WO2006114431A1 - Procede de fabrication d'objets en plastique extrudes metallises - Google Patents

Procede de fabrication d'objets en plastique extrudes metallises Download PDF

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Publication number
WO2006114431A1
WO2006114431A1 PCT/EP2006/061846 EP2006061846W WO2006114431A1 WO 2006114431 A1 WO2006114431 A1 WO 2006114431A1 EP 2006061846 W EP2006061846 W EP 2006061846W WO 2006114431 A1 WO2006114431 A1 WO 2006114431A1
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WIPO (PCT)
Prior art keywords
component
weight
plastic
metal
extruded
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PCT/EP2006/061846
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German (de)
English (en)
Inventor
Norbert Schneider
Gerald Lippert
Rene Lochtman
Heiko Maas
Jürgen PFISTER
Bettina Sobotka
Norbert Wagner
Norbert Niessner
Matthias Scheibitz
Michael Dahlke
Volker Warzelhan
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Basf Aktiengesellschaft
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Priority claimed from DE200510019983 external-priority patent/DE102005019983A1/de
Priority claimed from DE102005048161A external-priority patent/DE102005048161A1/de
Priority claimed from DE200510059323 external-priority patent/DE102005059323A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2006114431A1 publication Critical patent/WO2006114431A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • B24C1/003—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods using material which dissolves or changes phase after the treatment, e.g. ice, CO2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0415—Ornamental plaques, e.g. decorative panels, decorative veneers containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/013—Additives applied to the surface of polymers or polymer particles

Definitions

  • the invention relates to processes for the production of metallized, extruded plastic articles, wherein in a first step the melt mixing and extrusion of a plastic mixture comprising, based on the total weight of the components A, B, C, and D 1, which gives a total of 100 wt .-%,
  • the extruded plastic article is electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, this metal having a more positive normal potential in accordance with acidic, neutral or basic solution than component B.
  • the invention relates to metallized extruded plastic articles, the use of these objects and EMI shieldings such as absorbers, dampers or reflectors for electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects.
  • EMI shieldings such as absorbers, dampers or reflectors for electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects.
  • metal powder-containing plastic objects can be electrolessly and / or galvanically metallized.
  • Such metallized plastic objects can be used for example as electrical components due to the electrical conductivity.
  • a further object of the present invention is to provide metallized plastic articles which have qualitatively improved, in particular more homogeneous and / or better adhering, metal layers compared to metallized plastic bodies produced by known methods with comparably good processing properties and freedom of design.
  • a 5 to 50 wt .-% of a thermoplastic polymer as component A b 50 to 95 wt .-% of a metal powder having an average particle diameter of 0.01 to 100 microns (determined according to the method mentioned in the description), wherein the metal has a more negative normal potential in acidic solution than silver, as component B, c 0 to 10 wt .-% of a dispersant as component C, and d 0 to 40 wt .-% fibrous or particulate fillers or mixtures thereof as component D. .
  • the extruded plastic object is electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution, this metal having a more positive normal potential in accordance with acidic, neutral or basic solution than component B,
  • the plastic article after the step of melt mixing and extrusion and before the step of contacting with the Metal salt solution in the non-molten state is understood as the state within a temperature range of +/- 20 ° C. to the melting point Tm of the semicrystalline polymer, as a non-molten state in the case of non-crystalline polymers State in the temperature range from 0 to 70 0 C above the highest glass level of the non-crystalline polymer to understand) is surface-activated.
  • metallized extruded plastic articles the use of these articles and EMI shieldings such as absorbers, dampers or reflectors for electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects were found.
  • the methods according to the invention for producing metallized plastic articles are characterized in that, with comparably good processing properties and freedom of design of the plastic articles, for example in forming processes for the production of complex shaped components, compared to known methods for producing metallized plastic parts an improved electroless and galvanic Metallisieriana is possible.
  • the metallized plastic articles which can be produced by the process according to the invention have qualitatively improved, in particular more homogeneous and / or better adhering, metal layers compared to metallized plastic bodies produced by known processes with comparably good processing properties and freedom of design.
  • the first step of the processes according to the invention comprises melt mixing and extrusion of a plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100% by weight,
  • a 5 to 50% by weight preferably 10 to 40% by weight, particularly preferably 20 to 5 30% by weight of component A, b 50 to 95% by weight, preferably 60 to 90% by weight, more preferably 70 to
  • component B 80 wt .-% of component B, c 0 to 10 wt .-%, preferably 0 to 8 wt .-%, particularly preferably 0 to
  • a preferred embodiment of the invention is based on a dispersant-containing plastic mixture comprising, based on the total weight of components A, B, C and D, which gives a total of 100 wt .-%,
  • component A 50 to 94.9 wt .-%, preferably 60 to 89.5 wt .-%, particularly preferably 70 bis
  • component B 79 wt .-% of component B, c 0.1 to 10 wt .-%, preferably 0.5 to 8 wt .-%, particularly preferably 1 to 5 wt .-% of component C, and d 0 to 40 wt .-%, preferably 0 to 29.5 wt .-%, particularly preferably 0 to 9 wt .-% of component D.
  • the elongation at break of component A is by a factor of 1.1 to 100, preferably by a factor of 1.2 to 50, more preferably by a factor of 1.3 to 10 greater than the elongation at break of the plastic mixture comprising the components A, B, and if present C and D, and also the tensile strength of component A by a factor of 0.5 to 4, preferably by the factor 1 to 3, more preferably by a factor of 1 to 2.5 is greater than the tensile strength of the plastic mixture comprising the components A, B, and if present C and D (a factor less than 1 means that the tensile strength of the component A is smaller as the tensile strength of the plastic mixture comprising the components A, B, and if present C and D);
  • a plastic mixture comprising the following components can be used in the processes according to the invention.
  • thermoplastic polymers are suitable as component A, in particular those having an elongation at break in the range from 10% to 1000%, preferably in the range from 20 to 700, particularly preferably in the range from 50 to 500.
  • Suitable as component A are, for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene (impact-resistant or not impact-modified), ABS (acrylonitrile-butadiene-styrene), ASA (acrylonitrile-styrene-acrylate), MABS (transparent ABS, containing methacrylate units ), styrene-butadiene block copolymer (for example, Styroflex ® or from BASF Styrolux ® Aktiengesellschaft, K-Resin TM CPC), polyamides, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polybutylene terephthalate (PBT), polycarbonate (such as Makrolon ® of Bayer AG), polymethyl methacrylate (PMMA), poly (ether) sulfones, and polyphenylene oxide (PPO).
  • component A preference is given to using one or more polymers selected from the group of impact-modified vinylaromatic copolymers, thermoplastic elastomers based on styrene, polyolefins, polycarbonates and thermoplastic polyurethanes.
  • polyamides can be used.
  • Preferred impact-modified vinylaromatic copolymers are impact-modified copolymers of vinylaromatic monomers and vinyl cyanides (SAN).
