitrile, or from (α-methyl) stryol, maleimides , Methyl methacrylate and acrylonitrile.

In the case of these ABS polymers, the graft polymers A ^{K 'are} preferably obtained by means of emulsion polymerization. The mixing of the graft polymers A ^{K '} with the components A ^M ' and optionally further additives is generally carried out in a mixing apparatus, wherein a substantially molten polymer mixture is formed. It is advantageous to cool the molten polymer mixture as quickly as possible.

For the rest production and general as well as special embodiments the aforementioned ABS polymers in the German patent application DE-A 19728629 described in detail, to which hereby express reference is taken. The abovementioned ABS polymers may contain other customary auxiliary and fillers exhibit. Such substances are, for example, lubricants or mold release agents, Waxes, pigments, dyes, flame retardants, antioxidants, Stabilizers against exposure to light or antistatic agents.

According to a preferred embodiment of the invention, the viscosity number of the hard matrices A ^M and A ^M 'of the component A is 50-90, preferably 60-80.

Preferably, the hard matrices A ^M and A ^M 'of the component A are amorphous polymers. According to one embodiment of the invention, mixtures of a copolymer of styrene with acrylonitrile and of a copolymer of α-methylstyrene with acrylonitrile are used as hard matrices A ^M or A ^M 'of component A. The acrylonitrile content in these copolymers of hard matrices is 0-60 wt .-%, preferably 15-40 wt .-%, based on the total weight of the hard matrix. The hard matrices A ^M or A ^M 'of component A also include the free, ungrafted (α-methyl) styrene / acrylonitrile copolymers which are formed in the graft copolymerization to prepare component A ^K or A ^K '. Depending on the conditions used in the graft copolymerization for the preparation of the graft copolymers A ^K or A ^K ', it may be possible that a sufficient proportion of hard matrix has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately prepared hard matrix.

The additional, separately prepared hard matrices A ^M and A ^M 'of component A can be obtained by the conventional methods. Thus, according to one embodiment of the invention, the copolymerization of the styrene and / or α-methylstyrene with the acrylonitrile in bulk, solution, suspension or aqueous emulsion can be carried out. The components A ^M and A ^M 'preferably have a viscosity number of 40 to 100, preferably 50 to 90, in particular 60 to 80. The determination of the viscosity number is carried out according to DIN 53 726, thereby 0.5 g of material is dissolved in 100 ml of dimethylformamide.

The mixing of the components A ^K (or A ^K ') and A ^M (or A ^M ') can be carried out in any manner by all known methods. If these components have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, then jointly precipitate the polymers and work up the polymer mixture. Preferably, however, the mixing of these components is carried out by coextruding, kneading or rolling the components, wherein the components, if necessary, have previously been isolated from the solution or aqueous dispersion obtained in the polymerization. The products of the graft copolymerization obtained in aqueous dispersion can also be only partially dewatered and mixed as a moist crumb with the hard matrix, in which case the complete drying of the graft copolymers takes place during the mixing.

Thermoplastic elastomers based on styrene:

Preferred thermoplastic elastomers based on styrene (S-TPE) are those having an elongation at break of more than 300%, particularly preferably more than 500%, in particular more than 500% to 600%. Particularly preferred as S-TPE is mixed a linear or star-shaped styrene-butadiene block copolymer with outermost polystyrene blocks S and styrene-butadiene random styrene / butadiene _random copolymer blocks (S / B) _random or a styrene gradient (S / B) _taper to.

Of the Total butadiene content is preferably in the range of 15 to 50 wt .-%, most preferably in the range of 25 to 40 wt .-%, the total styrene content is suitably in the range of 50 to 85 wt .-%, especially preferably in the range of 60 to 75 wt .-%.

Preferably The styrene-butadiene block (S / B) consists of 30 to 75 wt .-% of styrene and 25 to 70% by weight of butadiene. Particularly preferred is a block (S / B) a Butadienanteil of 35 to 70 wt .-% and a styrene content from 30 to 65% by weight.

Of the Proportion of polystyrene blocks S is preferably in the range of 5 to 40 wt .-%, in particular in Range of 25 to 35 wt .-%, based on the total block copolymer. The proportion of copolymer blocks S / B is preferably in the range of 60 to 95 wt .-%, in particular in the range of 65 to 75 wt .-%.

Particular preference is given to linear styrene-butadiene block copolymers of the general structure S- (S / B) -S with one or more _random styrene / butadiene distribution blocks (S / B) _randomly situated between the two S blocks Block copolymers are obtainable by anionic polymerization in a non-polar solvent with the addition of a polar cosolvent or a potassium salt, as described, for example, in WO 95/35335 or WO 97/40079.

