WO2006114431A1 - Process for producing metal-plated, extruded plastic objects - Google Patents

Abstract

A process is disclosed for producing metal-plated, extruded plastic objects. In a first melt blending and extrusion step, a plastic mixture is processed comprising, in relation to the total weight of components A, B, C and D, which add up to 100 % by weight: (a) 5-50 % by weight of a thermoplastic polymer as component A; (b) 50-95 % by weight of a metal powder having an average particle diameter ranging from 0.1 to 100 νm (determined by the method defined in the description), the metal having a more negative normal potential in an acid solution than silver, as component B; (c) 0-10 % by weight of a dispersant as component C; and (d) 0-40 % by weight fibrous or particulate fillers or their mixture as component D. In a last step, the extruded plastic object is electrolessly or galvanically brought into contact with an acid, neutral or basic metal salt solution, that metal having a more positive normal potential in a correspondingly acid, neutral or basic solution than component B. The essential aspect of the invention is that the plastic object is surface-activated in the non-molten state after the melt blending and extrusion step and before the step in which it is brought into contact with an acid metal salt solution. Also disclosed are metal-plated extruded plastic objects, the use of these objects as EMI shieldings and absorbers, dampers or reflectors for electromagnetic radiation, oxygen scavengers, electroconducting components, gas barriers and decorative elements comprising these objects.

Description

Process for producing metallised, extruded plastic articles

description

The invention relates to processes for the production of 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 the components A, B, C, and D _1, which gives a total of 100 wt .-%,

a 5 to 50 wt .-% of a thermoplastic polymer as component A ₁ b 50 to 95 wt .-% of a metal powder having a mean particle diameter of 0.01 to 100 microns (determined according to the method mentioned in the description), wherein the metal 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, 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.

Furthermore, the invention relates to metallized extruded plastic articles, the use of these objects and EMI shieldings such as absorbers, dampers or reflectors for electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects.

Methods for producing metallized plastic films or molded articles are known and are used in a variety of applications.

Thus, metal powder-containing plastic objects can be electrolessly and / or galvanically metallized. Such metallized plastic objects can be used for example as electrical components due to the electrical conductivity. Furthermore, you will find widespread use, among others. in the decor sector, since they have the same appearance as completely made of metal objects advantages by lighter weight and less expensive production.

In general, in view of the mentioned fields of application and for the formation of dense and firmly adhering metal layers, it is desirable to achieve the highest possible metal powder content in the plastic. As the degree of filling increases, however, as a rule, the mechanical properties of the plastic mixtures deteriorate, so that at high degrees of filling, for example, toughness, bending stress and deformability are insufficient, which may result in an unacceptable deterioration of the processing properties and serious limitations of design freedom in forming processes. Plastic mixtures that still have good processability and design freedom in the shaping of the semi-finished plastic products produced from them, such as films, are therefore often only poorly or not metallizable due to limited Metallpulverfüllgrade.

It is therefore the object of the present invention to provide processes for the production of metalized plastic articles, which are distinguished by the fact that, with comparably good processing properties and freedom of design freedom, the plastic articles, for example in forming processes for the production of complex shaped components known methods for producing metallized plastic parts an improved electroless and galvanic metallizability is made possible. A further object of the present invention is to provide metallized plastic articles which have qualitatively improved, in particular more homogeneous and / or better adhering, metal layers compared to metallized plastic bodies produced by known methods with comparably good processing properties and freedom of design.

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 wt .-% of a thermoplastic polymer as component A, b 50 to 95 wt .-% of a metal powder having an average particle diameter of 0.01 to 100 microns (determined according to the method mentioned in the description), wherein the metal has 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, and in a last step, the extruded plastic object 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,

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 (in the case of semicrystalline polymers, the non-molten state is understood as the state within a temperature range of +/- 20 ^° C. to the melting point Tm of the semicrystalline polymer, as a non-molten state in the case of non-crystalline polymers State in the temperature range from 0 to 70 ⁰ C above the highest glass level of the non-crystalline polymer to understand) is surface-activated.

Furthermore, metallized extruded plastic articles, the use of these articles and EMI shieldings such as absorbers, dampers or reflectors for electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects were found.

The methods according to the invention for producing metallized plastic articles are characterized in that, with comparably good processing properties and freedom of design of the plastic articles, for example in forming processes for the production of complex shaped components, compared to known methods for producing metallized plastic parts an improved electroless and galvanic Metallisierbarkeit is possible. The metallized plastic articles which can be produced by the process according to the invention have qualitatively improved, in particular more homogeneous and / or better adhering, metal layers compared to metallized plastic bodies produced by known processes with comparably good processing properties and freedom of design.

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

Plastic mixture:

The first step of the processes according to the invention comprises 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% by weight,

a 5 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 20 to 5 30% by weight of component A, b 50 to 95% by weight, preferably 60 to 90% by weight, more 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 O d 0 to 40 wt .-%, preferably 0 to 30 wt .-%, particularly preferably 0 to 10 wt .-% of component 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 5 to 49.9 wt .-%, preferably 10 to 39.5 wt .-%, particularly preferably 20 to

29 wt .-% of component A, b 50 to 94.9 wt .-%, preferably 60 to 89.5 wt .-%, particularly preferably 70 bis

79 wt .-% of component B, c 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 5 wt .-% of 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 1 BA (Annex A of the cited standard: "small specimens").

A plastic mixture comprising the following components can be used in the processes according to the invention.

Component A

In principle, all thermoplastic polymers are suitable as component A, in particular those having an elongation at break in the range from 10% to 1000%, preferably in the range from 20 to 700, particularly preferably in the range from 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 from BASF Styrolux ^® Aktiengesellschaft, K-Resin ™ 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).