  • SAN vinylaromatic monomers and vinyl cyanides
  • ASA polymers and / or ABS polymers are used as impact-modified SAN, as well as (meth) acrylate-acrylonitrile-butadiene-styrene polymers ("MABS", transparent ABS), but also blends of SAN, ABS, ASA and MABS other thermoplastics such as polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, PVC, polyolefins.
  • the ASA and ABS usable as components A generally have breaking elongations of from 10% to 300%, preferably from 15 to 250%, particularly preferably from 20% to 200%.
  • ASA polymers are generally understood to be impact-modified SAN polymers in which rubber-elastic graft copolymers of vinylaromatic compounds, in particular styrene, and vinyl cyanides, in particular acrylonitrile, are present on polyalkyl acrylate rubbers in a copolymer matrix of, in particular, styrene and / or ⁇ -methylstyrene and acrylonitrile.
  • the plastic mixtures comprise ASA polymers
  • the elastomeric graft copolymer A ⁇ of the compo- nent A composed of
  • the graft A2 consists of at least one graft.
  • Component A1 consists of the monomers
  • Alkyl esters of acrylic acid preferably n-butyl acrylate and / or ethylhexyl acrylate as component A11, a12 0.01-20% by weight, preferably 0.1-5.0% by weight, of at least one polyfunctional crosslinking monomer, preferably diallyl phthalate and / or DCPA as component A12.
  • the average particle size of the component A ⁇ is 50-1000 nm and is distributed monomodally.
  • the particle size distribution of the component A is ⁇ bimodal, wherein 60-90 wt .-% have an average particle size of 50-200 nm and 10-40 wt .-% have an average particle size of 50-400 nm, based on the total weight of component A ⁇ .
  • the mean particle size or particle size distribution are the sizes determined from the integral mass distribution.
  • the mean particle sizes according to the invention are in all cases the weight average particle size as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymere 250 (1972), pages 782-796. Ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size.
  • the average particle diameter which is also referred to as the dso value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter corresponding to the dso value.
  • the dio and dgo values resulting from the integral mass distribution are used.
  • the dio or d 90 value of the integral mass distribution This is defined according to the d 5 o value with the difference that they are based on 10 or 90 wt .-% of the particles. The quotient
  • Rubber-elastic graft copolymers A ⁇ preferably have Q values of less than 0.5, in particular less than 0.35.
  • the acrylate rubbers A1 are preferably alkyl acrylate rubbers of one or more ds-alkyl acrylates, preferably C 4 -alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl acrylate. and 2-ethylhexyl acrylate.
  • These alkyl acrylate rubbers may contain up to 30% by weight of polymers which form hard polymers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate, vinyl ethers, in copolymerized form.
  • the acrylate rubbers furthermore contain 0.01-20% by weight, preferably 0.1-5% by weight, of crosslinking, polyfunctional monomers (crosslinking monomers).
  • 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 ⁇ is a graft copolymer.
  • the graft copolymers A ⁇ here have a median particle size dso of 50 - nm 1000, preferably of 50 - 800 nm and particularly preferably of 50 -. 600 nm These particle sizes can be achieved, if the graft base A1 particle sizes of 50 - nm 800, preferably of 50-500 nm, and more preferably 50-250 nm.
  • the graft copolymer A K is generally one or more stages, ie a polymer composed of a core and one or more shells. The polymer consists of a base (graft) A1 and one or - preferably - several stages grafted thereon A2 (graft), the so-called grafting or grafting.
  • graft sheaths may be applied to the rubber particles, each one of them Graft shell may have a different composition.
  • graft 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).
  • component A ⁇ consists of a multi-stage graft copolymer, wherein the grafting steps are generally prepared from resin-forming monomers and have a glass transition temperature T 9 above 3O 0 C, preferably above 50 0 C.
  • the multi-stage structure is used, inter alia, to achieve a (partial) compatibility of the rubber particles A ⁇ with the thermoplastic matrix.
  • Graft copolymers A ⁇ 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.
  • the graft base A1 is composed of 15-99% by weight of acrylate rubber, 0.1-5% by weight of crosslinker and 0-49.9% by weight of one of the stated further monomers or rubbers.
  • Suitable monomers for forming the graft A2 are styrene, ⁇ -methylstyrene, (meth) acrylic acid esters, acrylonitrile and methacrylonitrile, in particular acrylonitrile.
  • the graft A1 crosslinked acrylic acid ester polymers having a glass transition temperature below 0 0 C.
  • the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 0 C, especially below -30 ° C.
  • the graft A2 consists of at least one graft and the outermost graft thereof has a glass transition temperature of more than 30 ° C, wherein a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° C.
  • Suitable preparation processes for graft copolymers A ⁇ are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A ⁇ are preferably prepared by free radical emulsion polymerization in the presence of latices of component A1 at temperatures of 20 ° C - 90 0 C of water-soluble or oil-soluble initiators such as using peroxodisulfate or benzoyl peroxide, or by means of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described in DE-A 28 26 925, 31 49 358 and in DE-C 12 60 135.
  • the structure of the graft shells is preferably carried out in the emulsion polymerization process, as described in DE-A 32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • the defined setting of the particle sizes of 50 to 1000 nm according to the invention is preferably carried out according to Processes which are described in DE-C 12 60 135 and DE-A 28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
  • the use of polymers having different particle sizes is known for example from DE-A 28 26 925 and US Pat. No. 5,196,480.
  • the grafting base A1 is first prepared by the acrylic ester (s) used according to one embodiment of the invention and the polyfunctional, crosslinking monomers, optionally together with the further comonomers aqueous emulsion in a conventional manner at temperatures between 20 and 100 0 C, preferably between 50 and 8O 0 C, polymerized.
  • the usual emulsifiers such as, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or rosin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are used.
  • 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.
  • 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 ⁇ -methylstyrene to be used in the polymerization.
  • pH values of preferably 6-9 such as sodium bicarbonate and sodium pyrophosphate
  • a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
  • the exact polymerization conditions, in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above in such a way that the resulting latex of the crosslinked acrylic ester polymer has a d.sub.50 in the range of about 50-800 nm, preferably 50-500 nm, particularly preferably in the range of 80-250 nm.
  • the particle size distribution of the latex should preferably be narrow.
  • ⁇ of the resulting latex of the crosslinked acrylate-polymer is then in a next step in the presence according to an embodiment of the invention is polymerized, a monomer mixture of styrene and acrylonitrile, wherein the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention in the range of 100: 0 to 40: 60, preferably in the range of 65: 35 to 85: 15, lie. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylate polymer used as the grafting base again in aqueous emulsion under the customary conditions described above.
  • the graft copolymerization may suitably be carried out in the same system as the emulsion polymerization for the preparation of the grafting base A1, it being possible, if necessary, for further emulsifier and initiator to be added.
  • the monomer mixture of styrene and acrylonitrile to be grafted on in accordance with one embodiment of the invention can be added to the reaction mixture at once, batchwise in several stages or preferably continuously during the polymerization.
