WO2008015168A1

WO2008015168A1 - Method for applying a metal layer to a substrate

Info

Publication number: WO2008015168A1
Application number: PCT/EP2007/057754
Authority: WO
Inventors: Rene Lochtman; Jürgen Kaczun; Norbert Schneider; Jürgen PFISTER; Norbert Wagner; Christoffer Kieburg; Ketan Joshi
Original assignee: Basf Se
Priority date: 2006-08-03
Filing date: 2007-07-27
Publication date: 2008-02-07
Also published as: TW200825206A; BRPI0714608A2; IL196548A0; RU2009107274A; EP2049711A1; KR20090036600A; JP2009545671A; CN101522956A; US20100006442A1

Abstract

The invention relates to a method for applying a metal layer to a substrate by chemical and/or galvanic deposition of a metal from a metal salt solution, an essential feature being that the substrate surface comprises carbon nanotubes. The invention further relates to the use of carbon nanotubes for applying a metal layer to a substrate.

Description

Method for applying a metal layer on a substrate

description

The present invention relates to methods for depositing a metal layer on a substrate by depositing a metal from a metal salt solution, and to the use of carbon nanotubes for depositing a metal layer on a substrate.

Methods for metallizing usually electrically non-conductive materials, such as plastics, are known. Such metallized parts, such as metallized plastic parts, are used in a variety of applications, for example, due to their electrical conductivity as electrical components. Furthermore, you will find wide use u.a. in the decor sector, since they have the same appearance as completely made of metal objects advantages by lighter weight and less expensive production.

There are widespread methods for metallizing plastics, in which necessarily a comparatively complicated pretreatment of the plastic surface by chemical or physical roughening or etching processes, for example with chromium-sulfuric acid, and / or the application of e.g. precious metal-containing primer or adhesion promoter layers is necessary before the electroless and / or galvanic deposition of dense and firmly adhering metal layers is possible (see, for example, WO 01/77419).

Another well-known method of providing plastics that have electrical conductivity (which is a necessary prerequisite for electrodeposition) is the incorporation of carbon nanotubes, often referred to as "carbon nanotubes" or "carbon nanofibrils", in plastic. These electrically conductive carbon nanotubes also have the advantages, e.g. to have low weight over metal powders and to usually give plastics increased toughness (see, for example, US 2006/0025515 A1).

DE 102 59 498 A1 discloses electrically conductive thermoplastics containing both a particulate carbon compound such as carbon black or graphite, and carbon nanofibrils. The plastic mixtures described therein have, in addition to the electrical conductivity, good flowability, good surface quality and high toughness. They are particularly suitable for electrostatic painting and electrostatic finishing of plastics. However, the surface resistances disclosed in the document are not sufficient when using the conductive thermoplastics as a substrate in a galvanic metallization process. The object of the present invention is to provide improved methods for applying a metal layer to a substrate by chemical and / or galvanic deposition of a metal from a metal salt solution. In particular, methods should be provided in which metal layers with good adhesion to the substrate can be deposited inexpensively and in good quality on a substrate within comparatively short plating times, and in which the metallized substrates have a comparatively low weight.

Accordingly, the aforementioned methods for applying a metal layer on a substrate by chemical and / or electrodeposition of a metal have been found from a metal salt solution, in which it is essential that the substrate surface has carbon nanotubes.

Furthermore, the use of carbon nanotubes for depositing a metal layer on a substrate has been found.

The methods according to the invention enable an improved deposition of a metal layer on a substrate by chemical and / or galvanic deposition of a metal from a metal salt solution. In particular, according to the methods of the invention, metal layers with good adhesion to the substrate can be deposited on a substrate cost-effectively and in good quality within relatively short plating times. The metallized substrates produced in this way have a comparatively low weight.

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

An essential feature of the method according to the invention is that the substrate surface of the substrate to be metallized has carbon nanotubes. This means that carbon nanotubes are contained either in the substrate itself and thus also on its surface, or else that carbon nanotubes in the form of an adhesive polymer coating or a lacquer are applied to a substrate which itself has no carbon nanotubes be applied. The carbon nanotubes located in or on the substrate surface cause an electrical conductivity which is indispensable for the subsequent chemical and / or galvanic metal deposition process on the substrate. For example, in order to increase the electrical conductivity, other electrically conductive components, for example metal powder or soot particles, may be located in or on the substrate surface in addition to the carbon nanotubes; their presence is not essential to the invention. The carbon nanotubes as such and their preparation will be described below (components B and B ^' ). In preferred embodiments of the method according to the invention substrates are therefore used in the chemical and / or galvanic metal deposition process, which were prepared from a carbon nanotube-containing molding compound described in more detail below. In further preferred embodiments of the process according to the invention, substrates are used in the chemical and / or galvanic metal deposition process, which are provided with a dispersion described below in more detail carbon nanotubes and then at least partially dried and / or at least partially cured.

Carbon-nanotube-containing molding compounds

The substrates which can be used in the process according to the invention are based in a preferred embodiment on thermoplastic molding compositions comprising, based on the total weight of components A, B, C and D, which gives a total of 100% by weight,

a 20 to 99 wt .-%, preferably 55 to 95 wt .-%, particularly preferably 60 to 92

Wt .-% of component A, b 1 to 30 wt .-%, preferably 5 to 25 wt .-%, particularly preferably 8 to 20

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 0 to 40 wt .-%, preferably 0 to 30 wt .-%, particularly preferably 0 to 10 wt .-% of component D.

The individual components of these molding compositions are described below:

Component A

As component A, in principle, all thermoplastic polymers are suitable. In general, the thermoplastic polymers have 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 (these and all other mentioned in this application elongation at break and tensile strengths 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")).