As component A, preference is given to using one or more polymers selected from the group of impact-modified vinylaromatic copolymers, thermoplastic elastomers based on styrene, polyolefins, polycarbonates and thermoplastic polyurethanes.

As likewise preferred component A, polyamides can be used.

Impact-modified vinylaromatic copolymers:

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

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

ASA polymers are generally understood to be impact-modified SAN polymers in which rubber-elastic graft copolymers of vinylaromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, are present on polyalkyl acrylate rubbers in a copolymer matrix of, in particular, styrene and / or α-methylstyrene and acrylonitrile.

In a preferred embodiment, in which the plastic mixtures comprise ASA polymers, the elastomeric graft copolymer A ^κ of the compo- nent A, composed of

a1 1-99 wt .-%, preferably 55-80 wt .-%, in particular from 55 to 65 wt .-%, of a particulate graft base A1 with a glass transition temperature below 0 ⁰ C.

a2 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, of a graft A2 from the monomers, based on A2, a21 40-100% by weight, preferably 65-85% by weight, of units of styrene, of a substituted styrene or of a (meth) acrylic ester or mixtures thereof, in particular of styrene and / or α-methylstyrene as component A21 and a22 to 60% by weight, preferably 15-35% by weight, of units of the 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 wt.%, preferably 95-99.9 wt.%, of at least one Ci _-8-

Alkyl esters of acrylic acid, preferably n-butyl acrylate and / or ethylhexyl acrylate as component A11, a12 0.01-20% by weight, preferably 0.1-5.0% by weight, 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 ^κ is 50-1000 nm and is distributed monomodally.

According to a further embodiment of the invention, the particle size distribution of the component A is ^κ 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 component A ^κ .

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.-Polymere 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 average particle diameter, which is also referred to as the dso value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter corresponding to the dso value. Likewise, then 50 wt .-% of the particles have a larger diameter than the dso value. To characterize the width of the particle size distribution of the rubber particles, in addition to the dso value (average particle diameter), the dio and dgo values resulting from the integral mass distribution are used. The dio or d ₉₀ value of the integral mass distribution This is defined according to the d ₅ o value with the difference that they are based on 10 or 90 wt .-% of the particles. The quotient

(dgo - dioVdδo = Q

represents a measure of the distribution width of the particle size. Rubber-elastic graft copolymers A ^κ 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 ds-alkyl acrylates, preferably C ₄ -alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl acrylate. and 2-ethylhexyl acrylate. 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, in copolymerized form.

The acrylate rubbers furthermore contain 0.01-20% by weight, preferably 0.1-5% by weight, of crosslinking, polyfunctional monomers (crosslinking monomers). Examples of these are monomers which contain 2 or more double bonds capable of copolymerizing, which are preferably not conjugated in the 1,3-positions.

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. Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly advantageous crosslinking monomer (see DE-PC 12 60 135).

The component A ^κ is a graft copolymer. The graft copolymers A ^κ here have a median particle size dso of 50 - nm 1000, preferably of 50 - 800 nm and particularly preferably of 50 -. 600 nm These particle sizes can be achieved, if the graft base A1 particle sizes of 50 - nm 800, preferably of 50-500 nm, and more preferably 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 - several stages grafted thereon A2 (graft), the so-called grafting or grafting.

By simple grafting or multiple stepwise grafting, one or more graft sheaths may be applied to the rubber particles, each one of them Graft shell may have a different composition. In addition to the grafting monomers, it is also possible to graft polyfunctional monomers containing crosslinking or reactive groups (see, for example, EP-A 230 282, DE-AS 36 01 419, EP-A 269 861).

In a preferred embodiment, component A ^κ consists of a multi-stage graft copolymer, wherein the grafting steps are generally prepared from resin-forming monomers and have a glass transition temperature T ₉ above 3O ⁰ C, preferably above 50 ⁰ C. The multi-stage structure is used, inter alia, to achieve a (partial) compatibility of the rubber particles A ^κ with the thermoplastic matrix.

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

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

Suitable monomers for forming the graft A2 are styrene, α-methylstyrene, (meth) acrylic acid esters, acrylonitrile and methacrylonitrile, in particular acrylonitrile.

According to one embodiment of the invention serve as the graft A1 crosslinked acrylic acid ester polymers having a glass transition temperature below ^{0 0} C. The crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ⁰ C, especially below -30 ° C.

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

Suitable preparation processes for graft copolymers A ^κ are emulsion, solution, bulk or suspension polymerization. The graft copolymers A ^κ are preferably prepared by free radical emulsion polymerization in the presence of latices of component A1 at temperatures of 20 ° C - 90 ⁰ C of water-soluble or oil-soluble initiators such as using peroxodisulfate or benzoyl peroxide, or by means 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.

The structure of the graft shells is preferably carried out in the emulsion polymerization process, as described in DE-A 32 27 555, 31 49 357, 31 49 358, 34 14 118. The defined setting of the particle sizes of 50 to 1000 nm according to the invention is preferably carried out according to Processes which are 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 having different particle sizes is known for example from DE-A 28 26 925 and US Pat. No. 5,196,480.