  • the graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out in such a way that a degree of grafting of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, relates on the total weight of the component A ⁇ , resulting in the graft copolymer A ⁇ . Since the graft yield in the graft copolymerization is not 100%, a slightly larger amount of the monomer mixture of styrene and acrylonitrile must be used in the graft copolymerization than corresponds to the desired degree of grafting.
  • the control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A ⁇ 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. ).
  • regulators Chovel, Daniel, ACS Polymer Preprints 15 (1974), page 329 et seq.
  • 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 ⁇ in the polymerization product obtained in the graft copolymerization is determined by the method indicated above.
  • the graft copolymers A ⁇ In the preparation of the graft copolymers A ⁇ 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 ⁇ .
  • the component A ⁇ 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 ⁇ generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of grafting A1 and 1-99% by weight, preferably 20-45, more preferably 35-45 wt .-% of the graft A2, each based on the total graft copolymer.
  • ABS polymers are generally understood to be impact-modified SAN polymers in which diene polymers, in particular 1,3-polybutadiene, are present in a copolymer matrix of in particular styrene and / or ⁇ -methylstyrene and acrylonitrile.
  • the rubber-elastic graft copolymer A ⁇ ⁇ of the component A is composed of
  • a11 'from 60 to 100 preferably from 70 to 100,% by weight of at least one conjugated diene and / or C 1 - to C 10 -alkyl acrylate, in particular butadiene, isoprene, n-butyl acrylate and / or 2-ethylhexyl acrylate,
  • a13'0 to 10 preferably 0 to 6 wt .-% of at least one crosslinking monomer, preferably divinylbenzene, diallyl maleate, allyl esters of (meth) acrylic acid, dihydrodicyclopentadienyl, dinvinyl esters of dicarboxylic acids such as maleic and adipic acid and diallyl and divinyl ether bifunctional alcohols such as ethylene glycol or butane-1, 4-diol,
  • Monomers preferably styrene and / or ⁇ -methylstyrene, a22 'from 5 to 35, preferably from 10 to 30,% by weight of acrylonitrile and / or methacrylonitrile, preferably acrylonitrile,
  • component A ⁇ ⁇ is a graft rubber having a bimodal particle size distribution, based on A ⁇ ',
  • a11 from 70 to 100, preferably from 75 to 100,% by weight of at least one conjugated diene, in particular butadiene and / or isoprene,
  • the hard matrix A M of component A is at least one hard copolymer containing units derived from vinyl aromatic monomers, and wherein, based on the total weight of vinylaromatic monomers of dissipative units, 0 to 100 wt.%, preferably 40 to 100 wt.%, particularly preferably 60 to 100 wt.% of ⁇ -methylstyrene and 0 to 100 wt.%, preferably 0 to 60 wt %, more preferably 0-40% by weight of units derived from styrene, from, based on A M ,
  • 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.
  • the hard matrix A M 'of component A is at least one hard copolymer containing units derived from vinylaromatic monomers, and wherein, based on the Total weight of vinyl aromatic monomers dissipative units, 0 - 100 wt .-%, preferably 40 - 100 wt .-%, particularly preferably 60 to 100 wt .-% of ⁇ -methyl styrene and 0 - 100 wt .-%, preferably 0 60% by weight, more preferably 0-40% by weight, of styrene-derived units are present, based on A M ',
  • a M 1 '50 to 100 preferably 55 to 90 wt .-% of vinyl aromatic monomers, a M 2' 0 to 50 wt .-% of acrylonitrile or methacrylonitrile or mixtures thereof, a M 3 '0 to 50 wt .-% of at least one further monoethylenically unsaturated monomers, for example methyl methacrylate and N-alkyl or N-arylmaleimides such as N-phenylmaleimide.
  • component A M ' is at least one hard copolymer having a viscosity number VN (determined according to DIN 53726 at 25 0 C in 0.5 wt .-% - strength solution in dimethylformamide) of 50 to 120 ml / g, which contains units derived from vinyl aromatic monomers, and wherein, based on the total weight of vinyl aromatic monomers dissipative units, 0 - 100 wt .-%, preferably 40 - 100 wt.
  • VN viscosity number
  • % particularly preferably 60 to 100% by weight of ⁇ -methylstyrene and 0-100% by weight, preferably 0-60% by weight, more preferably 0-40% by weight, of units derived from styrene are, from, based on A M '
  • 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)
  • copolymers of ( ⁇ -methyl) styrene and maleic anhydride or maleimides from ( ⁇ -methyl) styrene, maleimides and methyl methacrylate or acrylonitrile, or from ( ⁇ -methyl) stryol, maleimides , Methyl methacrylate and acrylonitrile.
  • the graft polymers A ⁇ ' are preferably obtained by means of emulsion polymerization.
  • the mixing of the graft polymers A ⁇ ' with the Components A M 'and, if appropriate, further additives are generally carried out in a mixing device, forming a substantially molten polymer mixture. It is advantageous to cool the molten polymer mixture as quickly as possible.
  • ABS polymers may contain further customary auxiliaries and fillers.
  • auxiliaries and fillers are, for example, lubricants or mold release agents, waxes, pigments, dyes, flame retardants, antioxidants, light stabilizers or antistatic agents.
  • the viscosity number of the hard matrices A M and A M 'of the component A is 50-90, preferably 60-80.
  • the hard matrices A M and A M 'of the component A are amorphous polymers.
  • mixtures of a copolymer of styrene with acrylonitrile and of a copolymer of ⁇ -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 ( ⁇ -methyl) styrene / acrylonitrile copolymers which are formed in the graft copolymerization to prepare component A ⁇ or A ⁇ '.
  • component A ⁇ or A ⁇ ' 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.
  • the copolymerization of the styrene and / or ⁇ -methylstyrene with the acrylonitrile in bulk, solution, suspension or aqueous emulsion can be carried out.
  • the components A M and A M ' preferably have a viscosity number of 40 to 100, preferably 50 to 90, in particular 60 to 80. The determination of the viscosity number is carried out according to DIN 53 726, while 0.5 g of material in 100 ml of dimethylformamide solved.
  • the mixing of the components A ⁇ (or A ⁇ ' ) and A M (or A M ') can be carried out in any manner by all known methods. If these components For example, have been prepared by emulsion polymerization, it is possible to mix the polymer dispersions obtained with each other, then precipitate the polymers together and work up the Polymerisatgemisch. Preferably, however, the mixing of these components is carried out by coextruding, kneading or rolling the components, wherein the components, if necessary, have previously been isolated from the solution or aqueous dispersion obtained in the polymerization.
  • the products of the graft copolymerization obtained in aqueous dispersion can also be only partially dehydrated and mixed as moist crumbs with the hard matrix, during which the complete drying of the graft copolymers takes place during the mixing.
  • Thermoplastic elastomers based on styrene are Thermoplastic elastomers based on styrene:
  • thermoplastic elastomers based on styrene are those having an elongation at break of more than 300%, particularly preferably more than 500%, in particular more than 500% to 600%.