When Vinyl content is the relative proportion of 1,2-linkages the diene units based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages Understood. The 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range of 10 to 18%, particularly preferably in the range from 12-16%.

polyolefins:

The Polyolefins which can be used as components A generally have breaking elongations from 10% to 600%, preferably 15% to 500%, especially preferred 20% up to 400%.

When Component A are, for example, partially crystalline polyolefins, such as homo- or copolymers of ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1 and ethylene copolymers with vinyl acetate, vinyl alcohol, ethyl acrylate, Butyl acrylate or methacrylate. Preference is given as component A a High-density polyethylene (HDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Polypropylene (PP), ethylene-vinyl acetate copolymer (EVA) or Ethylene-acrylic copolymer used. A particularly preferred Component A is polypropylene.

polycarbonates:

The As components A usable polycarbonates usually have elongation at break from 20% to 300%, preferably from 30% to 250%, particularly preferably 40% up to 200%.

The polycarbonates suitable as component A preferably have a molecular weight (weight average M _w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range of 10,000 to 60,000 g / mol. They are obtainable, for example, according to the processes of DE-B-1 300 266 by interfacial polycondensation or according to the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as hereinafter referred to as bisphenol A.

Instead of bisphenol A, other aromatic dihydroxy compounds may also be used in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1 , 1-di (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or Dihydroxydiphenylcycloalkane, preferably Dihydroxydiphenylcyclohexane or Dihydroxylcyclopentane, in particular 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.

Especially preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the above aromatic dihydroxy compounds.

Particularly suitable as component A suitable polycarbonates are those which contain units derived from Resorcinol- or Alkylresorcinolestern, as described for example in WO 00/61664, WO 00/15718 or WO 00/26274; These polycarbonates are marketed, for example, General Electric Company under the trademark SollX ^®.

It can also copolycarbonates according to US-A 3,737,409 are used; Of particular interest are Copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, characterized by a high heat resistance distinguished. It is also possible Use mixtures of different polycarbonates.

The average molecular weights (weight average M _w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates according to the invention are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. The relative solution viscosities of the polycarbonates used preferably do not differ by more than 0.05, in particular not more than 0.04.

The Polycarbonates can be used both as regrind and in granulated form.

Thermoplastic polyurethane:

In general, suitable as component A is any aromatic or aliphatic thermoplastic polyurethane, preferably amorphous aliphatic thermoplastic polyurethanes which are transparent are suitable. Aliphatic thermoplastic polyurethanes and their preparation are known in the art, for example from EP-B1 567 883 or DE-A 10321081, and are commercially available, for example under the trade marks Texin ^® and Desmopan ^® Bayer Aktiengesellschaft.

preferred Aliphatic thermoplastic polyurethanes have a Shore D hardness of 45 to 70, and a breaking elongation from 30% to 800%, preferably 50% to 600%, especially preferred 80% up to 500%.

Especially Preferred components A are the thermoplastic elastomers Base of styrene.

component B

When Component B are all metal powders having an average particle diameter from 0.01 to 100 μm, preferably from 0.1 to 50 μm, more preferably from 1 to 10 μm, suitable (determined by laser diffraction measurement on a device Microtrac X100), if the metal has a more negative normal potential in acidic solution as silver.

suitable Metals are, for example, Zn, Ni, Cu, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi. The metals can in the form of the metal used or - when using different Metals - in Form of alloys of said metals with each other or with other metals are deposited. Suitable alloys are for example CuZn, CuSn, CuNi, SnPb, SnBi, SnCu, NiP, ZnFe, ZnNi, ZnCo and ZnMn. Preferably usable metal powders are iron powder and copper powder, especially iron powder.

The Metal powder particles can in principle have any shape, for example, needle-shaped, plate-shaped or are spherical metal particles can be used, preferably spherical and plate-shaped. Such metal powder are common commodities or can be easily prepared by known methods, such as 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, in particular in cooling media, for example gases or water.

In Particularly preferred are metal powder with spherical particles, especially carbonyl iron powder used.

The preparation of carbonyl iron powders by thermal decomposition of iron pentacarbonyl is known and is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599. The decomposition The iron pentacarbonyl may, for example, be carried out at elevated temperatures and elevated pressures in a heatable decomposer comprising a tube of a refractory material such as quartz glass or V2A steel in a preferably vertical position provided by a heater, for example consisting of heating bands, heating wires or one of a heating medium flowed through heating jacket is surrounded.

The average particle diameter of the separating carbonyl iron powder can by the process parameters and reaction in the decomposition in be controlled within wide ranges and are usually at 0.01 up to 100 μm, preferably from 0.1 to 50 μm, more preferably from 1 to 10 microns.

component C

When Component C are basically all the specialist for the application in plastic mixtures known and in the state of Technique described dispersants 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), Volume 5, pages 816 to 818, and in "Emulsion Polymerization and Emulsion Polymers, ed P. Lovell and M. EI-Asser, Publisher Wiley & Sons (1997), pages 224-226, described.