According to the process described in DE-C 12 60 135, the grafting base A1 is first prepared by the acrylic ester (s) used according to one embodiment of the invention and the polyfunctional, crosslinking monomers, optionally together with the further comonomers aqueous emulsion in a conventional manner at temperatures between 20 and 100 ⁰ C, preferably between 50 and 8O ⁰ C, polymerized. The usual emulsifiers, such as, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or rosin soaps can be used. Preferably, the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are used. According to one embodiment, the emulsifiers are used in amounts of from 0.5 to 5% by weight, in particular from 1 to 2% by weight, based on the monomers used in the preparation of the grafting base A1. In general, a weight ratio of water to monomers of 2: 1 to 0.7: 1 is used. The polymerization initiators are in particular the customary persulfates, such as potassium persulfate. However, redox systems can also be used. The initiators are generally used in amounts of from 0.1 to 1% by weight, based on the monomers used in the preparation of the grafting base A1. As further polymerization auxiliaries, it is possible to use the customary buffer substances by means of which pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric α-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 in such a way that the resulting latex of the crosslinked acrylic ester polymer has a d.sub.50 in the range of about 50-800 nm, preferably 50-500 nm, particularly 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 ^κ of the resulting latex of the crosslinked acrylate-polymer is then in a next step in the presence according to an embodiment of the invention is polymerized, a monomer mixture of styrene and acrylonitrile, wherein the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention in the range of 100: 0 to 40: 60, preferably in the range of 65: 35 to 85: 15, 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 grafting base A1, it being possible, if necessary, for further emulsifier and initiator to 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 in such a way that a degree of grafting of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, relates on the total weight of the component A ^κ , resulting in the graft copolymer A ^κ . 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 than 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 ^κ is familiar to the expert and can be done, for example, by the metering rate of the monomers or by addition of regulators (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 et seq. ). In the emulsion graft copolymerization, generally about 5 to 15% by weight, based on the graft copolymer, of free, ungrafted styrene / acrylonitrile copolymer are formed. The proportion of the graft copolymer A ^κ in the polymerization product obtained in the graft copolymerization is determined by the method indicated above.

In the preparation of the graft copolymers A ^κ 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 ^κ . In particular, the component A ^κ 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 ^κ generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of grafting A1 and 1-99% by weight, preferably 20-45, more preferably 35-45 wt .-% of the graft A2, each based on the total graft copolymer.

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

In a preferred embodiment, in which the plastic mixtures comprise ABS polymers, the rubber-elastic graft copolymer A ^{κ <of} the 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, dihydrodicyclopentadienyl, dinvinyl esters of dicarboxylic acids such as maleic and adipic acid 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 '50 to 100, preferably 55 to 90 wt .-% of at least one vinyl aromatic

Monomers, 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 ^{κ <is} a graft rubber having a bimodal particle size distribution, based on A ^κ ',

a1 "40 to 90, preferably 45 to 85% by weight of a rubber-elastic particulate grafting base A1 '1 obtainable by polymerization of, based on A1",

a11 "from 70 to 100, preferably from 75 to 100,% by weight 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 monoethylenically unsaturated monomer, in particular styrene, α-methylstyrene, n-butyl acrylate or mixtures thereof,

a2 "10 to 60, preferably 15 to 55% by weight of a grafting pad A2", based on A2 '\

a21 "65 to 95, preferably 70 to 90% by weight of at least one vinylaromatic monomer, preferably styrene,

a22 "5 to 35, preferably 10 to 30% by weight of acrylonitrile,

a23 "0 to 30, preferably 0 to 20% by weight 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 to 100 wt.%, preferably 40 to 100 wt.%, particularly preferably 60 to 100 wt.% of α-methylstyrene and 0 to 100 wt.%, preferably 0 to 60 wt %, more preferably 0-40% by weight of units derived from styrene, from, based on A ^M ,

a ^M 1 40-100% by weight, preferably 60-85% by weight, of vinyl aromatic units

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 comprise ABS polymers as component A, the hard matrix A ^M 'of component A is at least one hard copolymer containing units derived from vinylaromatic 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% by weight, more preferably 0-40% by weight, of styrene-derived units are present, based on A ^M ',

a ^M 1 '50 to 100, preferably 55 to 90 wt .-% of vinyl aromatic 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-arylmaleimides such as N-phenylmaleimide.

In a further preferred embodiment, in which the plastic mixtures ABS comprise as component A, component A ^{M 'is} at least one hard copolymer having a viscosity number VN (determined according to DIN 53726 at 25 ⁰ C in 0.5 wt .-% - strength 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% by weight of α-methylstyrene and 0-100% by weight, preferably 0-60% by weight, more preferably 0-40% by weight, of units derived from styrene are, from, based on A ^M '

on / ii "69 to 81, preferably 70 to 78 wt .-% of vinyl aromatic monomers, aiw2" 19 to 31, preferably 22 to 30 wt .-% acrylonitrile, awi3 "0 to 30, preferably 0 to 28 wt .-% at least another, monoethylenically unsaturated monomer, for example methyl methacrylate or N-alkyl or N-arylmaleimides 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 these ABS polymers, the graft polymers A ^{κ 'are} preferably obtained by means of emulsion polymerization. The mixing of the graft polymers A ^{κ '} with the Components A ^M 'and, if appropriate, further additives are generally carried out in a mixing device, forming a substantially molten polymer mixture. It is advantageous to cool the molten polymer mixture as quickly as possible.

Incidentally, there are described in detail preparation and general as well as special embodiments of the abovementioned ABS polymers in the German patent application DE-A 19728629, which is incorporated herein by reference. The abovementioned ABS polymers may contain further customary auxiliaries and fillers. Such substances are, for example, lubricants or mold release agents, waxes, pigments, dyes, flame retardants, antioxidants, light stabilizers 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 ^κ or A ^κ '. Depending on the conditions used in the graft copolymerization for the preparation of the graft copolymers A ^κ or A ^{κ '} , 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, while 0.5 g of material in 100 ml of dimethylformamide solved.