  • Particularly preferably mixed as S-TPE is a linear or star-shaped styrene-butadiene block copolymer with external polystyrene blocks S and intervening styrene-butadiene copolymer blocks with random styrene / butadiene distribution (S / B) ran ciom or a styrene gradient (S / B) taperZU.
  • the Automatbutadiengehalt is preferably in the range of 15 to 50 wt .-%, particularly preferably in the range of 25 to 40 wt .-%, the Automatstyrolgehalt is correspondingly preferably in the range of 50 to 85 wt .-%, particularly preferably in the area from 60 to 75% by weight.
  • the styrene-butadiene block (S / B) consists of 30 to 75% by weight of styrene and 25 to 70% by weight of butadiene.
  • a block (S / B) has a butadiene content of 35 to 70% by weight and a styrene content of 30 to 65% by weight.
  • the proportion of polystyrene blocks S is preferably in the range from 5 to 40% by weight, in particular in the range from 25 to 35% by weight, based on the total block copolymer.
  • the proportion of the copolymer blocks S / B is preferably in the range of 60 to 95 wt .-%, in particular in the range of 65 to 75 wt .-%.
  • linear styrene-butadiene block copolymers of the general structure S- (S / B) -S with one or more, lying between the two S blocks, a static styrene / butadiene distribution having blocks (S / B) ran do m .
  • block copolymers are obtainable by anionic polymerization in a non-polar solvent with the addition of a polar cosolvent or a potassium salt, as described, for example, in WO 95/35335 or WO 97/40079.
  • the vinyl content is understood to be the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages.
  • the 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.
  • the polyolefins which can be used as components A generally have breaking elongations of from 10% to 600%, preferably from 15% to 500%, particularly preferably from 20% to 400%.
  • Suitable components A are, for example, partially crystalline polyolefins, such as homo- or copolymers of ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1 and ethylene copolymers with vinyl acetate, vinyl alcohol, ethyl acrylate, butyl acrylate or methacrylate.
  • Component A is preferably a high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene.
  • LLDPE Polyethylene
  • PP polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • a particularly preferred component A is polypropylene.
  • the polycarbonates which can be used as components A generally have breaking elongations of from 20% to 300%, preferably from 30% to 250%, particularly preferably from 40% to 200%.
  • the polycarbonates suitable as component A preferably have a molecular weight (weight average M w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range of 10,000 to 60,000 g / mol. They are obtainable, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally referred to as bisphenol A, as in the following.
  • bisphenol A instead of bisphenol A, it is also possible to use other aromatic dihydroxy compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxynaphthalene.
  • aromatic dihydroxy compounds in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxynaphthalene.
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the abovementioned aromatic dihydroxy compounds.
  • suitable polycarbonates are those which contain units derived from Resorcinol- or Alkylresorcinolestem, as described for example in WO 00/61664, WO 00/15718 or WO 00/26274; These polycarbonates are, for example, sold by General Electric Company under the trademark Solix ®.
  • copolycarbonates according to US Pat. No. 3,737,409; Of particular interest are copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • the average molecular weights (weight average M w , determined by gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates according to the invention are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol.
  • polycarbonates relative solution viscosities in the range of 1, 1 to 1, 3 as measured in 0.5 wt .-% solution in dichloromethane at 25 0 C, aeration vorzugt of 1 15 to 1, 33, have ,
  • the relative solution viscosities of the polycarbonates used preferably do not differ by more than 0.05, in particular not more than 0.04.
  • the polycarbonates can be used both as regrind and in granulated form.
  • 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 are all metal powders having an average particle diameter of 0.01 to 100 .mu.m, preferably from 0.1 to 50 .mu.m, more preferably from 1 to 10 microns, suitable (determined by laser diffraction measurement on a device Microtrac X100), provided that the metal has a more negative normal potential in acidic solution than silver.
  • Suitable metals are, for example, Zn, Ni, Cu, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi.
  • the metals may be in the form of the metal used or, if different metals are used, in the form of alloys of the metals mentioned with one another or be deposited with other metals.
  • suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCu, NiP, ZnFe, ZnNi, ZnCo and ZnMn.
  • Preferably usable metal powders are iron powder and copper powder, in particular iron powder.
  • the metal powder particles can in principle have any desired shape, for example, needle-shaped, plate-shaped or spherical metal particles can be used, preferably spherical and plate-shaped. Such metal powders are common
  • metal powders with spherical particles in particular carbonyl iron powder, are used.
  • the preparation of carbonyl iron powders by thermal decomposition of iron pentacarbonyl is known and is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599.
  • the decomposition of the iron pentacarbonyl can be carried out, for example, at elevated temperatures and elevated pressures in a heatable decomposer comprising a tube made of a heat-resistant material, such as quartz glass or V2A steel, in a preferably vertical position, consisting of a heating device, for example from heating tapes, Heating wires or from a heating medium flowed through by a heating jacket, is surrounded.
  • the mean particle diameters of the carbonyl iron powder which separates out can be controlled in a wide range by the process parameters and reaction behavior during the decomposition and are generally from 0.01 to 100 ⁇ m, preferably from 0.1 to 50 ⁇ m, more preferably from 1 to 10 ⁇ m.
  • dispersants 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.
  • 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.
  • alkyl sulfates and alkyl or alkylaryl sulfonates having 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms can be used as anionic surfactants.
  • Particularly suitable compounds are alkali dodecyl sulfates, e.g. Sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali salts of C12-C16 paraffin sulfonic acids. Also suitable are sodium dodecylbenzenesulfonate and sodium di-sulfosuccinate.
  • 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.
  • quaternary ammonium salts e.g. Hexadecyltrimethylammoni- bromide used by trialkylamines.
  • the alkyl radicals preferably have 1 to 20 carbon atoms therein.
  • nonionic surfactants can be used as component C.
  • Nonionic surfactants are described, for example, in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "nonionic surfactants".
  • Suitable nonionic surfactants include for example polyethylene oxide or polypropylene oxide-based substances such as Pluronic ® and Tetronic ® from BASF Aktiengesellschaft.
  • Polyalkylene glycols suitable as nonionic surfactants generally have a molecular weight M n in the range from 1000 to 15000 g / mol, preferably 2000 to 13000 g / mol, particularly preferably 4000 to 11000 g / mol.
  • Preferred nonionic surfactants are polyethylene glycols.
  • the polyalkylene glycols are known per se or can be prepared by processes known per se, for example by anionic polymerization with alkali hydroxides, such as sodium or potassium hydroxide or alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropoxide, as catalysts and with addition of at least one starter molecule, containing 2 to 8, preferably 2 to 6, bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids such as antimony pentachloride, boron fluoride etherate or bleaching earth, prepared as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical become.