Examples of anionic surfactants are alkali metal salts of organic carboxylic acids having chain lengths of 8-30 carbon atoms, preferably 12-18 carbon atoms. These are commonly referred to as soaps. They are usually used as sodium, potassium or ammonium salts. In addition, alkyl sulfates and alkyl or alkylaryl sulfonates having 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms, can be used as anionic surfactants. Particularly suitable compounds are alkali dodecyl sulfates, for example sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali metal salts of C ₁₂ -C ₁₆ paraffin sulfonic acids. Furthermore, sodium dodecylbenzenesulfonate and sodium dioctylsulfone succinate are suitable.

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

Especially can nonionic according to the invention Surfactants are used as component C. Nonionic surfactants For example, in CD Römpp Chemistry Lexicon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "nonionic surfactants" described.

Suitable nonionic surfactants include for example polyethylene oxide or polypropylenoxidbasierte substances such as Pluronic ^® and Tetronic ^® from BASF Aktiengesellschaft. Polyalkylene glycols suitable as nonionic surfactants generally have a molecular weight M _n in the range from 1000 to 15000 g / mol, preferably 2000 to 13000 g / mol, particularly preferably 4000 to 11000 g / mol. Preferred nonionic surfactants are polyethylene glycols.

The Polyalkylene glycols are known per se or can be known per se Process, for example by anionic polymerization with alkali hydroxides, such as sodium or potassium hydroxide or alkali alcoholates, such as sodium methylate, Sodium or potassium ethylate or potassium isopropylate, as catalysts and with the addition of at least one starter molecule containing 2 to 8, preferably Contains 2 to 6 bonded to reactive hydrogen atoms, or by cationic Polymerization with Lewis acids, such as Antimony pentachloride, borofluoride etherate or bleaching earth, as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms be prepared 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 individually, alternating successively or used as mixtures. As starter molecules For example: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid or terephthalic acid, aliphatic or aromatic, optionally N-mono-, N, N- or N, N'-dialkyl substituted diamines with 1 to 4 carbon atoms in the alkyl radical, such as 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.

When starter molecules further contemplated are: alkanolamines, e.g. Ethanolamine, N-methyl- and N-ethyl-ethanolamine, Dialkanolamines, e.g. Diethanolamine, N-methyl- and N-ethyl-diethanolamine, and Trialkanolamines, e.g. Triethanolamine, and ammonia. Preferably be used polyvalent, in particular two-, trivalent or higher Alcohols, such as ethanediol, 1,2-propanediol and 1,3-diethylene glycol, Dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, Pentaerythritol, and sucrose, sorbitol and sorbitol.

When Component C also suitable are esterified polyalkylene glycols, for example, the mono-, di-, tri- or polyesters of the mentioned Polyalkylene glycols by reaction of the terminal OH groups of said Polyalkylene glycols with organic acids, preferably adipic acid or terephthalic acid, can be produced in a conventional manner. As component C is Polyethylene glycol adipate or polyethylene glycol terephthalate preferred.

Especially suitable nonionic surfactants are by alkoxylation of compounds substances produced with active hydrogen atoms, for example Addition products of ethylene oxide with fatty alcohols, oxo alcohols or alkylphenols. Ethylene oxide is preferred for the alkoxylation or 1,2-propylene oxide used.

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

sugar ethers are by reaction of fatty alcohols with sugars obtained alkyl glycosides, sugar esters are obtained by reacting sugars with fatty acids. The for the production of the substances mentioned Sugars, fatty alcohols and fatty acids are known in the art.

suitable Sugar, for example, Beyer / Walter, textbook of organic Chemie, S. Hirzel Verlag Stuttgart, 19th edition, 1981, pp. 392 to 425 described. Particularly suitable sugars are D-sorbitol and those by Dehydration of D-sorbitol-derived sorbitans.

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, such as in CD Römpp Chemistry Lexicon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "fatty acids" are called. Preferred fatty acids are lauric acid, Palmitic acid, stearic acid and oleic acid.

suitable Fatty alcohols have the same carbon skeleton as those described as suitable fatty acids Links.

sugar ethers, Sugar esters and the processes for their preparation are those skilled in the art known. Preferred sugar ethers are prepared by known methods by reacting said sugars with said fatty alcohols produced. Preferred sugar esters are prepared by known methods Implementation of the mentioned sugars made with said fatty acids. Preferred 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 dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate, Sorbitan tristearate and sorbitan sesquioleate, a mixture of sorbitan mono- and diesters of oleic acid.