The mixing of the components A ^κ (or A ^{κ '} ) and A ^M (or A ^M ') can be carried out in any manner by all known methods. If these components For example, have been prepared by emulsion polymerization, it is possible to mix the polymer dispersions obtained with each other, then precipitate the polymers together and work up the Polymerisatgemisch. 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 dehydrated and mixed as moist crumbs with the hard matrix, during which 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 preferably mixed as S-TPE is a linear or star-shaped styrene-butadiene block copolymer with external polystyrene blocks S and intervening styrene-butadiene copolymer blocks with random styrene / butadiene distribution (S / B) _ran ciom or a styrene gradient (S / B) taperZU.

The Gesamtbutadiengehalt is preferably in the range of 15 to 50 wt .-%, particularly preferably in the range of 25 to 40 wt .-%, the Gesamtstyrolgehalt is correspondingly preferably in the range of 50 to 85 wt .-%, particularly preferably in the area from 60 to 75% by weight.

Preferably, the styrene-butadiene block (S / B) consists of 30 to 75% by weight of styrene and 25 to 70% by weight of butadiene. Particularly preferably, a block (S / B) has a butadiene content of 35 to 70% by weight and a styrene content of 30 to 65% by weight.

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

Particularly preferred are linear styrene-butadiene block copolymers of the general structure S- (S / B) -S with one or more, lying between the two S blocks, a static styrene / butadiene distribution having blocks (S / B) _ran do _m . Such 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. The vinyl content is understood to be the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages. The 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.

polyolefins:

The polyolefins which can be used as components A generally have breaking elongations of from 10% to 600%, preferably from 15% to 500%, particularly preferably from 20% to 400%.

Suitable components 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. Component A is preferably a high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene.

Polyethylene (LLDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA) or ethylene-acrylic copolymer used. A particularly preferred component A is polypropylene.

polycarbonates:

The polycarbonates which can be used as components A generally have breaking elongations of from 20% to 300%, preferably from 30% to 250%, particularly preferably from 40% 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, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols. Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally referred to as bisphenol A, as in the following.

Instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxynaphthalene. Dihydroxydiphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxyclopentanes, in particular 1,1-bis (4-hydroxyphenyl) - 3,3,5-trimethylcyclohexane and mixtures of the abovementioned dihydroxy compounds.

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

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

It is also possible to use copolycarbonates according to US Pat. No. 3,737,409; Of particular interest are copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to 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 relative solution viscosities in the range of 1, 1 to 1, 3 as measured in 0.5 wt .-% solution in dichloromethane at 25 ⁰ C, aeration vorzugt of 1 15 to 1, 33, have , 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 elongation at break of 30% to 800%, preferably 50% to 600%, particularly preferably 80% to 500%.

Particularly preferred components A are the thermoplastic elastomers based on styrene.

Component B

As component B are all metal powders having an average particle diameter of 0.01 to 100 .mu.m, preferably from 0.1 to 50 .mu.m, more preferably from 1 to 10 microns, suitable (determined by laser diffraction measurement on a device Microtrac X100), provided that the metal has a more negative normal potential in acidic solution than silver.

Suitable metals are, for example, Zn, Ni, Cu, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi. The metals may be in the form of the metal used or, if different metals are used, in the form of alloys of the metals mentioned with one another or be deposited with other metals. Examples of suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCu, NiP, ZnFe, ZnNi, ZnCo and ZnMn. Preferably usable metal powders are iron powder and copper powder, in particular iron powder.

The metal powder particles can in principle have any desired shape, for example, needle-shaped, plate-shaped or spherical metal particles can be used, preferably spherical and plate-shaped. Such metal powders are common

Trade 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.

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

The preparation of carbonyl iron powders by thermal decomposition of iron pentacarbonyl is known and is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599. The decomposition of the iron pentacarbonyl can be carried out, for example, at elevated temperatures 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, consisting of a heating device, for example from heating tapes, Heating wires or from a heating medium flowed through by a heating jacket, is surrounded.

The mean particle diameters of the carbonyl iron powder which separates out can be controlled in a wide range by the process parameters and reaction behavior during the decomposition and are generally from 0.01 to 100 μm, preferably from 0.1 to 50 μm, more preferably from 1 to 10 μm.

Component C

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

Cationic and anionic surfactants are described, for example, in "Encyclopedia of Polymer Science and Technology", J. Wiley & Sons (1966), Vol. 5, pp. 816-818, and in "Emulsion Polymerization and Emulsion Polymers", editors P. Lovell and M. El-Asser, published by Wiley & Sons (1997), pages 224-226.

Examples of anionic surfactants are alkali metal salts of organic carboxylic acids having chain lengths of 8-30 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, e.g. Sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali salts of C12-C16 paraffin sulfonic acids. Also suitable are sodium dodecylbenzenesulfonate and sodium di-sulfosuccinate.

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

In particular, according to the invention nonionic surfactants can be used as component C. Nonionic surfactants are described, for example, in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "nonionic surfactants". Suitable nonionic surfactants include for example polyethylene oxide or polypropylene oxide-based substances such as Pluronic ^® and Tetronic ^® from BASF Aktiengesellschaft. Polyalkylene glycols suitable as nonionic surfactants generally have a molecular weight M _n in the range from 1000 to 15000 g / mol, preferably 2000 to 13000 g / mol, particularly preferably 4000 to 11000 g / mol. Preferred nonionic surfactants are polyethylene glycols.