  • alkali hydroxides such as sodium or potassium hydroxide or alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropoxide
  • Lewis acids such as antimony pentachloride, boron fluoride etherate or bleaching earth
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 2 or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and / or 1, 2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • Aliphatic or aromatic optionally N-mono-, N 1 N- or N, water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid or terephthalic acid, 1 N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in:
  • Possible starter molecules are, for example, in consideration Alkyl radical, such as mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, Triethylentetra- min, 1, 3-propylenediamine, 1, 3 or 1, 4-butylenediamine, 1,2-, 1,3-, 1, 4- , 1, 5 or 1, 6-hexamethylenediamine.
  • alkanolamines e.g. Ethanolamine, N-methyl and N-ethyl-ethanolamine
  • dialkanolamines e.g. Diethanolamine, N-methyl and N-ethyldiethanolamine
  • trialkanolamines e.g. Triethanolamine, and ammonia.
  • polyhydric, in particular dihydric, trihydric or polyhydric alcohols such as ethanediol, propanediol-1, 2 and 1,3, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, Trimethylolpropane, pentaerythritol, and sucrose, sorbitol and sorbitol.
  • esterified polyalkylene glycols for example the mono-, di-, tri- or polyesters of the polyalkylene glycols mentioned, which are obtained by reaction of the terminal OH groups of said polyalkylene glycols with organic acids, preferably adipic acid or terephthalic acid, in per se can be produced in a known manner.
  • organic acids preferably adipic acid or terephthalic acid
  • 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.
  • nonionic surfactants are alkoxylated or non-alkoxylated sugar esters or sugar ethers.
  • Sugar ethers are alkyl glycosides obtained by reaction of fatty alcohols with sugars, and sugar esters are obtained by reacting sugars with fatty acids.
  • the sugar, fatty alcohols and fatty acids necessary for the preparation of the substances mentioned are known to the person skilled in the art.
  • Suitable sugars are described for example in Beyer / Walter, textbook of organic chemistry, S. Hirzel Verlag Stuttgart, 19th edition, 1981, pages 392 to 425. Particularly suitable sugars are D-sorbitol and sorbitans obtained by dehydration of D-sorbitol.
  • Suitable fatty acids are saturated or mono- or polyunsaturated unbranched or branched carboxylic acids having 6 to 26, preferably 8 to 22, particularly preferably 10 to 20 C atoms, as described, for example, in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "fatty acids" are called.
  • Preferred fatty acids are lauric acid, palmitic acid, stearic acid and oleic acid.
  • Suitable fatty alcohols have the same carbon skeleton as the compounds described as suitable fatty acids.
  • sugar ethers, sugar esters and the processes for their preparation are known in the art.
  • Preferred sugar ethers are prepared by known processes by reacting the said sugars with the stated fatty alcohols.
  • Preferred sugar esters are prepared by known processes by reacting the said sugars with said fatty acids.
  • Preferred sugar esters are mono-, di- and triesters of sorbitans with fatty acids, in particular sorbitan monolaurate, sorbitan diethylate, sorbitan trilaurate, sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan monopalmitate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate and sorbitan sesquioleate, of a mixture of sorbitan mono- and diesters of oleic acid.
  • Very particularly suitable components C are alkoxylated sugar ethers and sugar esters which are obtained by alkoxylation of the cited sugar ethers and sugar esters become.
  • Preferred alkoxylating agents are ethylene oxide and 1,2-propylene oxide.
  • the degree of alkoxylation is generally between 1 and 20, preferably 2 and 10, particularly preferably 2 and 6.
  • Particularly preferred alkoxylated sugar esters are polysorbates which are obtained by ethoxylation of the sorbitan esters described above, for example described in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Polysorbate”.
  • polyvinyl lysorbate are polyethoxysorbitan, stearate, palmitate, tristearate, oleate, trioleate, especially polyethoxysorbitan, which is available for example as Tween ® 60 from ICI America Inc. (described for example in CD Rompp Chemie Lexikon - Version 1.0 , Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Tween ® ").
  • the plastic mixtures contain fibrous or particulate fillers or mixtures thereof. These are preferably commercially available products, for example carbon fibers and glass fibers.
  • Useful glass fibers may be of E, A or C glass and are preferably equipped with a size and a primer. Their diameter is generally between 6 and 20 ⁇ m. 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.
  • fillers or reinforcing agents such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powder and wollastonite may be added.
  • the plastic mixture may also contain other additives that are typical and common in plastics processing.
  • additives examples include: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the light stability, to increase the resistance to hydrolysis and chemical resistance, means against the heat decomposition and in particular the lubricants / lubricants for the production of moldings or moldings are expedient.
  • the dosing of these other additives can be done at any stage of the manufacturing process, but preferably at an early stage, to take advantage of the stabilizing effects (or other specific effects) of the additive at an early stage.
  • Heat stabilizers or oxidation inhibitors are usually metal halides (chlorides, bromides, iodides), which are derived from metals of group I of the Periodic Table of the Elements (such as Li, Na, K, Cu).
  • Suitable stabilizers are the usual hindered phenols, but also vitamin E or analogously constructed compounds.
  • Hindered amine light stabilizers, benzophenones, resorcinols, salicylates, benzotriazoles such as Tinuvin®RP (UV absorber 2- (2H-benzotriazol-2-yl) -4-methylphenol from CIBA) and other compounds are also suitable. These are usually used in amounts of up to 2 wt .-% (based on the total mixture of Kunststoffsoffmischung).
  • 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 .-%.
  • silicone oils, oligomeric isobutylene or similar substances are suitable as additives, the usual amounts are from 0.05 to 5 wt .-%.
  • Pigments, dyes, color healers such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylenetetracarboxylic acid are also usable.
  • Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01-5 wt .-%.
  • the first step of the process according to the invention is the melt mixing and extrusion of the described plastic mixture.
  • plastic articles accessible by extrusion can be shaped by the processes according to the invention.
  • Preferred extruded plastic articles are films, sheets, profiles, tubes and strands. These can in principle be produced by extrusion processes known to the person skilled in the art.
  • composite layer films or sheets can be produced by coextrusion, laminating or laminating methods.
  • injection molding casting behind or pressing back with thermoplastic molding materials or foam or Hinterpressen with thermosetting molding compounds multilayer moldings are accessible.
  • thermoplastic molding compositions for producing the extruded films or sheets of the components A, B and, if present, C and D is carried out by methods known in the art, for example by mixing the components in the melt with known in the art devices at temperatures, the depending on the nature of the polymer A employed usually in the range of 150 to 300 0 C, particularly at 200 to 28O 0 C. 1
  • the components can be supplied in each case pure form the mixing devices. However, it is also possible for individual components, for example A and B, to be premixed first and then mixed with further components A or B or other components, for example C and D.
  • a concentrate, for example components B, C or D in component A is first prepared (so-called additive batches) and then mixed with the desired amounts of the remaining components.
  • the plastic mixtures can after the
  • the screw extruder is designed as a single-screw extruder with at least one distributively mixing screw element.
  • the screw extruder is designed as a twin-screw extruder with at least one distributively mixing screw element.
  • the methods of extruding the films or plates may be by methods known to those skilled in the art and described in the art, e.g. Slot extrusion as adapter or die coextrusion, and with devices known to those skilled in the art and described in the prior art.