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 ™ CPC), polyamides, polyethylene terephthalate (PET), Polyethylene terephthalate glycol (PETG), polybutylene terephthalate (PBT), aliphatic-aromatic copolyesters (such as Ecoflex ^® from BASF Aktiengesellschaft), 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, aliphatic-aromatic copolyesters, 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). ASA polymers and / or ABS polymers are preferably 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 .alpha.-methylstyrene and acrylonitrile.

In a preferred embodiment in which the thermoplastic molding compositions comprise ASA polymers, the rubber-elastic graft copolymer A ^κ of component A is composed of

a1 1 - 99 wt .-%, preferably 55 - 80 wt .-%, in particular 55-65 wt .-%, of a particulate graft A1 with a glass transition temperature below 0 ⁰ C, a2 1 - 99 wt .-%, 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 s

Alkyl esters of acrylic acid, preferably n-butyl acrylate and / or Ethylhexylacry- lat as component A1 1, a12 0.01 to 20 wt .-%, preferably 0.1 to 5.0 wt .-%, of at least one poly-functional onellen 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, 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 are in all cases the weight average particle sizes, 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 (mean particle diameter), the dio and dgo values resulting from the integral mass distribution are used. The dio or dgo value of the integral mass distribution is correspondingly The dso value is defined with the difference that they are based on 10 or 90 wt .-% of the particles. The quotient

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 A1 is preferably alkyl acrylate rubbers of one or more Ci-8-alkyl acrylates, preferably C _4- 8 alkyl acrylates, preferably wherein at least some 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, 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 have ^κ while an average particle size dso of 50 - 1000 nm, preferably from 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 - 800 nm, 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 multistage graft copolymer, wherein the grafting steps are generally prepared from resin-forming monomers and have a glass transition temperature T ₉ above 30 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 grafting base A1 is composed of 15-99% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent 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 ⁰ C.

In a preferred embodiment, the graft A2 consists of at least one graft and the outermost graft shell thereof has a glass transition temperature of more than 30 ⁰ 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 ^K are preferably prepared by free-radical emulsion polymerization in the presence of latices 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.

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 50-1000 nm is preferably carried out by the 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 28th 26,925 and US-A 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 80 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 precise 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 acid ester polymer has a dδo value 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 is then in a next step in the presence of the thus obtained latex of the crosslinked acrylic acid ester polymer ge According to one embodiment of the invention, a monomer mixture of styrene and acrylonitrile is polymerized, 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 graft base again in aqueous emulsion under the usual 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, 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 ^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 more preferably 55-65% by weight of grafting A1 and 1-99% by weight, preferably 20-45, particularly 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 thermoplastic molding compositions comprise ABS polymers, the rubber-elastic graft copolymer A ^κ '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 '60 to 100, preferably 70 to 100 wt .-% 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 succinic 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', based on A2 ¹ ,

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 thermoplastic molding compositions 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 monoethylenic unsaturated monomer, in particular styrene, α-methylstyrene, n-butyl acrylate or mixtures thereof,

a2 "from 10 to 60, preferably from 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 wt .-% of at least one further monoethylenically unsaturated monomer, preferably methyl methacrylate and n-butyl acrylate.

In a preferred embodiment in which the thermoplastic molding compositions include 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 vinyl aromatic 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 .-%, particularly preferably 0 - 40 wt .-% of styrene-derived units are contained, 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 thermoplastic molding compositions comprise ABS polymers as component A, the hard matrix A ^{M '} of component A is at least one hard copolymer which contains units derived from vinylaromatic monomers, and wherein, based on the total weight of vinylaromatic monomer-removing units, 0-100% by weight, preferably 40-100% by weight, particularly preferably 60-100% by weight of α- Methylstyrene and 0-100% by weight, preferably 0-60% by weight, particularly preferably 0-40% by weight of units derived from styrene, from, 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 thermoplastic molding compositions 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 .-% 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. %, more preferably 60 to 100 wt .-% of α-methyl styrene and 0 to 100 wt .-%, preferably 0 to 60 wt .-%, particularly preferably 0-40 wt .-% of styrene-derived units are, from, based on A ^{M '}

3M1 "69 to 81, preferably 70 to 78 wt .-% of vinyl aromatic monomers, a _M 2" 19 to 31, preferably 22 to 30 wt .-% of acrylonitrile, αιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιιι 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 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 ^κ 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. 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 other 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-

Methyl styrene can be carried out with the acrylonitrile in bulk, solution, suspension or aqueous emulsion. The component A ^M or A ^{M '} preferably has 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 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 coextrusion, Kneading or rolling the components, wherein the components have been previously isolated, if necessary, 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 preferred are mixed as TPE-S is a linear or star-shaped styrene-butadiene block copolymer with external polystyrene blocks S and, between these, styrene-butadiene copolymer blocks with a random styrene / butadiene distribution (S / B) _random, or with a styrene gradient NDOM

(S / B) _tap Erzu (eg Styroflex ^® or Styrolux ^® of BASF Aktiengesellschaft, K-Resin ™ CPC).

The Gesamtbutadiengehalt is preferably in the range of 15 to 50 wt .-%, more 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 range 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 wt .-% and a styrene content of 30 to 65 wt .-%.

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 .-%.

Especially preferred are linear styrene-butadiene block copolymers of the general structure S- (S / B) -S lying with one or more, between the two S blocks, a random styrene / butadiene distribution having blocks (S / B) _ra NDOM , Such block copolymers are obtainable by anionic polymerization in a nonpolar solvent with the addition of a polar cosolvent or a potassium salt, as described, for example, in WO 95/35335 and WO 97/40079, respectively.