Especially suitable components C are alkoxylated sugar ethers and sugar esters which are obtained by alkoxylation of the cited 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, particularly preferably 2 and 6. Particularly preferred alkoxylated sugar esters 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". Particularly preferred polysorbates are polyethoxysorbitan, stearate, palmitate, tristearate, oleate, trioleate, especially polyethoxysorbitan which eg as Tween ^® 60 from ICI America Inc. (described for example in CD Rompp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Tween ^® ").

component D

When Component D contain the plastic mixtures fibrous or particulate fillers or their mixtures. This is preferably a commercial one available Products, such as carbon fibers and glass fibers.

usable Glass fibers can be made of E, A or C glass and are preferably with a sizing and a bonding agent. Their diameter is generally between 6 and 20 microns. It can both Continuous fibers (rovings) as well as chopped glass fibers (staple) with a Length of 1-10 mm, preferably 3-6 mm, are used.

Farther can Filling or Reinforcing materials, such as glass beads, mineral fibers, whiskers, alumina fibers, mica, Quartz flour and wollastonite are added.

The Plastic mixture can further contain other additives used in plastics processing typical and in use are.

Examples of such additives include dyestuffs, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the stability to light, to increase the hydrolysis resistance and resistance to chemicals, anti-heat decomposition agents and, in particular, lubricants tel, which are useful for the production of moldings or moldings. The dosing of these other additives can be done at any stage of the manufacturing process, but preferably at an early stage, to take advantage of the stabilizing effects (or other specific effects) of the additive at an early stage. Heat stabilizers or antioxidants are usually metal halides (chlorides, bromides, iodides), which are derived from metals of Group I of the Periodic Table of the Elements (such as Li, Na, K, Cu).

suitable Stabilizers are the usual hindered Phenols, but also vitamin E or analogous compounds. Also HALS stabilizers (hindered amine light stabilizers), benzophenones, Resorcinols, salicylates, benzotriazoles such as TinuvinRP (UV absorber 2 - (2 N -benzotriazol-2-yl) -4-methylphenol the CIBA) and other compounds are suitable. These are usually in amounts of up to 2% by weight (based on the total mixture of the plastic mixture) used.

suitable Lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid ester or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12-30 carbon atoms. The quantities of these additives are in the range of 0.05-1 Wt .-%.

Also Silicone oils, oligomeric isobutylene or the like Substances come as additives in question, the usual amounts are 0.05-5 wt .-%. Pigments, dyes, color-whiteners, such as ultramarine blue, phthalocyanines, Titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid also usable.

processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are becoming common in amounts of 0.01-5 % By weight used.

Method:

Of the first step of the method according to the invention is the melt mixing and extrusion of the described plastic mixture.

Basically all accessible by extrusion Plastic items according to the inventive method malleable. Preferred extruded plastic articles are films, plates, profiles, Pipes and strands. These can in principle be produced by extrusion processes known to the person skilled in the art.

To the methods of the invention are also accessible multilayer plastic objects. This can be achieved by coextrusion, laminating or laminating For example, produce composite layer films or plates. By Injection, casting behind or backing with thermoplastic molding materials or foam or Backpresses with thermosetting molding compounds are multilayered Moldings accessible.

preferred Plastic items and their preparation will be described below.

method for the production of extruded films or plates

The Production of the thermoplastic molding compositions for the production of extruded films or sheets of components A, B and, if present, C and D are carried out by methods known to those skilled in the art, for example, by mixing the components in the melt with known in the art devices at temperatures that vary depending on the type of the polymer A used usually in the range of 150 to 300 ° C, especially at 200 to 280 ° C, lie. The components can be supplied in each case pure form the mixing devices. It can but also individual components, such as A and B, premixed first and subsequently with other components A or B or other components, for example C and D, are mixed. In one embodiment, a first Concentrate, for example components B, C or D in the component A produced (so-called additive batches) and then with the desired Quantities of the remaining components mixed. The plastic mixtures can after processes known to the person skilled in the art are processed into granules, at a later date to the films of the invention or sheets to be extruded. But you can also directly afterwards to the mixing process or in one step with the mixing process (i.e., simultaneous melt blending and extrusion), preferably by means of a screw extruder, extruded into the films or plates according to the invention become.

In a preferred embodiment the inventive method is the screw extruder as a single screw extruder with at least executed a distributive mixing screw element.

In a further preferred embodiment the inventive method is the screw extruder as a twin-screw extruder with at least executed a distributive mixing screw element.

The processes for the extrusion of the films or plates can be carried out by methods known to the person skilled in the art and described in the prior art, for example Slot extrusion as adapter or die coextrusion, and with devices known to those skilled in the art and described in the prior art.

Depending on the polymer used as component A, the type and amount of the other components are chosen so that the plastic mixtures comprising the components A, B and, if present, C and D have tear strengths within the following ranges:
from 10% to 1000%, preferably from 20% to 700%, preferably from 50% to 500% (for S-TPE and polyethylene as component A),
from 10% to 300%, preferably from 12% to 200%, preferably from 15% to 150% (for polypropylene as component A),
from 20% to 300%, preferably from 30% to 250%, particularly preferably from 40% to 200% (for polycarbonates as component A),
from 10% to 300%, preferably from 15 to 250%, more preferably from 20% to 200% (for styrene polymers and PVC as component A).