  • the type and amount of the other components are chosen so that the plastic mixtures comprising the components A, B and, if present, C and D have tear strengths within the following ranges:
  • the extruded films or plates generally have a total thickness of 20 microns to 5 mm, preferably from 70 .mu.m to 3 mm, more preferably 100 .mu.m to 1, 5 mm.
  • the extruded films or plates are suitable in particular as a cover layer (3) of multilayer composite layer plates or films which, in addition to the cover layer, have at least one further substrate layer (1) made of thermoplastic material.
  • the composite layer plates or sheets may comprise additional layers (2), for example color, adhesion promoter or intermediate layers, which are arranged between the cover layer (3) and the substrate layer (1).
  • the substrate layer (1) can in principle be constructed from any thermoplastic material.
  • the substrate layer (1) is preferably prepared from the impact-modified vinylaromatic copolymers described above in connection with the extruded films or plates, thermoplastic elastomers based on styrene, polyolefins, polycarbonates and thermoplastic polyurethanes or mixtures thereof from ASA, ABS, SAN, polypropylene and polycarbonate or mixtures thereof.
  • Layer (2) is different from layers (1) and (3), for example because of a different polymer composition from and / or different from these additive contents, such as colorants or effect pigments.
  • Layer (2) can be, for example, a coloring layer which may preferably contain dyes, color pigments or effect pigments known to the person skilled in the art, such as mica or aluminum flakes or mica.
  • layer (2) can also serve to improve the mechanical stability of the composite layer plates or films, or to provide adhesion between the layers (1) and (3).
  • An embodiment of the invention relates to a composite layered sheet or film of a substrate layer (1), cover layer (3) as described above and an intervening intermediate layer (2) consisting of aliphatic thermoplastic Polyurethane, impact polymethyl methacrylate (PMMA), polycarbonate or styrene (co) polymers such as SAN, which may be impact-modified, for example ASA or ABS, or mixtures of these polymers is constructed.
  • an intervening intermediate layer (2) consisting of aliphatic thermoplastic Polyurethane, impact polymethyl methacrylate (PMMA), polycarbonate or styrene (co) polymers
  • SAN which may be impact-modified, for example ASA or ABS, or mixtures of these polymers is constructed.
  • aliphatic thermoplastic polyurethane When aliphatic thermoplastic polyurethane is used as the material of the intermediate layer (2), the aliphatic thermoplastic polyurethane described under layer (3) can be used.
  • polycarbonate is used as intermediate layer (2), then the polycarbonate described under layer (3) can be used.
  • High Impact PMMA is a polymethyl methacrylate which is impact-modified by suitable additives. Suitable impact-modified PMMA are described, for example, by M. Stickler, T. Rhein in Ullmann's encyclopedia of industrial chemistry Vol. A21, pages 473-486, VCH Publishers Weinheim, 1992, and H. Domininghaus, Die Kunststoffe u. Publisher Dusseldorf, 1992.
  • the layer thickness of the above composite layer plates or films is usually 15 to 5000 .mu.m, preferably 30 to 3000 .mu.m, more preferably 50 to 2000 microns.
  • the composite layer plates or sheets consist of a substrate layer (1) and a cover layer (3) with the following layer thicknesses: substrate layer (1) 50 ⁇ m to 1.5 mm; Cover layer (3) 10 - 500 ⁇ m.
  • the composite layer plates or sheets consist of a substrate layer (1), an intermediate layer (2) and a cover layer (3).
  • Composite layer plates or foils comprising a substrate layer (1), an intermediate layer (2) and a cover layer (3) preferably have the following layer thicknesses: Substrate layer (1) 50 ⁇ m to 1.5 mm; Intermediate layer (2) 50 to 500 ⁇ m; Cover layer (3) 10 - 500 ⁇ m.
  • the composite layer plates or foils may also have on the side of the substrate layer (1) facing away from the cover layer (3) further layers, preferably an adhesion promoter layer, which results in improved adhesion of the composite layer plates or foils to the carrier layer which will be described below serve.
  • adhesion promoter layers are preferably prepared from a material which is compatible with polyolefins, such as, for example, SEBS (styrene-ethylene-butadiene-styrene copolymer, marketed, for example, under the trademark Kraton® ). If such a primer layer is present, it preferably has a thickness of 10 to 300 ⁇ m.
  • the composite laminate sheets or films may be prepared by known methods described in the prior art (for example in WO 04/00935), for example by adapter or coextrusion or laminating or laminating the layers to one another.
  • the components forming the individual layers are rendered flowable in extruders and brought into contact with one another via special devices so that the composite layer plates or films result with the layer sequence described above.
  • the components may be coextruded through a slot die or a multi-layer die tool. This process is explained in EP-A2-0 225 500.
  • the composite laminate sheets and films can be made by laminating or laminating films or sheets in a heatable gap. Initially, corresponding films or plates are produced separately for the layers described. This can be done by known methods. Then, the desired layer sequence is produced by corresponding superimposition of the films or plates, whereupon they are guided, for example, through a heatable roll nip and joined under pressure and heat to form a composite layer plate or film.
  • matching of the flow properties of the individual components is advantageous for the formation of uniform layers in the composite layer plates or foils.
  • extruded sheets or sheets and the composite sheets or sheets comprising the extruded sheets or sheets of the present invention may be used to make molded articles.
  • These extruded films or sheets and composite laminated sheets or foils are particularly preferably used for the production of molded parts which require very good toughness, good adhesion of the individual layers to one another and good dimensional stability, so that, for example, destruction due to detachment of the surfaces is minimized becomes.
  • Particularly preferred moldings comprise monofilms or composite laminate sheets or foils. holding the extruded sheets or plates and a back-injected, foam-backed, back-pressed or behind-pressed carrier layer made of plastic.
  • the production of molded parts from the extruded films or sheets or the composite laminate sheets or films can be carried out by known processes described, for example, in WO 04/00935 (the processes for the further processing of composite laminate sheets or films are described below, but these processes are can also be used for the further processing of the extruded films or plates according to the invention).
  • the composite laminate sheets or films can be back-injected, backfoamed, back-poured or back-pressed without further processing stage.
  • the use of the described composite layer plates or foils makes it possible to produce easily three-dimensional components without prior thermoforming.
  • the composite laminates or sheets may also be subjected to a previous thermoforming process.
  • composite laminates or sheets having the substrate layer, interlayer and topcoat three-layer structure or the substrate layer / topcoat two-layer structure may be thermoformed to produce more complex components.
  • Both positive and negative thermoforming processes can be used.
  • Corresponding methods are known to the person skilled in the art.
  • the composite layer plates or films can be subjected to further shaping steps, for example contour cutting.
  • the molded parts according to the invention can be produced from the composite layer plates or sheets, if appropriate after the described thermoforming processes, by insert molding, back-foaming, back-casting or backpressing. These processes are known to the person skilled in the art and are described, for example, in DE-A1 100 55 190 or DE-A1 199 39 111.