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 12th- 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, semicrystalline polyolefins, such as homopolymers 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. As component A, preference is given to 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 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 from 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'-dihydroxydiphenylsulfone, 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 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 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 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, measured in 0.5 wt .-% solution in dichloromethane at 25 ° C, preferably from 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, the thermoplastic molding compositions contain carbon nanotubes. Carbon nanotubes and their preparation are known in the art and described in the literature, for example in US 2005/0186378 A1. The synthesis of carbon nanotubes can be carried out, for example, in a reactor containing a carbon-containing gas and a metal catalyst (see, for example, US Pat. No. 5,643,502). Carbon nanotubes are commercially available, for example from the company Hyperion Catalysis or the company Applied Sciences Inc.

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

The addition of the carbon nanotubes can be carried out before, during or after the polymerization of the monomers to form the thermoplastic polymer of component A. If the addition of the nanotubes takes place after the polymerization, it is preferably carried out by adding to the thermoplastic melt in an extruder or preferably in a kneader. As a result of the compounding process in the kneader or extruder, in particular the aggregates already described can be largely or even completely comminuted and the carbon nanotubes are dispersed in the thermoplastic matrix.

In a preferred embodiment, the carbon nanotubes can be added as highly concentrated masterbatches in thermoplastics which are preferably selected from the group of thermoplastics used as component A. The concentration of the carbon nanotubes in the masterbatches is usually in the range of 5 to 50, preferably 8 to 30, particularly preferably in the range of 12 to 22 wt .-%. The preparation of masterbatches is described, for example, in US Pat. No. 5,643,502. Through the use of masterbatches, in particular the comminution of the aggregates can be improved. The carbon nanotubes may have shorter length distributions than originally used due to the processing into the molding compound or molding in the molding compound or in the molding.

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. Further preferred are the commercially available, oligomeric and polymeric dispersants known to the person skilled in the art, as described in CD Römpp Chemie Lexikon - Version 3.0, Stuttgart / New York: Georg Thieme Verlag 2006, keyword "dispersing assistant". Examples are polycarboxylic acids, polyamines, salts of long-chain polyamines and polycarboxylic acids, amine / amide functional polyesters and polyacrylates, soya lecithins, polyphosphates, modified caseins. The polymeric dispersants may be present as block copolymers, comb polymers or random copolymers.

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

Examples of anionic surfactants are alkali metal salts of organic carboxylic acids having chain lengths of 8-30 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 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, 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 1000 g / mol. Preferred nonionic surfactants are polyethylene glycols.

The polyalkylene glycols are known per se or can be prepared by processes known per se, for example by anionic polymerization with alkali 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. Suitable starter molecules are, for example: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid or terephthalic acid, aliphatic or aromatic, optionally N-mono-, N, N- or N, N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in the Alkyl radical, such as mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetra- min, 1, 3-propylenediamine, 1, 3 or 1, 4-butylenediamine, 1, 2, 1, 3, 1, 4 , 1, 5 or 1, 6-hexamethylenediamine. Also suitable as starter molecules are: alkanolamines, for example ethanolamine, N-methyl- and N-ethyl-ethanolamine, dialkanolamines, for example diethanolamine, N-methyl- and N-ethyl-diethanolamine, and trialkanolamines, for example triethanolamine, and ammonia. Preference is given to using polyhydric, in particular dihydric, trihydric or polyhydric alcohols, such as ethanediol, propanediol 1, 2 and 1, 3, diethylene glycol, dipropylene glycol, butanediol 1, 4, hexanediol 1, 6, Glycerol, trimethylolpropane, pentaerythritol, and sucrose, sorbitol and sorbitol.

Also suitable 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 a manner known per se can be produced. 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.

Component D

As component D, the thermoplastic molding compositions contain fibrous or particulate fillers other than component B 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 microns. 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 thermoplastic molding compositions may further contain other additives that are typical and common for plastic mixtures.

Examples of such additives are: dyes, pigments, colorants, antistatics, antioxidants, stabilizers to improve the thermal stability, to increase the stability to light, to increase the hydrolysis resistance and the resistance to chemicals, agents against the decomposition of heat and in particular the lubricants / lubricants, 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 oxidation inhibitors are usually metal halides (chlorides, bromides, iodides) derived from Group I metals 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. HALS stabilizers (Hindered Amine Light Stabilizers), benzophenones, resorcinols, salicylates, benzotriazoles such as Tinuvin ^® RP (UV absorber 2 - (2H-benzotriazole-2-yl) -4-methylphenol from CIBA) and other compounds are suitable. These are usually used in amounts of up to 2 wt .-% (based on the total mixture of the thermoplastic molding compositions).

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, colorants such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are also useful.

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

Process for the preparation of metallizable substrates

The preparation of the thermoplastic molding compositions from 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, depending on the type of polymer A used Usually in the range of 150 ⁰ C to 300 ⁰ C, in particular at 200 ° C to 280 ⁰ C. 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 or A and C, to be premixed first and then mixed with further components A, B and / or C or other components, for example 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 thermoplastic molding compositions can be processed into granules by processes known to the person skilled in the art in order to be processed at a later time, for example by extrusion, injection molding, calendering or pressing, into metallizable moldings (ie substrates), for example films or sheets or composite films or sheets , But you can also directly following the Mixing process or in one step with the Mi seh process (ie simultaneous melt mixing and preferably extrusion, preferably by means of a screw extruder, or injection molding) to metallizable moldings, such as films or plates, processed, in particular extruded or injection molded, are.

In a preferred embodiment of the method by means of extrusion, 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 method, the screw extruder is designed as a twin-screw extruder with at least one distributively mixing screw element.

The processes for extruding the metallizable moldings may be carried out by methods known to those skilled in the art and described in the art, e.g. Broad slit extrusion as adapter or die coextrusion, and with devices known to those skilled in the art and described in the prior art. The methods for injection molding, calendering or pressing the metallizable moldings are also known in the art and described in the prior art.