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

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

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

Also suitable as component C are esterified polyalkylene glycols, for example the mono-, di-, tri- or polyesters of the polyalkylene glycols mentioned, which are obtained by reaction of the terminal OH groups of said polyalkylene glycols with organic acids, preferably adipic acid or terephthalic acid, in per se can be produced in a known manner. As component C, polyethylene glycol adipate or polyethylene glycol terephthalate is preferred. Particularly suitable nonionic surfactants are substances prepared by alkoxylation of compounds having active hydrogen atoms, for example adducts of ethylene oxide with fatty alcohols, oxo alcohols or alkylphenols. For the alkoxylation, preference is given to using ethylene oxide or 1,2-propylene oxide.

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

Sugar ethers are alkyl glycosides obtained by reaction of fatty alcohols with sugars, and sugar esters are obtained by reacting sugars with fatty acids. The sugar, fatty alcohols and fatty acids necessary for the preparation of the substances mentioned are known to the person skilled in the art.

Suitable sugars are described for example in Beyer / Walter, textbook of organic chemistry, S. Hirzel Verlag Stuttgart, 19th edition, 1981, pages 392 to 425. Particularly suitable sugars are D-sorbitol and sorbitans obtained by dehydration of D-sorbitol.

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

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

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

Very particularly suitable components C are alkoxylated sugar ethers and sugar esters which are obtained by alkoxylation of the cited sugar ethers and sugar esters become. 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 polyvinyl lysorbate are polyethoxysorbitan, stearate, palmitate, tristearate, oleate, trioleate, especially polyethoxysorbitan, which is available for example 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

As component D, the plastic mixtures contain fibrous or particulate fillers or mixtures thereof. These are preferably commercially available products, for example carbon fibers and glass fibers.

Useful glass fibers may be of E, A or C glass and are preferably equipped with a size and a primer. Their diameter is generally between 6 and 20 μm. Both continuous fibers (rovings) and chopped glass fibers (staple) with a length of 1 to 10 mm, preferably 3 to 6 mm, can be used.

Furthermore, fillers or reinforcing agents such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powder and wollastonite may be added.

The plastic mixture may also contain other additives that are typical and common in plastics processing.

Examples of such additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the light stability, to increase the resistance to hydrolysis and chemical resistance, means against the heat decomposition and in particular the lubricants / lubricants for the production of moldings or moldings are expedient. 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 oxidation inhibitors 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 analogously constructed compounds. Hindered amine light stabilizers, benzophenones, resorcinols, salicylates, benzotriazoles such as Tinuvin®RP (UV absorber 2- (2H-benzotriazol-2-yl) -4-methylphenol from CIBA) and other compounds are also suitable. These are usually used in amounts of up to 2 wt .-% (based on the total mixture of Kunstsoffmischung).

Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures having 12-30 carbon atoms. The amounts of these additives are in the range of 0.05 to 1 wt .-%.

Also, silicone oils, oligomeric isobutylene or similar substances are suitable as additives, the usual amounts are from 0.05 to 5 wt .-%. Pigments, dyes, color healers such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are also usable.

Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01-5 wt .-%.

Method:

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

In principle, all plastic articles accessible by extrusion can be shaped by the processes according to the invention. Preferred extruded plastic articles are films, sheets, profiles, tubes and strands. These can in principle be produced by extrusion processes known to the person skilled in the art.

The process according to the invention also makes it possible to access multilayer plastic articles. Thus, for example, composite layer films or sheets can be produced by coextrusion, laminating or laminating methods. By injection molding, casting behind or pressing back with thermoplastic molding materials or foam or Hinterpressen with thermosetting molding compounds multilayer moldings are accessible.

Preferred plastic articles and their preparation are described below. Process for producing extruded films or sheets

The preparation of the thermoplastic molding compositions for producing the extruded films or sheets of the components A, B and, if present, C and D is carried out by methods known in the art, for example by mixing the components in the melt with known in the art devices at temperatures, the depending on the nature of the polymer A employed usually in the range of 150 to 300 ⁰ C, particularly at 200 to 28O ⁰ C. ₁ The components can be supplied in each case pure form the mixing devices. However, it is also possible for individual components, for example A and B, to be premixed first and then mixed with further components A or B or other components, for example C and D. In one embodiment, a concentrate, for example components B, C or D in component A is first prepared (so-called additive batches) and then mixed with the desired amounts of the remaining components. The plastic mixtures can after the

Professional processes known to be processed into granules to be extruded at a later date to the films or sheets of the invention. However, they can also be extruded directly after the mixing operation or in one working step with the mixing process (i.e., simultaneous melt mixing and extrusion), preferably by means of a screw extruder, to the films or sheets according to the invention.

In a preferred embodiment of the method according to the invention, the screw extruder is designed as a single-screw extruder with at least one distributively mixing screw element.

In a further preferred embodiment of the process according to the invention, the screw extruder is designed as a twin-screw extruder with at least one distributively mixing screw element.

The methods of extruding the films or plates may be by methods known to those skilled in the art and described in the art, e.g. 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 films or plates generally have a total thickness of 20 microns to 5 mm, preferably from 70 .mu.m to 3 mm, more preferably 100 .mu.m to 1, 5 mm.

Composite layer plates or foils

The extruded films or plates are suitable in particular as a cover layer (3) of multilayer composite layer plates or films which, in addition to the cover layer, have at least one further substrate layer (1) made of thermoplastic material. In further embodiments, the composite layer plates or sheets may comprise additional layers (2), for example color, adhesion promoter or intermediate layers, which are arranged between the cover layer (3) and the substrate layer (1).

The substrate layer (1) can in principle be constructed from any thermoplastic material. The substrate layer (1) is preferably prepared from the impact-modified vinylaromatic copolymers described above in connection with the extruded films or plates, thermoplastic elastomers based on styrene, polyolefins, polycarbonates and thermoplastic polyurethanes or mixtures thereof from ASA, ABS, SAN, polypropylene and polycarbonate or mixtures thereof.