  • the molded parts according to the invention are obtained.
  • Thermoplastic molding compositions based on ASA or ABS polymers, SAN polymers, poly (meth) acrylates, polyethersulfones, polybutylene terephthalate, polycarbonates, polypropylene (PP) or polyethylene (PE) are preferred for injection molding, back-molding or back-casting as plastic materials.
  • ASA or ABS polymers and polycarbonates or polybutylene terephthalate and blends of polycarbonates and polybutylene terephthalate used, it being advisable when using PP and / or PE to provide the substrate layer previously with a bonding agent layer.
  • Particularly suitable are amorphous thermoplastics or their blends. Preference is given to ABS or SAN polymers used as plastic material for the back molding. For backfoaming and backpressing, thermosetting molding compounds known to those skilled in the art are used in a further preferred embodiment. In a preferred embodiment these plastic materials are glass fiber reinforced, suitable variants are described in particular in DE-A1 100 55 190. When foam-backing polyurethane foams are preferably used, as described for example in DE-A1 199 39 111.
  • the composite layer plate or film is deformed by hot forming, then inserted into a mold and back molded with thermoplastic molding compounds, back-poured or behind-pressed, or backfoamed with thermosetting molding compounds or behind.
  • the composite laminate sheet or film may undergo a contour cut after hot working and prior to loading into the back mold.
  • the contour cut can also be made only after removal from the Deutschenformwerkmaschine.
  • the surface activation according to the invention by mechanical abrasion in particular sandblasting, dry ice blasting or sanding, and / or chemical abrasion, in particular etching, take place.
  • mechanical abrasion in particular sandblasting, dry ice blasting or sanding, and / or chemical abrasion, in particular etching.
  • a suitable surface activation is generally achieved by sand blasting times of less than 1 minute, preferably less than 30 seconds, more preferably less than 10 seconds.
  • dry ice blasting but dry ice is used instead of sand as the abrasive material.
  • Corresponding methods for dry ice blasting are known to the person skilled in the art and described in the prior art.
  • the surface activation according to the invention can also be achieved by stretching (often also referred to as stretching or stretching) of the extruded plastic articles in the non-molten state by a factor of 1.1 to 10, preferably 1.2 to 5, particularly preferably 1.3 to 3, respectively.
  • 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.
  • a unidirectional stretching is preferably carried out; in the case of sheet-like plastic objects, a multidirectional, in particular bidirectional, stretching is preferred, for example in the blow molding or thermoforming process of films or plates.
  • multidirectional stretching it is essential that the said stretching factor is achieved in at least one stretching direction.
  • stretching methods known to the person skilled in the art and described in the literature can be used as the stretching method.
  • Preferred stretching methods for films are, for example, blow molding processes.
  • the stretching of the plastic objects takes place at temperatures which depend on the processing properties of the particular component A used. Examples of play occurs, the stretching with the use of S-TPE, as component A, usually at temperatures from 105 to 140 0 C, in particular 110 to 13O 0 C.
  • the surface activation process step can, in principle, be carried out directly after the extrusion or coextrusion of the plastic articles.
  • extruded foils for example, can first be laminated and / or back-injected, poured, pressed or foamed after extrusion.
  • the composite films, sheets or multilayer moldings thus obtained are then subsequently surface-activated.
  • the surface activation preferably takes place directly after the extrusion, only after the surface activation are the desired process steps for producing multilayer plastic articles carried out, if desired.
  • extruded and surface-activated plastic articles produced as described are particularly suitable for producing metallized plastic articles without the need for further special pretreatment of the surface.
  • the extruded plastic articles are electrolessly or galvanically brought into contact with an acidic, neutral or basic metal salt solution after the last shaping process, the metal of this metal salt solution having a more positive normal potential corresponding to acidic, neutral or basic solution than component B.
  • Preferred metals with more positive normal potential in acidic neutral or basic solution as component B are gold and silver (if component B is copper), or copper, nickel and silver, in particular copper (if component B is iron).
  • a currentless or electrodeposited layer Ms is applied in this way.
  • Preferred layers Ms are gold and silver layers (if component B is copper), or copper, nickel or silver layers, in particular copper layers (if component B is iron).
  • the thickness of the electrolessly depositable layer Ms is in the usual range known to the person skilled in the art and is not essential to the invention.
  • One or more metal layers M 9 can be applied to the electrolessly depositable layer Ms by methods known to the person skilled in the art and described in the literature.
  • copper, chromium, silver, gold and / or nickel layers are electrodeposited.
  • the galvanic deposition of layers M 9 of aluminum is preferred.
  • Application by direct metallization by means of vacuum vapor deposition, irradiation / spraying or sputtering by methods known to those skilled in the art is also possible.
  • the thicknesses of the one or more deposited layers M 9 are in the usual range known to the person skilled in the art and are not essential to the invention.
  • Particularly preferred metallized plastic articles for use as electrically conductive components, in particular printed circuit boards, have an electrolessly deposited copper layer and at least one further, electrodeposited layer.
  • Particularly preferred metallized plastic articles for use in the decorative sector have an electrolessly deposited copper layer, on which a galvanic deposited nickel layer and deposited on this deposited chromium, silver or gold layer.
  • the metallized plastic articles which can be produced by the process according to the invention and comprise an electrolessly depositable metal layer M s are readily applied to a deposited metal layer M 9 as electrically conductive components, in particular printed circuit boards, transponder antennas, switches, sensors and MIDs, EMI shielding (ie shielding for Avoidance of so-called “electro-magnetic interference”) such as absorbers, dampers or reflectors suitable for electromagnetic radiation or gas barriers.
  • EMI shielding ie shielding for Avoidance of so-called “electro-magnetic interference”
  • the metallized plastic articles which can be produced by the process according to the invention and comprise an electrolessly depositable metal layer M s and at least one deposited metal layer M 9 are as electrically conductive components, in particular printed circuit boards, transponder antennas, switches, sensors and MIDs, as EMI shieldings such as absorbers, dampers or Reflectors for electromagnetic radiation or gas barriers or decorative parts, in particular decorative parts in the automotive, sanitary, toy, household and office sector, suitable.
  • Examples of such applications are: computer cases, electronic component housings, military and non-military shields, shower and washbasin faucets, showerheads, shower rods and holders, metalized door handles and door knobs, toilet paper roll holders, bath tub handles, metallized trim on furniture and mirrors, frame for shower enclosures.
  • 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.
  • 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.
  • 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.
  • the metallized plastic articles insofar as they comprise magnetizable metals, find applications in areas of magnetizable functional parts, such as magnetic boards, magnetic games, magnetic surfaces, e.g. Refrigerator doors. In addition, they find application in areas where a good thermal conductivity is advantageous, for example in films for seat heaters, underfloor heating, insulation materials.
  • the processes according to the invention for the production of metallized plastic articles are characterized in that, with comparably good processing properties and freedom of design, the plastic articles,
  • the plastic articles For example, in forming processes for the production of complex shaped components, compared to known methods for producing metallized plastic parts an improved electroless and galvanic metallization is possible.