Metallizable moldings in the form of films or plates generally have a total thickness of 10 microns to 5 mm, preferably from 10 .mu.m to 3 mm, more preferably 20 .mu.m to 1, 5 mm, especially 100 .mu.m to 400 .mu.m.

The metallizable moldings can be subjected to further molding processes customary in plastics processing technology.

Moldings obtainable by further shaping processes:

The metallizable films or sheets or composite laminate sheets or films can be used to make further moldings. In this case, any shaped parts, preferably flat, especially large area, accessible. These foils or sheets and composite laminated sheets or foils are particularly preferably used for the production of further 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 by detachment of the Surfaces is minimized. Particularly preferred molded parts obtainable by further shaping processes comprise monofilms or composite layer plates or foils and a back-injected, foam-backed, back-poured or back-pressed carrier layer made of plastic. The production of such shaped parts from the metallizable films or plates or the metallizable composite layer plates or films can be carried out by known processes described, for example, in WO 04/00935 (the processes for the further processing of composite layer plates or films are described below, these processes but can also be used for further processing of the films or plates). 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 sheets or films may also be subjected to a previous thermoforming process.

For example, composite laminates or films having the three-layer structure of carrier layer, intermediate layer and cover layer or the two-layer structure of carrier layer and cover layer for the production of more complex components by thermoforming can be transformed. Both positive and negative thermoforming processes can be used. Corresponding methods are known to the person skilled in the art. The composite layer plates or foils are stretched in the thermoforming process. Since the surface quality and metallizability of the composite layered sheets or films does not decrease with stretching at high draw ratios, for example up to 1: 5, the thermoforming processes are almost free from any limitations in terms of stretching. After the thermoforming process, the composite layer plates or films may be subjected to further shaping steps, for example contour cutting.

From the composite layer plates or foils can, if necessary, after the described thermoforming processes, by injection molding, backfoaming, rear casting or backpressing the other metallizable moldings 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 11.

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, in a further preferred embodiment, the person skilled in the art is knew duroplastic molding compounds used. In a preferred embodiment, these plastic materials are glass fiber reinforced, suitable variants are described in particular in DE-A1 100 55 190. In the case of foam backing, polyurethane foams are preferably used, as described, for example, in DE-A1 199 39 11 1.

In a preferred manufacturing method, the metallizable composite layer plate or film is deformed by hot forming, then inserted into a mold and back molded with thermoplastic materials, back-molded or pressed behind, or back foamed with thermosetting plastics or back pressed.

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.

Carbon-nanotube-containing dispersions

In a further preferred embodiment, the substrates which can be used in the methods according to the invention for the chemical and / or electrodeposition of a metal are those in which the substrate is provided with a dispersion containing carbon nanotubes prior to the chemical and / or galvanic metallization step at least partially dried and / or at least partially cured.

Preferred carbon nanotube-containing dispersions contain, based on the total weight of the components A ^' , B ^' and C, which gives a total of 100 wt .-%,

a ^' 0.1 to 99.9 wt .-%, preferably 2 to 89.5 wt .-%, particularly preferably 4 to 84 wt .-% of component A ^' , b ^' 0.1 to 30 wt .-% , preferably 0.5 to 20 wt .-%, particularly preferably 1 to 10

Wt .-% of component B ^' , and c ^' 0 to 99.8 wt .-%, preferably 10 to 97.5 wt .-%, particularly preferably 15 to

95% by weight of component C.

The dispersion can except the above components A ^' to C at least one of the components

d ^' 0.1 to 50 wt .-%, preferably 0.5 to 40 wt .-%, particularly preferably 1 to 20 wt .-%, based on the total weight of the components A ^' - C one

Dispersant component D ^' ; such as e ^' 0 to 50 wt .-%, preferably 0.1 to 40 wt .-%, particularly preferably 0.5 to 30 wt .-%, based on the total weight of the components A ^' - C of a different component B ^' filler component E included.

The individual components of the dispersion are described below:

Component A ^'

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

The binder component A ^' is preferably a polymer or polymer mixture.

Preferred polymers as binders are ABS (acrylonitrile-butadiene-styrene); ASA (acrylonitrile-styrene-acrylate); acrylated acrylates; alkyd resins; Alkylvinylacetate; Alkylene vinyl acetate copolymers, in particular methylene vinyl acetate, ethylene vinyl acetate, butylene vinyl acetate; Alkylenvinylchlorid copolymers; amino resins; Aldehyde and ketone resins; Celluloses and cellulose derivatives, in particular hydroxyalkylcellulose, cellulose esters, such as - acetates, propionates, butyrates, carboxyalkylcelluloses, cellulose nitrate; epoxy acrylates; epoxy resins; modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, vinyl ethers, ethylene-acrylic acid copolymers; Hydrocarbon resins; MABS (containing transparent ABS with acrylate units); Melamine resins, maleic anhydride copolymers; Methacrylates; Natural rubber; synthetic rubber; Chlorinated rubber; Natural resins; rosins; Shellac; Phenol resins; Polyester; Polyester resins, such as phenolic ester resins; polysulfones; polyether; polyamides; polyimides; polyanilines; Polypyrrole; Polybutylene terephthalate (PBT); Polycarbonate (for example, Makrolon ^® of Bayer AG); polyester; polyether; polyethylene; Polyethylenthiophene; Polyethylene naphthalates; Polyethylene terephthalate (PET); Polyethylene terephthalate glycol (PETG); polypropylene; Polymethyl methacrylate (PMMA); Polyphenylene oxide (PPO); Polystyrenes (PS), polytetrafluoroethylene (PTFE); polytetrahydrofuran; Polyethers (for example polyethylene glycol, polypropylene glycol), polyvinyl compounds, in particular polyvinyl chloride (PVC), PVC copolymers, PVdC, polyvinyl acetate and copolymers thereof, optionally partially hydrolyzed polyvinyl alcohol, polyvinyl acetals, polyvinyl acetates, polyvinylpyrrolidone, polyvinyl ethers, polyvinyl acrylates and methacrylates in solution and as a dispersion and its copolymers, polyacrylic acid esters and polystyrene copolymers; Polystyrene (impact or not impact modified); Polyurethanes, non-crosslinked or crosslinked with isocyanates; polyurethane acrylates; Styrene-acrylic copolymers; Styrene-butadiene block copolymers (for example, Styroflex ^® or Styrolux ^® from BASF AG, K-Resin ™ CPC, Kraton D and Kraton G Kraton Polymers); Proteins, such as casein; SIS; Triazine resin, bismaleimide triazine resin (BT), cyanate ester resin (CE), allylated polyphenylene ether (APPE).