Layer (2) is different from layers (1) and (3), for example because of a different polymer composition from and / or different from these additive contents, such as colorants or effect pigments. Layer (2) can be, for example, a coloring layer which may preferably contain dyes, color pigments or effect pigments known to the person skilled in the art, such as mica or aluminum flakes or mica. However, layer (2) can also serve to improve the mechanical stability of the composite layer plates or films, or to provide adhesion between the layers (1) and (3).

An embodiment of the invention relates to a composite layered sheet or film of a substrate layer (1), cover layer (3) as described above and an intervening intermediate layer (2) consisting of aliphatic thermoplastic Polyurethane, impact polymethyl methacrylate (PMMA), polycarbonate or styrene (co) polymers such as SAN, which may be impact-modified, for example ASA or ABS, or mixtures of these polymers is constructed.

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

If polycarbonate is used as intermediate layer (2), then the polycarbonate described under layer (3) can be used.

High Impact PMMA (PMMA: HI-PMMA) is a polymethyl methacrylate which is impact-modified by suitable additives. 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, Die Kunststoffe u. Publisher Dusseldorf, 1992.

The layer thickness of the above composite layer plates or films is usually 15 to 5000 .mu.m, preferably 30 to 3000 .mu.m, more preferably 50 to 2000 microns.

In a preferred embodiment of the invention, the composite layer plates or sheets consist of 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 foils comprising a substrate layer (1), an intermediate layer (2) and a cover layer (3) preferably have the following layer thicknesses: 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 material which is compatible with polyolefins, 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 may be prepared by known methods described in the prior art (for example in WO 04/00935), for example by adapter or coextrusion or laminating or laminating the layers to one another. In the coextrusion processes, the components forming the individual layers are rendered flowable in extruders and brought into contact with one another via special devices so that the composite layer plates or films result with the layer sequence described above. For example, the components may be coextruded through a slot die or a multi-layer die tool. This process is explained in EP-A2-0 225 500.

In addition, they can be produced by the adapter coextrusion process, as described in the conference proceedings of the conference Extrusion Technology "Coextrusion of Films", 8./9. October 1996, VDI publishing house Duesseldorf, in particular contribution of Dr. med. Networks is described. This economical process is used in most coextrusion applications.

Furthermore, the composite laminate sheets and films can be made by laminating or laminating films or sheets in a heatable gap. Initially, corresponding films or plates are produced separately for the layers described. This can be done by known methods. Then, the desired layer sequence is produced by corresponding superimposition of the films or plates, whereupon they are guided, for example, through a heatable roll nip and joined under pressure and heat to form a composite layer plate or film.

Particularly in the case of the adapter coextrusion method, matching of the flow properties of the individual components is advantageous for the formation of uniform layers in the composite layer plates or foils.

moldings

The extruded sheets or sheets and the composite sheets or sheets comprising the extruded sheets or sheets of the present invention may be used to make molded articles. In this case, any shaped parts, preferably flat, especially large area, accessible. These extruded films or sheets and composite laminated sheets or foils are particularly preferably used for the production of molded parts which require very good toughness, good adhesion of the individual layers to one another and good dimensional stability, so that, for example, destruction due to detachment of the surfaces is minimized becomes. Particularly preferred moldings comprise monofilms or composite laminate sheets or foils. holding the extruded sheets or plates and a back-injected, foam-backed, back-pressed or behind-pressed carrier layer made of plastic.

The production of molded parts from the extruded films or sheets or the composite laminate sheets or films can be carried out by known processes described, for example, in WO 04/00935 (the processes for the further processing of composite laminate sheets or films are described below, but these processes are can also be used for the further processing of the extruded films or plates according to the invention). The composite laminate sheets or films can be back-injected, backfoamed, back-poured or back-pressed without further processing stage. In particular, the use of the described composite layer plates or foils makes it possible to produce easily three-dimensional components without prior thermoforming. However, the composite laminates or sheets may also be subjected to a previous thermoforming process. For example, composite laminates or sheets having the substrate layer, interlayer and topcoat three-layer structure or the substrate layer / topcoat two-layer structure may be thermoformed to produce more complex components. Both positive and negative thermoforming processes can be used. Corresponding methods are known to the person skilled in the art. After the thermoforming process, the composite layer plates or films can be subjected to further shaping steps, for example contour cutting.

The molded parts according to the invention can be produced from the composite layer plates or sheets, if appropriate after the described thermoforming processes, by insert molding, back-foaming, back-casting or backpressing. 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-molding, back-foaming, back-casting or rear-pressing of the composite layer films with a plastic material, the molded parts according to the invention are obtained. Thermoplastic molding compositions based on ASA or ABS polymers, SAN polymers, poly (meth) acrylates, polyethersulfones, polybutylene terephthalate, polycarbonates, polypropylene (PP) or polyethylene (PE) are preferred for injection molding, back-molding or back-casting as plastic materials. and blends of ASA or ABS polymers and polycarbonates or polybutylene terephthalate and blends of polycarbonates and polybutylene terephthalate used, it being advisable when using PP and / or PE to provide the substrate layer previously with a bonding agent 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 backfoaming and backpressing, thermosetting molding compounds known to those skilled in the art are used in a further preferred embodiment. In a preferred embodiment these plastic materials are glass fiber reinforced, suitable variants are described in particular in DE-A1 100 55 190. When foam-backing polyurethane foams are preferably used, as described for example in DE-A1 199 39 111.

In a preferred manufacturing method of the moldings, the composite layer plate or film is deformed by hot forming, then inserted into a mold and back molded with thermoplastic molding compounds, back-poured or behind-pressed, or backfoamed with thermosetting molding compounds or behind.