The Extruded sheets or plates usually have a total thickness of 20 μm to 5 mm, preferably 70 μm up to 3 mm, more preferably 100 μm to 1.5 mm.

Laminated sheets or sheets

The extruded films or plates are particularly suitable as a cover layer (3) multilayer composite sheets or films other than the Cover layer at least one substrate layer (1) of thermoplastic Plastic have. In further embodiments, the composite layer plates or films additional layers (2), for example color, adhesion promoter or intermediate layers, comprise, between the cover layer (3) and the substrate layer (1) are arranged.

The Substrate layer (1) can in principle from any thermoplastic Be constructed plastic. The substrate layer (1) is preferred from the above, related to the extruded sheets or plates impact-modified vinyl aromatic copolymers, thermoplastic elastomers Base of styrene, polyolefins, polycarbonates and thermoplastic Polyurethanes or mixtures thereof prepared, particularly preferred from ASA, ABS, SAN, polypropylene and polycarbonate or mixtures thereof.

layer (2) is different from the layers (1) and (3), for example due to one of these different polymer composition and / or differing additive levels such as colorants or Effect pigments. Layer (2) may, for example, a coloring Layer, preferably dyes known to those skilled in the art, Color pigments or effect pigments, such as mica or aluminum flakes or Mica, may contain. Layer (2) can also be an improvement the mechanical stability composite laminates or films, or an adhesion promoter between layers (1) and (3).

A embodiment The invention relates to a composite layer plate or film a substrate layer (1), covering layer as described above (3) and an intervening intermediate layer (2) consisting of aliphatic thermoplastic polyurethane, impact polymethyl methacrylate (PMMA), polycarbonate or styrene (co) polymers such as SAN, which impact can be modified For example, ASA or ABS, or mixtures of these polymers constructed is.

Becomes aliphatic thermoplastic polyurethane as the material of the intermediate layer (2), the aliphatic one described under layer (3) may be used thermoplastic polyurethane can be used.

Becomes Polycarbonate used as an intermediate layer (2), so under Layer (3) described polycarbonate can be used.

Impact-resistant PMMA (high impact PMMA: HI-PMMA) is a polymethyl methacrylate, which can be replaced by additions impact equipped is. Suitable impact-modified PMMA are described for example by M. Stickler, T. Rhein in Ullmann's encyclopedia of industrial chemistry Vol. A21, pages 473-486, VCH Publishers Weinheim, 1992, and H. Domininghaus, The Plastics and Their Properties, VDI-Verlag Düsseldorf, 1,992th

The Layer thickness of the above composite laminated sheets or foils is usually 15 to 5000 μm, preferably 30 to 3000 μm, more preferably 50 to 2000 microns.

In a preferred embodiment The invention consists of the composite layer plates or sheets a substrate layer (1) and a cover layer (3) with the following Layer thicknesses: substrate layer (1) 50 μm to 1.5 mm; Cover layer (3) 10-500 μm.

In a further preferred embodiment of the invention, the composite layer plates or sheets consist of a substrate layer (1), an intermediate layer (2) and a cover layer (3). Composite layer plates or sheets of a substrate layer (1), an intermediate layer (2) and a cover layer (3) preferably have the following Layer thicknesses on: substrate layer (1) 50 μm to 1.5 mm; Intermediate layer (2) 50 to 500 μm; Cover layer (3) 10-500 μm.

In addition to the layers mentioned, the composite layer plates or foils may also have on the side of the substrate layer (1) facing away from the cover layer (3) further layers, preferably an adhesion promoter layer, which results in improved adhesion of the composite layer plates or foils to the carrier layer which will be described below serve. Such adhesion promoter layers are preferably prepared from a polyolefin-compatible material, such as, for example, SEBS (styrene-ethylene-butadiene-styrene copolymer, marketed, for example, under the trademark ^Kraton® ). If such a primer layer is present, it preferably has a thickness of 10 to 300 μm.

The Composite laminate sheets or films can be made according to known and in Method described in the prior art (for example in WO 04/00935), for example, by adapter or coextrusion or stacking or laminating the layers. In the coextrusion process become the components forming the individual layers in extruders made flowable and over special devices so brought into contact with each other the composite laminate sheets or foils having the above-described Layer sequence result. For example, the components may be through a slot die or a multi-layer die tool be coextruded. This method is described in EP-A2-0 225 500 explained.

moreover can they are made by the adapter coextrusion process, such as it in the proceedings of the symposium Extrusion Technology "Coextrusion of Films", 8./9. October 1996, VDI-Verlag Düsseldorf, especially contribution of Dr. med. Networks is described. This economic Process is used in most coextrusion applications.