Furthermore, mixtures of two or more polymers may form the organic binder component A ^' .

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

Component B ^'

As component B ^' , the carbon nanotubes already described as component B can be used.

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

In a preferred embodiment the pre carried out incorporation of the carbon nanotubes in the binder component A ^', the carbon nanotubes as a highly concentrated master batches in polymers, preferably selected from the group of the component ^A' are metered be selected is set polymers. The concentration of the carbon nanotubes in the masterbatches is usually in the range of 5 to 50, preferably 8 to 30, particularly preferably in the range of 12 to 22 wt .-%. The production of masterbatches is, for example, in US-A 5643502 described. Through the use of masterbatches, in particular the comminution of the aggregates can be improved.

Due to the incorporation into the dispersion or by the previous incorporation into component A ^' , the carbon nanotubes may have shorter length distributions than originally used.

Component C

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

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

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

Component D ^'

The dispersion can furthermore contain, as dispersant component D ^', the dispersants already described as component C.

Component E ^'

Furthermore, the dispersion as filler component E ^' may contain the fillers already described as component D.

Furthermore, the dispersions in addition to the aforementioned components A ^' , B ^' , C and optionally D ^' and / or E ^' contain other additives, such as processing aids and stabilizers such as UV stabilizers, lubricants, corrosion inhibitors and flame retardants.

Furthermore, further additives, such as thixotropic agents, for example silica, silicates, such as aerosils or bentonites or organic thixotropic agents and thickeners, such as polyacrylic acid, polyurethanes, hydrogenated castor oil, dyes, fatty acids, fatty acid amides, plasticizers, wetting agents, defoamers, Lubricants, drying agents, crosslinkers, photoinitiators, complexing agents, waxes, pigments, conductive polymer particles, can be used.

The proportion of further additives, based on the total weight of the dispersion, is usually from 0.01 to 30% by weight. Preferably, the proportion is 0.1 to 10% by weight.

Preferred methods for preparing the dispersion include the steps

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

b ^' ) dispersing the mixture,

c ^' ) optionally adding the proportion of component C not used in step a ^' ) to adjust the viscosity for the particular application method.

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

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

In one embodiment of the method according to the invention for producing a metal layer on at least part of the surface of a substrate, the following steps are included:

a) applying a carbon-nanotube-containing dispersion to the substrate;

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

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

Suitable substrates are electrically non-conductive materials such as polymers. Suitable polymers are epoxy resins, for example bifunctional or polyfunctional, aramid-reinforced or glass-fiber-reinforced or paper-reinforced epoxy resins (for example FR4), glass fiber reinforced plastics, liquid cristal polymers (LCP), polyphenylene sulfides (PPS), polyoxymethylenes (POM), polyaryl ether ketones ( PAEK), polyetheretherketones (PEEK), polyamides (PA), polycarbonates (PC), polybutylene terephthalates (PBT), polyethylene terephthalates (PET), polyimides (PI), polyimide resins, cyanate esters, bismaleimide-triazine resins, nylon, vinyl ester resins , Polyesters, polyester resins, polyamides, polyanilines, phenolic resins, polypyrroles, polynaphthalene terephthalates, polymethylmethacrylate, polyethylenedioxythiophenes, phenolic resin coated aramid paper, polytetrafluoroethylene (PTFE), melamine resins, silicone resins, fluorine resins, dielectrics, APPE, polyetherimides (PEI ), Polyphenylene oxides (PPO), polypropylenes (PP), polyethylenes (PE), polysulfones (PSU), polyethersulfones (PES), polyarylamides (P AA), polyvinyl chlorides (PVC), polystyrenes (PS), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene acrylates (ASA), styrene acrylonitriles (SAN) and mixtures (blends) of two or more of the abovementioned polymers, which can be present in a wide variety of forms. The substrates may have additives known to the person skilled in the art, for example flame retardants.

In principle, all polymers listed under component A ^' can also be used. Furthermore, suitable substrates composites, foam-like polymers, Styropor® ^®, styrodur ^®, polyurethanes (PU), ceramic surfaces, textiles, paperboard, cardboard, paper, polymer coated paper, wood, mineral materials, silicon, glass, plant tissue and animal tissue or resin-impregnated Tissues pressed into plates or rolls.

In the context of this embodiment of the present invention, a "non-electrically conductive substrate" is preferably understood to mean that the surface resistance of the substrate is more than 10 ⁹ ohm / cm.

The dispersion may be applied to the substrate / support by methods known to those skilled in the art.

The application to the substrate surface can take place on one or more sides and extend to one, two or three dimensions. In general, the substrate may have any geometry adapted to the intended use.

The dispersion can be structured in step a) or applied in a planar manner. It is preferable that the steps of applying [step a)], drying and / or curing [step b)] and depositing a metal [step c)] are carried out in a continuous mode. This is possible by simply carrying out steps a), b) and c). However, it is of course possible a batchwise or semi-continuous process.