The composite laminate sheet or film may undergo a contour cut after hot working and prior to loading into the back mold. The contour cut can also be made only after removal from the Hinterformwerkzeug.

surface activation

It is essential to the invention that, in the process according to the invention, after the first step of melt mixing and extrusion of the plastic articles and prior to the last metallization step described below, surface activation of the extruded plastic articles takes place in the non-molten state.

The surface activation according to the invention by mechanical abrasion, in particular sandblasting, dry ice blasting or sanding, and / or chemical abrasion, in particular etching, take place. Methods for carrying out the mechanical abrasion and / or chemical abrasion are known to the person skilled in the art and described in the prior art.

In the case of sandblasting, a suitable surface activation is generally achieved by sand blasting times of less than 1 minute, preferably less than 30 seconds, more preferably less than 10 seconds. The same applies to dry ice blasting, but dry ice is used instead of sand as the abrasive material. Corresponding methods for dry ice blasting are known to the person skilled in the art and described in the prior art.

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

Of course, the mentioned embodiments of mechanical and / or chemical abrasion and stretching can also be used in combination with one another for surface activation. The stretching can be unidirectional or multi-directional. In the case of extruded profiles, strands or tubes, a unidirectional stretching is preferably carried out; in the case of sheet-like plastic objects, a multidirectional, in particular bidirectional, stretching is preferred, for example in the blow molding or thermoforming process of films or plates. In the case of multidirectional stretching, it is essential that the said stretching factor is achieved in at least one stretching direction.

In principle, all stretching methods known to the person skilled in the art and described in the literature can be used as the stretching method. Preferred stretching methods for films are, for example, blow molding processes.

The stretching of the plastic objects takes place at temperatures which depend on the processing properties of the particular component A used. Examples of play occurs, the stretching with the use of S-TPE, as component A, usually at temperatures from 105 to 140 ⁰ C, in particular 110 to 13O ⁰ C.

The surface activation process step can, in principle, be carried out directly after the extrusion or coextrusion of the plastic articles. In principle, however, extruded foils, for example, can first be laminated and / or back-injected, poured, 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 producing multilayer plastic articles carried out, if desired.

Metallized plastic objects

The extruded and surface-activated plastic articles produced as described, in particular films or sheets, composite layer films or sheets and molded parts, are particularly suitable for producing metallized plastic articles without the need for further special pretreatment of the surface.

In principle, all processes known to the person skilled in the art and described in the literature for the electroless and galvanic deposition of metals on plastic surfaces are suitable as the last process step of the process according to the invention for producing the metallized plastic articles (see, for example, Hollar Ebneth et al., Metallizing of plastics: Practical experience with physically, chemically and galvanically metallized high polymers, Expert Verlag, Renningen-Malmsheim, 1995, ISBN 3-8169-1037-8; Kurt Heymann et al., Kunststoffmetallisie- tion: Handbook for Theory and Practice, Series Electroplating and Surface Treatment 22, Saulgau: Leuze, 1991; Mittal, KL (ed.), Metallized Plastics Three: Fundamental and Applied Aspects, Third Electrochemical Society Symposium on Metallized Plastics: Proceedings, Phoenix, Arizona, October 13-18, 1991, New York, Plenum Press).

Normally, the extruded plastic articles are electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution after the last shaping process, the metal of this metal salt solution having a more positive normal potential corresponding to acidic, neutral or basic solution than 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 the extruded plastic objects, a currentless or electrodeposited layer Ms is applied in this way. Preferred layers Ms 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 Ms 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 ₉ , preferably galvanically, ie, applying external voltage and current flow, can be applied to the electrolessly depositable layer Ms by 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 galvanic deposition of layers M ₉ of aluminum is preferred. Application by direct metallization by means of vacuum vapor deposition, irradiation / spraying or sputtering by methods known to those skilled in the art is also possible.

The thicknesses of the one or more deposited layers M ₉ are in the usual range known to the person skilled in the art and are not essential to the invention.

Particularly preferred metallized plastic articles for use as electrically conductive components, in particular printed circuit boards, have an electrolessly deposited copper layer and at least one further, electrodeposited layer.

Particularly preferred metallized plastic articles for use in the decorative sector have an electrolessly deposited copper layer, on which a galvanic deposited nickel layer and deposited on this deposited chromium, silver or gold layer.

The metallized plastic articles which can be produced by the process according to the invention and comprise an electrolessly depositable metal layer M _s are readily applied to a deposited metal layer M ₉ as electrically conductive components, in particular printed circuit boards, transponder antennas, switches, sensors and MIDs, EMI shielding (ie shielding for Avoidance of so-called "electro-magnetic 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 ₉ are as electrically conductive components, in particular printed circuit boards, transponder antennas, switches, sensors and MIDs, as EMI shieldings such as absorbers, dampers or Reflectors for electromagnetic radiation or gas barriers or decorative parts, in particular decorative parts in the automotive, sanitary, toy, household and office sector, suitable.

Examples of such applications are: computer cases, 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, metallized trim on furniture and mirrors, frame for shower enclosures.

Also to be mentioned are: metallised plastic surfaces in the automotive sector, such as e.g. Trim strips, exterior mirrors, radiator grills, front-end metallization, wind deflectors, body exterior parts, door sills, tread plate replacement, wheel covers. In particular, such parts are made of plastic, which were previously made partially or entirely of metals. Examples include: Tools such as pliers, screwdrivers, drills, chuck, saw blades, ring and open-end wrench.

Furthermore, the metallized plastic articles, insofar as they comprise magnetizable metals, find applications in areas of magnetizable functional parts, such as magnetic boards, magnetic games, magnetic surfaces, e.g. 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, insulation materials.