  • the metallized plastic articles which can be produced by the process according to the invention have qualitatively improved, in particular more homogeneous and / or better adhering, metal layers compared to metallized plastic bodies produced by known processes with comparably good processing properties and freedom of design.
  • Styroflex ® 2G66 an S-TPE from BASF Aktiengesellschaft with an elongation at break of 480% (determined in a tensile test according to ISO 527-2: 1996 on test specimens of type 1 BA (Annex A of the mentioned standard: "small specimens”))
  • Styrolux ® 3G55 from BASF Aktiengesellschaft
  • pressed films having a thickness of 100 ⁇ m and a pressure of 200 bar and a temperature of 200 ° C. were produced from the resulting plastic mixture.
  • the resulting films were each placed in an injection mold (60x60x2 mm platelets with tape casting) and back-injected with Styrolux ® 3G55 at 200 0 C (injection machine from Netstal with semi-automatic control, screw diameter 32 mm, needle valve nozzle, cone gate, plate tool with 4 mm thickness and 200 x 100 mm surface, screw speed 100 rpm, screw feed rate: 50 mm / s, cycle time: 50 s, injection time: 2 s, holding time: 10 s, cooling time: 30 s, dosing time: 18 s, cylinder temperature: 200 - 220 0 C, mold surface temperature: 45 0 C.
  • plastic articles (specimens and back-injected films) produced in the described manner were surface-activated by the methods mentioned in Table 1 and then immersed in acidic (pH 1-2), 5 wt .-% copper (II) sulfate solution at 23 ° C. and applying a voltage of 1 V metallized at a current of 2 amperes.
  • Table 1 shows the quality of each after a GaI- vanubenmaschinesdauer one minute copper layer obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Procédé de fabrication d'objets en plastique extrudés métallisés, selon lequel, lors d'une première étape, un mélange de plastique est mélangé à l'état fondu et extrudé, ledit mélange contenant, par rapport au poids total des constituants A, B, C et D correspondant en tout à 100 % en poids, (a) 5 à 50 % en poids d'un polymère thermoplastique en tant que constituant A, (b) 50 à 95 % en poids d'une poudre de métal à diamètre moyen des particules de 0,1 à 100 νm (déterminée selon la méthode définie dans le descriptif), ledit métal ayant un potentiel normal plus négatif que l'argent dans une solution acide, en tant que constituant B, (c) 0 à 10 % en poids d'un dispersant en tant que constituant C et (d) 0 à 40 % en poids de matières de charge sous forme de fibres ou de particules ou leur mélange en tant que constituant D. Lors d'une dernière étape, l'objet en plastique extrudé est amené en contact sans courant ou de manière galvanique avec une solution de sel métallique acide, neutre ou basique, ce métal ayant un potentiel normal plus positif, dans une solution acide, neutre ou basique correspondante, que le constituant B. Selon une caractéristique essentielle de la présente invention, l'objet en plastique est soumis à une activation de surface à l'état non fondu après l'étape du mélange à l'état fondu et de l'extrusion et avant l'étape de la mise en contact avec la solution de sel métallique acide. La présente invention concerne également des objets en plastique extrudés, l'utilisation de ces objets ainsi que des éléments de blindage contre l'interférence électromagnétique tels que des absorbeurs, des atténuateurs ou des réflecteurs pour le rayonnement électromagnétique, des pièges à oxygène, des composants électroconducteurs, des barrières de gaz et des pièces décoratives contenant ces objets.
PCT/EP2006/061846 2005-04-27 2006-04-26 Procede de fabrication d'objets en plastique extrudes metallises WO2006114431A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE200510019983 DE102005019983A1 (de) 2005-04-27 2005-04-27 Verfahren zur Herstellung metallisierter, extrudierter Kunststoff-Gegenstände
DE102005019983.6 2005-04-27
DE102005048161.2 2005-10-06
DE102005048161A DE102005048161A1 (de) 2005-10-06 2005-10-06 Verfahren zur Hestellung metallisierter, extrudierter Kunststoff-Gegenstände
DE200510059323 DE102005059323A1 (de) 2005-12-09 2005-12-09 Verfahren zur Herstellung metallisierter, extrudierter Kunststoff-Gegenstände
DE102005059323.2 2005-12-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009543931A (ja) * 2006-07-17 2009-12-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 金属組成物、熱画像形成ドナーおよびそれらから得られたパターン化多層組成物
DE102009006708A1 (de) * 2009-01-29 2010-08-05 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Herstellen eines Elastomerlagers
CN102127764A (zh) * 2011-01-28 2011-07-20 厦门建霖工业有限公司 一种在塑胶基材表面实施半干法电镀的方法

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Publication number Priority date Publication date Assignee Title
US3692722A (en) * 1970-02-20 1972-09-19 Edgar W Clarke Polymeric compositions and methods of treating
US4038042A (en) * 1975-12-18 1977-07-26 E. I. Du Pont De Nemours And Company Electroplating of polypropylene compositions
EP0146946A1 (fr) * 1983-12-28 1985-07-03 Societe Nationale Elf Aquitaine Electrode de fer et procédé de fabrication
US4564424A (en) * 1983-04-15 1986-01-14 Rhone-Poulenc Recherches Metallization of electrically insulating polymeric film substrates
EP0306553A1 (fr) * 1985-09-16 1989-03-15 Richard E. Seeger Corps composite apte à recevoir un revêtement, article ainsi obtenu et procédé pour obtenir cet article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692722A (en) * 1970-02-20 1972-09-19 Edgar W Clarke Polymeric compositions and methods of treating
US4038042A (en) * 1975-12-18 1977-07-26 E. I. Du Pont De Nemours And Company Electroplating of polypropylene compositions
US4564424A (en) * 1983-04-15 1986-01-14 Rhone-Poulenc Recherches Metallization of electrically insulating polymeric film substrates
EP0146946A1 (fr) * 1983-12-28 1985-07-03 Societe Nationale Elf Aquitaine Electrode de fer et procédé de fabrication
EP0306553A1 (fr) * 1985-09-16 1989-03-15 Richard E. Seeger Corps composite apte à recevoir un revêtement, article ainsi obtenu et procédé pour obtenir cet article

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009543931A (ja) * 2006-07-17 2009-12-10 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 金属組成物、熱画像形成ドナーおよびそれらから得られたパターン化多層組成物
DE102009006708A1 (de) * 2009-01-29 2010-08-05 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Herstellen eines Elastomerlagers
DE102009006708B4 (de) * 2009-01-29 2013-05-23 Bayerische Motoren Werke Aktiengesellschaft Verfahren zum Herstellen eines Elastomerlagers
CN102127764A (zh) * 2011-01-28 2011-07-20 厦门建霖工业有限公司 一种在塑胶基材表面实施半干法电镀的方法
CN102127764B (zh) * 2011-01-28 2013-03-27 厦门建霖工业有限公司 一种在塑胶基材表面实施半干法电镀的方法

Also Published As

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