Farther can laminating the composite laminates and sheets together or laminating films or sheets in a heatable gap getting produced. First, the described layers corresponding films or plates produced separately. This can done by known methods. Then the desired layer sequence by appropriate overlapping the films or plates made, whereupon this example be passed through a heated nip and under pressure and the effect of heat be connected to a composite layer plate or film.

Especially In the case of the adapter coextrusion process, a matching of the flow properties of the individual components advantageous for the formation of uniform layers in the composite laminate sheets or foils.

moldings

The extruded sheets or sheets and the composite sheets or films comprising the extruded films of the invention or Plates can be used for the production of moldings. Any are Molded parts, preferably flat, especially large area, accessible. Particularly preferred are these extruded sheets or plates and composite laminates or foils for the production of molded parts used, where it is very good toughness, good adhesion the individual layers to each other and a good dimensional stability arrives, so that, for example, a destruction by peeling off the surfaces is minimized. Particularly preferred moldings have monofilms or composite laminates or foils comprising the extruded ones Foils or plates and a back-injected, foam-backed, back-poured or behind pressed carrier layer made of plastic.

The Production of molded parts from the extruded films or plates or the composite laminate sheets or foils may be known in the art and, for example, in WO 04/00935 method described (In the following the methods for the further processing of composite layer plates or However, these methods are also for further processing the extruded invention Foils or plates can be used). The composite layer plates or films can behind injected, backfoamed, back-poured without further processing stage or be pressed behind. In particular, the use of the described allows Laminated sheets or foils also make a manufacture easily three-dimensional components without a prior thermoforming. The However, composite laminates or foils can also be a previous one For example, composite laminates may be subjected or films with the three-layer structure of substrate layer, intermediate layer and Cover layer or the two-layer structure of substrate layer and cover layer For the production of more complex components formed by thermoforming become. It can both positive and negative thermoforming used become. Corresponding methods are known to the person skilled in the art. To the thermoforming process can the composite layer plates or films of further shaping steps, For example, contour cuts, be subjected.

From the composite layer plates or foils can, if necessary, after the described thermoforming processes, by back injection, foam back, Casting or rear molding the moldings of the invention are produced. These processes are known to the person skilled in the art and are described, for example, in DE-A1 100 55 190 or DE-A1 199 39 111.

By Injection, backfoaming, back-casting or backing the composite laminations with a plastic material receives one the moldings according to the invention. Preference is given to injection molding, back-molding or back-casting as plastic materials thermoplastic molding compositions based on ASA or ABS polymers, SAN polymers, Poly (meth) acrylates, polyethersulfones, polybutylene terephthalate, Polycarbonates, polypropylene (PP) or polyethylene (PE) and blends from ASA or ABS polymers and polycarbonates or polybutylene terephthalate and blends of polycarbonates and polybutylene terephthalate used, wherein it is useful when using PP and / or PE, the substrate layer previously provided with a primer layer. Particularly suitable are amorphous thermoplastics or their blends. Preference is given to ABS or SAN polymers used as plastic material for the back molding. For foam backing and Hinterpressen are in a further preferred embodiment of the Professional known thermoset molding compounds used. In a preferred embodiment these plastic materials are glass fiber reinforced, suitable variants are in particular described in DE-A1 100 55 190. When backfoaming will be preferably used polyurethane foams, as described for example in DE-A1 199 39 111.

In A preferred manufacturing method of the molded parts is the composite layer plate or foil deformed by hot forming, then in a Hinterformwerkzeug inserted and with thermoplastic molding compounds back-injected, back-poured or behind-pressed, or with duroplastic Backfoamed molding compounds or behind-pressed.

The Composite layered sheet or foil can after hot forming and experience an outline cut before inserting into the back mold. The contour cut can only after removal from the Hinterformwerkzeug respectively.

surface activation

essential to the invention is that in the method according to the invention after the first step of melt mixing and extrusion of the Plastic items and before the last procedural step described below the metallization surface activation the extruded plastic objects in the non-molten state he follows.

The surface activation can according to the invention mechanical abrasion, in particular sandblasting, dry ice blasting or sanding, and / or chemical abrasion, in particular etching, take place. Method of implementation the mechanical abrasion and / or chemical abrasion are the Known in the art and described in the prior art.

in the Case of sandblasting will be a suitable surface activation usually by sand blasting times of less than 1 minute, preferably less than 30 seconds, more preferably less than 10 seconds, achieved. The same applies to the dry ice blasting, however, instead of sand as abrasive Material dry ice is used. Appropriate method for Dry ice blasting is known to those skilled in the art and in the art described.

The surface activation can also be achieved by Stretching (often referred to as stretching or stretching) of the extruded plastic objects in the non-molten state by the factor 1.1 to 10, preferably 1.2 to 5, particularly preferred 1.3 to 3, done.