The processes according to the invention for the production of metallized plastic articles are characterized in that, with comparably good processing properties and freedom of design, the plastic articles, For example, in forming processes for the production of complex shaped components, compared to known methods for producing metallized plastic parts an improved electroless and galvanic metallization is possible. The metallized plastic articles which can be produced by the process according to the invention have qualitatively improved, in particular more homogeneous and / or better adhering, metal layers compared to metallized plastic bodies produced by known processes with comparably good processing properties and freedom of design.

The invention will be explained in more detail below with reference to examples.

As component A were used:

A1. Styroflex ^® 2G66, an S-TPE from BASF Aktiengesellschaft with an elongation at break of 480% (determined in a tensile test according to ISO 527-2: 1996 on test specimens of type 1 BA (Annex A of the mentioned standard: "small specimens")) A3: Styrolux ^® 3G55 from BASF Aktiengesellschaft

As component B was used:

B1. Carbonyl iron powder from BASF Aktiengesellschaft

From 1 part by weight of A1 and 17 parts by weight of B1 were prepared mixture at temperatures of 140-190 ⁰ C, depending on a Kunststoffvor- a kneader (IKA Type VISC MKD laboratory kneader H60). In each case, a free-flowing powder was obtained, which was then subsequently compounded in a mini extruder from DSM with an amount of component A3 such that the proportion by weight of component B1 based on the total weight of the plastic mixtures was 89%.

Thereafter, the plastic mixture thus obtained in each case at 220 ⁰ C according to the in ISO 527-2: 1996 (Appendix A of said standard: "small specimens") injection molded into test specimens of the type 1BA.

Furthermore, pressed films having a thickness of 100 μm and a pressure of 200 bar and a temperature of 200 ^° C. were produced from the resulting plastic mixture. The resulting films were each placed in an injection mold (60x60x2 mm platelets with tape casting) and back-injected with Styrolux ^® 3G55 at 200 ⁰ C (injection machine from Netstal with semi-automatic control, screw diameter 32 mm, needle valve nozzle, cone gate, plate tool with 4 mm thickness and 200 x 100 mm surface, screw speed 100 rpm, screw feed rate: 50 mm / s, cycle time: 50 s, injection time: 2 s, holding time: 10 s, cooling time: 30 s, dosing time: 18 s, cylinder temperature: 200 - 220 ⁰ C, mold ^surface temperature: 45 ⁰ C. The plastic articles (specimens and back-injected films) produced in the described manner were surface-activated by the methods mentioned in Table 1 and then immersed in acidic (pH 1-2), 5 wt .-% copper (II) sulfate solution at 23 ° C. and applying a voltage of 1 V metallized at a current of 2 amperes. Table 1 shows the quality of each after a GaI- vanisierungsdauer one minute copper layer obtained.

Table 1 :

*: Tests marked with V are for comparison

Claims

claims

1. A process for the production of a metallized, extruded plastic article, wherein in a first step, the melt mixing and extrusion of a plastic mixture comprising, based on the total weight of the components A ₁ B, C, and D, a total of 100 wt .-% reveals

a from 5 to 50% by weight of a thermoplastic polymer as component A, b from 50 to 95% by weight of a metal powder having an average particle diameter of from 0.01 to 100 μm (determined according to the method mentioned in the description) the metal has 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 their Gem see than Component D ₁

takes place, in a final step, the extruded plastic object is electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, said metal having a more positive normal potential in accordance with acidic, neutral or basic solution as a component

B ₁

characterized in that the plastic article is surface activated after the step of melt blending and extrusion and before the step of contacting with the metal salt solution in the non-molten state.

2. The method according to claim 1, characterized in that the surface activation by stretching the plastic article by a factor of 1.1 to 10 takes place.

3. The method according to claim 2, characterized in that the stretching unidirectional or bidirectional, wherein the plastic article is stretched in at least one stretching direction by a factor of 1, 1 to 10.

4. The method 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.

5. The 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 _{9 are} deposited.

6. The method according to claims 1 to 5, characterized in that the plastic article is an extruded film, plate, an extruded profile, tube or an extruded strand.

7. The method according to claims 1 to 6, characterized in that before or after the surface activation 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.

8. Process according to Claims 1 to 7, characterized in that one or more polymers selected from the group of impact-modified vinylaromatic copolymers, thermoplastic elastomers based on styrene, polyolefins, polycarbonates and thermoplastic polyurethanes are used as component A.

9. The method according to claims 1 to 8, characterized in that the metal salt solution is a silver and / or copper and / or nickel salt solution, and component B is iron.

10. The method according to claims 1 to 9, characterized in that is used as component B carbonyl iron powder.

11. The method according to claims 5 to 10, characterized in that the one or more further deposited metal layers M ₉ made of copper and / or chromium and / or nickel and / or silver and / or gold, and were electrodeposited.

12. Metallized, extruded plastic articles, producible according to one of claims 1 to 11.

13. Use of metallized, extruded plastic articles, producible according to claims 1 to 11 as electrically conductive components, EMI Shieldings such as absorbers, dampers or reflectors for electromagnetic radiation or as gas barriers.

14. Use of metallized, extruded plastic articles, producible according to claims 5 to 11 as decorative parts, in particular decorative parts in the automotive, sanitary, toy, household and office sector.

15. Electrically conductive components, EMI shieldings such as absorbers, dampers or

Reflectors for electromagnetic radiation and gas barriers comprising metallized, extruded plastic articles producible according to claims 1 to 11.

16. decorative parts, in particular decorative parts in the automotive, sanitary, toy, household and office sector, comprising metallized, extruded plastic articles produced according to claims 5 to 11.