The coating may be the usual and well-known coating processes (casting, brushing, knife coating, brushing, printing (gravure printing, screen printing, FIE xodruck, pad printing, inkjet, offset, LaserSonic procedure ^® as described in DE10051850, etc.), pouring , Brushing, knife coating, brushing, spraying, dipping, rolling, powdering, fluidized bed or the like, etc.). The layer thickness preferably varies between 0.01 and 100 μm, more preferably between 0.1 and 50 μm, particularly preferably between 1 and 25 μm. The layers can be applied both over the entire surface as well as structured.

The drying or curing of the structured or full surface coating is carried out by conventional methods. Thus, for example, the dispersion can be cured chemically, for example by polymerization, polyaddition or polycondensation of the binder, for example by UV radiation, electron radiation, microwave radiation, IR radiation or temperature, or by purely physical means by evaporation of the solvent are dried. A combination of drying in a physical and chemical way is also possible. The layer obtained after application of the dispersion and at least partial drying and / or at least partial curing enables a subsequent chemical and / or galvanic deposition of a metal on the at least partially dried and / or at least partially cured dispersion layer.

Galvanic metal deposition on substrate

The substrates whose surfaces have carbon nanotubes, for example the carbon nanotube-containing thermoplastic molding compositions or the substrates coated with carbon nanotube-containing dispersions, are particularly suitable for the electrodeposition of metal layers, i. for the production of metallized substrates, without the need for elaborate pretreatment of the substrate surface.

In principle, all processes known to the person skilled in the art and described in the literature for the electrodeposition of metals on plastic surfaces are suitable as methods for producing the metallized substrates (see, for example, Harald Ebneth et al., Metallizing of Plastics: Practical Experiences with Physically, Chemically and Galvanically Metallized High Polymers , Expert Verlag, Reningen-Malmsheim, 1995, ISBN 3-8169-1037-8; Kurt Heymann et al., Kunststoffmetallisierung: 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).

The metallizable substrates are preferably connected cathodically by the application of an electrical voltage after the last molding process and brought into contact with an acidic, neutral or basic metal salt solution, wherein on the surface of the metallizable substrates containing the carbon nanotubes the metal of this metal salt solution is electrodeposited. Preferred metals for deposition are chromium, nickel, copper, gold and silver, in particular copper. It is also possible for a plurality of metal layers to be electrodeposited in succession, for example by introducing the metallizable substrates in each case while applying external voltage and current flow in immersion baths with solutions of different metals.

Although prior to the chemical and / or galvanic metallization, a special pre-treatment of the surface of the metallizable substrates is not necessary, in principle, however, surface activation can be carried out by methods known to the person skilled in the art. Surface activation of the substrate surface may be used to improve adhesion or to accelerate metal deposition can be used by the surface is roughened targeted, or exposed carbon nanotubes on the surface targeted. Exposing the nanotubes also has the advantage that a smaller proportion in the polymer matrix is needed to achieve metallization. Surface activation can be accomplished, for example, by mechanical abrasion, in particular by brushing, grinding, abrasive polishing or jet blasting, sandblasting or supercritical carbon dioxide (dry ice) blasting, physically, for example by heating, laser, UV light, corona or plasma discharge and / or chemical abrasion, in particular by etching and / or oxidation. Methods for carrying out the mechanical abrasion and / or chemical abrasion are known to the person skilled in the art and described in the prior art.

As abrasives for polishing, it is possible to use all abrasives known to the person skilled in the art. A suitable abrasive is, for example, pumice. In order to remove the uppermost layer of the cured dispersion by the pressure jet with the water jet, the water jet preferably contains small solid particles, for example pumice flour (AI2O3) with an average particle size distribution of 40 to 120 μm, preferably 60 to 80 μm, and quartz flour (SiO 2). with a particle size> 3 μm.

The surface activation can also be carried out by stretching (often also referred to as stretching or stretching) of the metallizable substrate, in particular by the factor 1, 1 to 10, preferably 1, 2 to 5, particularly preferably 1, 3 to 3. 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, preferably a multidirectional, in particular bidirectional, stretching, 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.

In the case of chemical abrasion, preference is given to using a chemical or chemical mixture suitable for the polymer of the substrate. In the case of a chemical abrasion, either the polymer can be at least partially dissolved and washed down, for example by a solvent on the surface, or it can be determined by means of suitable reagents, the chemical structure of the Matrix material are at least partially destroyed, whereby the carbon nanotubes are exposed. Also, reagents that swell the matrix material are suitable for exposing the carbon nanotubes. The swelling causes cavities in which the metal ions to be deposited can penetrate from the electrolyte solution, as a result of which a larger number of carbon nanotubes can be metallized. Due to the higher number of exposed carbon nanotubes, the process speed during metallization is higher.