Of course, the mentioned embodiments mechanical and / or chemical abrasion and stretching too be used in combination for surface activation.

The Stretching can be unidirectional or multidirectional. In the case of extruded profiles, strands or pipes is preferably a unidirectional stretching, in the case of flat Plastic articles Preferably, a multidirectional, in particular bidirectional Stretching, for example in the blow molding or thermoforming process of Foils or plates. In the case of multidirectional stretching is essential that in at least one direction of stretching said stretching factor is achieved.

When Stretching processes are basically all known to those skilled in the art and in the literature described stretching methods can be used. preferred Stretching method for Films are for example blow molding.

The Stretching the plastic objects occurs at temperatures that vary according to the processing characteristics the particular component A used. For example, done stretching using S-TPE as component A usually at temperatures of 105 to 140 ° C, in particular 110 to 130 ° C.

The process step of the surface activation can in principle directly after the Extrusion or coextrusion of the plastic objects done. In principle, however, extruded films, for example, can first be laminated and / or back-injected, casted, pressed or foamed after extrusion. The composite films, sheets or multilayer moldings thus obtained are then subsequently surface-activated. However, the surface activation preferably takes place directly after the extrusion, only after the surface activation are the desired process steps for the production of multilayer plastic articles carried out, if desired.

metallized Plastic items

The extruded and surface activated as prepared Plastic objects, in particular Films or sheets, laminated films or sheets and shaped articles, are particularly suitable for the production of metallized plastic objects, without that requires a further special pretreatment of the surface is.

When last step of the process of the invention for the preparation The metallized plastic objects are in principle all those skilled in the art known and described in the literature method for electroless and electrodeposition of metals on plastic surfaces (See, for example, Harold Ebneth et al., Plating of Plastics: Practical experience with physical, chemical and galvanic metallized high polymers, Expert Verlag, Renningen-Malmsheim, 1995, ISBN 3-8169-1037-8; Kurt Heymann et al., Plastics Metallization: Manual for Theory and Practice, Series Electroplating and Surface Treatment 22, Saulgau: Leuze, 1991; Mittal, K.L. (ed.), Metallized Plastics Three: Fundamental and Applied Aspects, Third Electrochemical Society Symposium on Metallized Plastics: Proceedings, Phoenix, Ariz., October 13-18, 1991, New York, Plenary Press) ..

Usually, the extruded plastic articles after the last molding process are electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, the metal of this metal salt solution having a more positive normal potential in accordance with acidic, neutral or basic solution as component B. Preferred metals with more positive normal potential in acidic neutral or basic solution as component B are gold and silver (if component B is copper), or copper, nickel and silver, in particular copper (if component B is iron). On the component B containing layer of extruded plastic objects, a currentless or electrodeposited layer M _{S is} applied in this way. Preferred layers M _S are gold and silver layers (if component B is copper), or copper, nickel or silver layers, in particular copper layers (if component B is iron).

The thickness of the electrolessly depositable layer M _S is in the usual range known to the person skilled in the art and is not essential to the invention.

One or more metal layers M _g , preferably galvanically, ie, applying external voltage and current flow, can be applied to the electrolessly depositable layer M _S according to methods known to the person skilled in the art and described in the literature. Preferably, copper, chromium, silver, gold and / or nickel layers are electrodeposited. The electrodeposition of layers M _g of aluminum is also preferred. Application by direct metallization by means of vacuum vapor deposition, irradiation / sputtering or by methods known to the person skilled in the art is also possible.

The thicknesses of the one or more deposited layers M _g are in the usual range known to the person skilled in the art and are not essential to the invention.

Especially preferred metallized plastic articles for use as electrical conductive components, in particular printed circuit boards, have a de-energized deposited copper layer and at least one more, galvanic deposited layer on.

Especially have preferred metallized plastic objects for use in the decorative area an electrolessly deposited copper layer, then a galvanic deposited nickel layer and a deposited on this chromium, Silver or gold layer on.

The produced by the inventive method metallized plastic objects comprising an electroless depositable metal layer M _S are readily application of a deposited metal layer M _g as electrically conductive components, in particular printed circuit boards, transponders, antennas, switches, sensors and MID's EMI shielding systems (i.e., shielding Avoiding so-called "electromagnetic interference") such as absorbers, dampers or reflectors suitable for electromagnetic radiation or gas barriers.

The metallized plastic articles which can be produced by the process according to the invention and comprise an electrolessly depositable metal layer M _S and at least one deposited metal layer M _g are electrically conductive components, in particular printed circuit boards, transponder antennas, Switches, sensors and MID's, as EMI shielding such as absorbers, dampers or reflectors for electromagnetic radiation or gas barriers or decorative parts, especially decorative parts in the automotive, sanitary, toy, household and office area suitable.