For example, when the matrix material is an epoxy resin, a modified epoxy resin, an epoxy novolac, a polyacrylic acid ester, ABS, a styrene-butadiene copolymer or a polyether, the carbon nanotubes are exposed with an oxidizing agent. The oxidizing agent breaks up bonds in the matrix material, which allows the binder to be peeled off and thereby expose the particles. Suitable oxidizing agents are, for example, manganates, for example potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen, oxygen in the presence of catalysts such as manganese, molybdenum, bismuth, tungsten and cobalt salts, ozone, vanadium pentoxide, Selenium dioxide, ammonium polysulfide solution, sulfur in the presence of ammonia or amines, manganese dioxide, potassium ferrate, dichromate / sulfuric acid, chromic acid in sulfuric acid or in acetic acid or in acetic anhydride, nitric acid, hydroiodic acid, hydrobromic acid, pyridinium dichromate, chromic acid-pyridine complex, chromic anhydride, chromium ( VI) oxide, periodic acid, lead tetraacetate, quinone, methylquinone, anthraquinone, bromine, chlorine, fluorine, iron (III) salt solutions, disulfate solutions, sodium percarbonate, salts of oxohalogenic acids, such as, for example, chlorates or bromates or iodates, salts of halogenated acids, such as sodium periodate or sodium perchlorate, Sodium perborate, dichromates, such as, for example, sodium dichromate, salts of persulphuric acid, such as potassium peroxodisulfate, potassium peroxomonosulfate, pyridinium chlorochromate, salts of hypohalogenic acids, for example sodium hypochlorite, dimethyl sulfoxide in the presence of electrophilic reagents, tert-butyl hydroperoxide, 3-chlorobenzobenzoic acid, 2,2- Dimethylpropanal, des-Martin periodinane, oxalyl chloride, urea-hydrogen peroxide adduct, urea peroxide, 2-iodoxybenzoic acid, potassium peroxomonosulfate, m-chloroperbenzoic acid, N-methylmorpholine-N-oxide, 2-methylprop-2-yl-hydroperoxide, peracetic acid, pivaldehyde, Osmium tetraoxide, oxones, ruthenium (III) and (IV) salts, oxygen in the presence of 2,2,6,6-tetramethylpiperidinyl-N-oxide, triacetoxiperiodinane, trifluoroperacetic acid, trimethylacetaldehyde, ammonium nitrate. Optionally, to improve the exposure process, the temperature may be increased during the process.

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

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

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

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

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

The thicknesses of the one or more chemically and / or electrodeposited metal layers are within the usual range known to the person skilled in the art and are not essential to the invention.

Particularly preferred metallized substrates for use as electrically conductive components, in particular printed circuit boards, have at least one chemical and / or electrodeposited metal layer, in particular copper, silver or gold layer, on.

Particularly preferred metallized substrates for use in the decorative sector include a chemically and / or electrodeposited copper layer, on top of which a chemically and / or galvanically deposited nickel layer and a chromium, silver or gold layer deposited thereon.

The metallized substrates are, if appropriate after production of Leiterbahnstruk- structures according to known to the expert and described in the literature, as electrically conductive components, in particular printed circuit boards, RFID antennas, transponder antennas or other antenna structures, switches, sensors, and ^MIDs, EMI -Shieldings (that is, shielding to avoid so-called "electro-magnetic interference") such as absorbers, dampers or reflectors for electromagnetic radiation see or as gas barriers or decorative parts, especially decorative parts in the automotive, sanitary, toy, household and office area, suitable.

Examples of such applications are: computer cases, electronic component housings, military and non-military shielding devices, shower and washbasin faucets, shower heads, 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 substrates, 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 methods according to the invention enable an improved deposition of a metal layer on a substrate by chemical and / or galvanic deposition of a metal from a metal salt solution. In particular, metal layers with good adhesion to the substrate can be achieved by the process according to the invention comparatively short plating times cost-effectively and in good quality on a substrate. The metallized substrates produced in this way have a comparatively low weight.

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

Examples

Experimental part 1: Substrates made of a carbon nanotube-containing molding composition:

As component A were used:

Ai Styroflex ^® 2G66, an S-TPE from BASF Aktiengesellschaft. A-ii Polypropylene PP4821 from Borealis, melt flow index (determined to ISO 1133 at 230 ° C and 2.16 kg) 2.4 g / 10min.

As component B was used:

Bi Baytubes ^® C150P, multi-wall carbon nanotubes from Bayer Material Science AG with a carbon content> 95% by weight, an average particle diameter of 13 to 16 nm and a length of 1 to 10 μm.

For non-inventive comparative experiments, the following components were used:

Vi: ^Vulcan® XC 72R, Conductivity Black from Cabot Corp.

Production of metallizable substrates:

To the proportions of component A mentioned in Table 1 were in a kneader IKA Duplex at temperatures between 120 ⁰ C and 150 ⁰ C mentioned in Table 1 amounts of the other components added in portions and mixed (data in wt .-%, respectively on the total weight of all components). The molding compositions obtained after kneading for about 30 minutes were injection-molded into flat test specimens of 50 × 50 mm edge length.

Surface Activation:

The following surface activation was additionally performed on the test specimens identified in Table 1: The specimens were immersed over a period of 2 min in a 80 ⁰ C hot aqueous solution containing 6 wt .-% KMnO ₄ and 4.5 wt .-% NaOH (in each case based on the total weight of the aqueous solution). The specimens were then rinsed with running water for 30 seconds. Finally, the samples were immersed over a period of 1 min in an aqueous solution containing 2 wt .-% H2O2 and 10 wt .-% H2SO4 (in each case based on the total weight of the aqueous solution).

metallization:

The specimens were prepared by immersing and applying a voltage of 1 V in a commercially available cupric acid cupric acid copper bath Cupracid ^® HS (containing 21 wt .-% CuSO ₄ , 5.5 wt .-% H ₂ SO ₄ , 0.2 wt. % Brightener, 0.5% by weight leveler HS and 0.02% by weight NaCl, in each case based on the total weight of the solution, in aqueous solution) from Atotech over a period of 30 minutes. The metallizability of a specimen was considered to be present when a visually homogeneous copper layer had been deposited on the entire specimen after the 30-minute galvanization.

Table 1 shows the metallizability of the specimens.

Table 1 :

Examples marked with "V" are comparative examples, and the metallizability of a specimen was rated "yes" if a visually homogeneous copper layer had been deposited on the entire specimen after the 30-minute galvanization mentioned in the description. Test Part 2: Coating of a Substrate with a Carbon Nanotube-Containing Dispersion

As component A ^' were used:

A ^'-i Styroflex® ^® 2G66, a S-TPE from BASF Aktiengesellschaft.

As component B ^' was used:

B ^'-i Baytubes C150P ^®, multi-wall carbon nanotubes from Bayer MaterialScience AG with a carbon content> 95 wt .-%, a mean particle diameter of 13-16 nm and a length of 1 -1 Oμm.