Examples for such Applications are: Computer Cases, casing for electronic Components, military and non-military Shielding devices, shower and washbasin taps, showerheads, shower rods and holders, metallized door handles and Door knobs, toilet paper roll holder, Bathtub handles, metallized trim on furniture and Mirror, frame for Shower enclosures.

Farther may be mentioned: Metallized plastic surfaces in the automotive sector, such as e.g. Decorative stripes, outside mirrors, grille, Front-end metallization, wind deflectors, body exterior parts, door sills, Tread plate replacement, wheel covers. In particular, such parts made of plastic, which so far partially or completely off Metals were produced. Examples include: tools such as pliers, screwdrivers, drills, chuck, saw blades, and spanner.

Farther find the metallized plastic objects - if they are magnetizable Metals include - applications in areas of magnetizable functional parts, such as magnetic boards, Magnetic games, magnetic surfaces at e.g. Refrigerator doors. Also find They apply in areas where good thermal conductivity is advantageous, for example in films for seat heaters, underfloor heating, Insulation materials.

The inventive method for the production of metallized plastic objects characterized by that with comparably good processing properties and freedom of design freedom the plastic objects, For example, in forming processes for the production of complex shaped Components, opposite known method for producing metallized plastic parts an improved electroless and galvanic metallizability is made possible. The according to the inventive method producible metallized plastic objects have opposite to known Method produced metallized plastic bodies comparable good processing properties and formative Design freedom qualitatively improved, in particular more homogeneous and / or more adherent metal layers.

Claims (16)

A process for producing a metallized, extruded plastic article, wherein in a first step the melt blending and extrusion of a plastic mixture comprises, based on the total weight of components A, B, C and D, a total of 100% by weight, a 5 to 50% by weight of a thermoplastic polymer as component A, b 50 to 95% by weight of a metal powder having a mean particle diameter of 0.01 to 100 μm (determined according to the method mentioned in the description), the metal being a more negative Normal potential in acidic solution than silver, as component B, c 0 to 10 wt .-% of a dispersant as component C, and d 0 to 40 wt .-% fibrous or particulate fillers or mixtures thereof as component D, takes place in a last step, the extruded plastic article is electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, wherein this metal positi Veres normal potential in accordance with acidic, neutral or basic solution as component B, characterized in that the plastic article is surface-activated after the step of melt mixing and extrusion and before the step of contacting with the metal salt solution in the non-molten state. Method according to claim 1, characterized in that the surface activation by stretching of the plastic article by a factor of 1.1 to 10. Method according to claim 2, characterized in that the stretching unidirectional or bidirectional takes place, wherein the plastic article in at least one direction of stretching is stretched by a factor of 1.1 to 10. Process according to claims 1 to 3, characterized in that the Surface activation by mechanical abrasion, in particular sandblasting, dry ice blasting or sanding, and / or chemical abrasion, in particular etching, takes place. A method according to claims 1 to 4, characterized in that after the step of contacting with the metal salt solution one or more further metal layers M _{g are} deposited. Process according to claims 1 to 5, characterized in that the plastic article is an extruded Foil, plate, an extruded profile, tube or an extruded one Strand is. Process according to claims 1 to 6, characterized in that before or after the Oberflä chenaktivierung at least one coextrusion, laminating, laminating, Hinterspritz-, Hintergieß-, Hinterpress- or Hinterschäumprozess with plastic, and the plastic article is a composite or molded part comprising a plurality of plastic layers. Process according to claims 1 to 7, characterized in that as component A one or more Polymers selected from the group impact-modified vinylaromatic copolymers based on thermoplastic elastomers of styrene, polyolefins, polycarbonates and thermoplastic polyurethanes be used. Process according to claims 1 to 8, characterized in that the metal salt solution is a silver and / or Copper and / or nickel salt solution is, and component B is iron. Process according to claims 1 to 9, characterized in that as component B carbonyl iron powder is used. Process according to claims 5 to 10, characterized in that the one or more further deposited metal layers M _g consist of copper and / or chromium and / or nickel and / or silver and / or gold, and have been electrodeposited. Metallized, extruded plastic objects, manufacturable according to one the claims 1 to 11. Use of metallized extruded plastic articles, producible according to claims 1 to 11 as electrically conductive components, EMI shielding such as absorber, damper or Reflectors for electromagnetic radiation or as gas barriers. Use of metallized extruded plastic articles, producible according to claims 5 to 11 as decorative parts, in particular decorative parts in the motor vehicle, sanitary, toy, household and office area. Electrically conductive components, EMI shielding like absorber, damper or reflectors for electromagnetic Radiation and gas barriers, including metallized, extruded Plastic items can be produced according to claims 1 to 11th Decorative parts, in particular decorative parts in motor vehicle, Sanitary-, Toy, household and office space, comprising metallized, extruded plastic articles producible according to claims 5 to 11th