As component C was used:

C ^' -i n-butyl acetate.

As component E ^' was used:

E ^'-i: Vulcan ^® XC 72R, a conductive carbon black ( "Conductive Carbon Black") Cabot Corp.

Preparation of the dispersions:

To the proportions of component A ^' mentioned in Table 2 were added in a kneader IKA Duplex at temperatures of 120 ⁰ C mentioned in Table 2 amounts of component B ^{' in} portions and mixed (in wt .-%, each based on the Total weight of all components).

The mixtures thus obtained were mixed in a mixer "Skandex DAS 200" for a period of 1 h in the presence of glass bodies with the proportions of component C mentioned in Table 2 and optionally other components (data in% by weight, based in each case on the Total weight of all components). The glass bodies were then separated.

Coating the substrate:

The further processing of the dispersions thus obtained was carried out according to two alternative methods (and identified in Table 2): α) The dispersions were applied to a film of polyethylene terephthalate as substrate. This was followed by a ten-minute drying of the dispersion at 80 ⁰ C to form an approximately 25 micron thick layer on the substrate; or ß) The dispersions were analyzed by means of a gravure color proofer "Saueressig

CP90 / 200 "in the form of an RFID antenna printed on a sheet of polyethylene terephthalate as substrate and then dried to form sheets with a layer thickness of about 3 microns.

Surface Activation:

In the case of the coated substrates marked correspondingly in Table 2, the following surface activation was additionally carried out:

The coated substrates were immersed over a period of 2 minutes in a 80 ⁰ C hot aqueous solution containing 6 wt .-% KMnO ₄ and 4.5 wt .-% NaOH (each based on the total weight of the aqueous solution). The coated substrates were then rinsed with running water for 30 seconds. Finally, the coated substrates were immersed over a period of 1 min in an aqueous solution containing 2 wt .-% H2O2 and 10 wt .-% H2SO4 (each based on the total weight of the aqueous solution).

metallization:

The coated substrates were (by dipping and applying an electric voltage of 1 V in a commercially available acidic copper sulfate bath Cupracid ^® HS weight containing 21 wt .-% CuSO _4, 5.5 wt .-% H ₂ SO _4, 0.2. % Of brightener, 0.5% by weight leveler HS and 0.02% by weight NaCl, in each case based on the total weight of the solution, in aqueous solution) from Atotech over a period of 30 minutes. The metallizability of a coated substrate was considered to be true when a visually homogeneous copper layer had been deposited on the entire substrate after 30 minutes of electroplating.

Table 2 shows the metallizability of the coated substrates.

Table 2:

the metallizability of a coated substrate was then rated "yes" if a visually homogeneous copper layer had been deposited on the entire substrate after the 30-minute galvanization referred to in the description.

Claims

claims

A method of depositing a metal layer on a substrate by depositing a metal from a metal salt solution, characterized in that the substrate surface comprises carbon nanotubes.

2. The method according to claim 1, characterized in that are used as carbon nanotubes mono- or multi-walled carbon nanotubes with a length in the range of 0.5 to 1000 microns and a diameter in the range of 0.002 to 0.5 microns.

3. Process according to Claims 1 to 2, characterized in that the substrate comprises a thermoplastic molding composition, the thermoplastic molding composition, based on the total weight of components A, B, C and D, which gives a total of 100% by weight,

a 20 to 99 wt .-% of a thermoplastic polymer as component A, b 1 to 30 wt .-% carbon nanotubes 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,

includes.

4. The method according to claim 3, characterized in that as component A one or more polymers selected from the group of impact-modified vinyl-aromatic copolymers, thermoplastic elastomers based on styrene, polyolefins, polycarbonates and thermoplastic polyurethanes are used.

5. The method according to claims 1 to 2, characterized in that the substrate is provided with a dispersion, the dispersion at least partially dried and / or at least partially cured and after the at least partial drying and / or at least partially curing of the dispersion, the chemical and / or galvanic deposition of the metal, wherein the

dispersion

a ^' 0.1 to 99.9 wt .-% based on the total weight of the components

A ^' , B ^' and C of an organic binder component A ^' ;

b ^' 0.1 to 30% by weight, based on the total weight of components A ^' , B ^' and C, of carbon nanotubes as component B ^' ; c ^'0 with respect to 99.8 wt .-% based on the total weight of components ^A', B ^'and C, a solvent component C,

includes.

6. The method according to claim 5, characterized in that the dispersion further comprises at least one of the components

d ^' 0.1 to 50 wt .-% based on the total weight of the components A ^' ,

B ^' and C of a dispersant component D ^' ; such as

e ^'from 0.1 to 50% by weight, based on the total weight of the components A ^' ,

B ^' and C contains a filler component E ^' .

7. The method according to claim 5 to 6, characterized in that the binder component A ^' consists of a polymer or polymer mixture.

8. Process according to Claims 5 to 7, characterized in that the application of the dispersion to the substrate is structured or flat.

9. Process according to Claims 1 to 8, characterized in that the carbon nanotube substrate surface is surface-activated before the chemical and / or galvanic deposition of a metal.

10. Use of carbon nanotubes for applying a metal layer to a substrate.

1 1. Substrate surface at least partially comprising an electrically conductive metal tallschicht obtainable from the method according to one of claims 1 to 9.

12. Use of a substrate surface according to claim 11 for conducting electrical current, heat, as a decorative metal surface, for shielding electromagnetic radiation and for magnetization.

13. Use according to claim 12 as a printed circuit board, RFI D antenna, Transponderan- antenna or other antenna structure, seat heating, flat cable, foil conductor, contactless chip card, printed conductors in solar cells or in LCD or plasma screens or for the production of chemically and / or electroplated Products in any form.