WO2007039323A1 - Objets en plastique pour la metallisation a proprietes de façonnage ameliorees - Google Patents

Objets en plastique pour la metallisation a proprietes de façonnage ameliorees Download PDF

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Publication number
WO2007039323A1
WO2007039323A1 PCT/EP2006/061847 EP2006061847W WO2007039323A1 WO 2007039323 A1 WO2007039323 A1 WO 2007039323A1 EP 2006061847 W EP2006061847 W EP 2006061847W WO 2007039323 A1 WO2007039323 A1 WO 2007039323A1
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Prior art keywords
weight
component
metal
extruded
composite layer
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PCT/EP2006/061847
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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
Wolfgang Gutting
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Basf Aktiengesellschaft
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Priority claimed from DE102005019923A external-priority patent/DE102005019923A1/de
Priority claimed from DE200510048122 external-priority patent/DE102005048122A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2007039323A1 publication Critical patent/WO2007039323A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/10—Applying flat materials, e.g. leaflets, pieces of fabrics
    • B44C1/14—Metallic leaves or foils, e.g. gold leaf
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • 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
    • 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
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0092—Metallizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2325/00—Polymers of vinyl-aromatic compounds, e.g. polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2369/00—Polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • 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

Definitions

  • the invention relates to metallizable extruded films or plates made of a plastic mixture comprising, based on the total weight of the components A, B, C, D and E 1, which gives a total of 100 wt .-%,
  • a from 5 to 49.45% by weight of a thermoplastic polymer as component A b from 50 to 94.45% by weight of a metal powder having a mean particle diameter of from 0.01 to 100 ⁇ m (determined according to the method defined in the description) wherein the metal has a more negative normal potential in acidic solution than silver, as component B, c 0.5 to 10 wt .-% of a dispersant as component C, d 0.05 to 5 wt .-% of a stabilizer as component D, and e 0 to 40% by weight of fibrous or particulate fillers or mixtures thereof as component E.
  • thermoplastic molding compositions for producing such metallizable extruded films or sheets, granules comprising such thermoplastic molding compositions, composite layers or sheets and moldings comprising such metallizable extruded sheets or plates, metallized polymer bodies comprising these extruded sheets or sheets, composite sheets or plates and moldings , Process for the preparation of these objects, the use of these objects and absorbers for electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these objects.
  • Metal powder-containing plastic materials and metallized plastic films or moldings are known and used in a variety of applications.
  • JP-A 2003-193103 describes polymer foils filled with metal powder as absorbers for electromagnetic radiation.
  • WO 03/10226 discloses single and multilayer, metal-filled polymer films as oxygen scavengers.
  • US Pat. No. 5,147,718 describes multilayered, metal powder-filled plastic films as suitable radar absorbers.
  • 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.
  • WO 86/02882 disclose the application of iron-containing binder or coating systems to plastic bodies, in which case electroless copper deposition followed by galvanic metallization is carried out.
  • No. 6,410,847 teaches the electroless deposition of copper or nickel layers on metal-filled, injection-molded polymer moldings.
  • the object of the present invention is to provide metallizable plastic parts which have improved mechanical properties, in particular improved toughness, flexural properties, with comparably good application properties with respect to, for example, electroless plating capability, absorption of electromagnetic radiation or absorption of oxygen compared to known metallizable plastic parts.
  • strength and deformability, as well as improved processing properties, for example in forming processes for the production of complex shaped components, have, and can be metallized without special pretreatment of the plastic surface.
  • the above-mentioned extruded sheets or plates were prepared from a plastic mixture comprising, based on the total weight of the components A, B, C, D and E, which gives a total of 100 wt .-%,
  • component E a from 5 to 49.45% by weight of a thermoplastic polymer as component A, b from 50 to 94.45% by weight of a metal powder having a mean particle diameter of from 0.01 to 100 ⁇ m (determined according to the method defined in the description) wherein the metal has a more negative normal potential in acidic solution than silver, as component B 1 c 0.5 to 10 wt .-% of a dispersant as component C, d 0.05 to 5 wt .-% of a stabilizer as component D, and e 0 to 40% by weight of fibrous or particulate fillers or mixtures thereof as component E,
  • thermoplastic molding compositions for producing such extruded films or sheets for producing such extruded films or sheets, granules comprising such thermoplastic molding compositions, composite sheets or sheets and moldings comprising such extruded sheets or plates, metallized polymer bodies comprising these extruded sheets or sheets, composite sheets or sheets and moldings, methods of preparation of these items, the use of these items as well as absorbers of electromagnetic radiation, oxygen scavengers, electrically conductive components, gas barriers and decorative parts comprising these items found.
  • the extruded films or sheets according to the invention have improved mechanical properties, in particular improved toughness, flexural strength and deformability, as well as improved processing properties, for example in forming processes for production, with comparatively good application properties with respect to, for example, electroless plating, absorption of electromagnetic radiation or oxygen absorption compared to known metallizable plastic parts Complex molded components, on, and are metallizable without special pretreatment of the plastic surface.
  • the extruded films or sheets of the present invention, as well as the other articles, methods and uses of the present invention are described below.
  • extruded films or sheets according to the invention are based on a plastics mixture comprising, based on the total weight of components A, B 1 C, D and E, which gives a total of 100% by weight,
  • a 5 to 49.45 wt .-% preferably 10 to 38.95 wt .-%, particularly preferably 20 to 27.5 wt .-% of component A, b 50 to 94.45 wt .-%, preferably 60 to 88.95% by weight, particularly preferably 70 to 77.5% by weight of component B, c 0.5 to 10% by weight, preferably 1.0 to 10% by weight, particularly preferably 1, 5 to 8
  • Wt .-% of component C d 0.05 to 5 wt .-%, preferably 0.05 to 4 wt .-%, particularly preferably 1, 0 to 3
  • Wt .-% of component D and e 0 to 40 wt .-%, preferably 0 to 28.95 wt .-%, particularly preferably 0 to 7.5 wt .-% of component E.
  • the elongation at break of component A by the factor of 1, 1 to 100, preferably by a factor of 1, 2 to 50, particularly preferably by a factor of 1, 3 to 10 greater than the elongation at break of Kunststoffmi- tion comprising the components A, B, C, D, and if present E, and the tensile strength of component A by a factor of 0.5 to 4, preferably by a factor of 1 to 3, particularly preferably by a factor of 1 to 2.5 greater than the tensile strength of the plastic mixture comprising the components A, B, C, D, and if present E (a factor less than 1 means that the tensile strength of the component A is less than the tensile strength of the plastic mixture comprising the components A, B, C, D. , and if present E);
  • the extruded films or sheets of the invention generally have a total thickness of 50 microns to 5 mm, preferably from 70 .mu.m to 3 mm, more preferably 100 .mu.m to 1, 5 mm.
  • the extruded sheets or sheets of the invention are made from a plastic blend comprising the following components.
  • 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 Styrolux ® of BASF Aktiengesellschaft, K-Resin TM CPC), polyamides, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polybutylene terephthalate (PBT), polycarbonate (such as Makrolon ® of Bayer AG ), Polymethyl methacrylate (PMMA), poly (ether) sulfones and polyphenylene oxide (PPO).
  • 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 preferably used as impact-modified SAN, as well as (meth) acrylonitrile-butadiene-styrene polymers ("MABS", transparent ABS), but also blends of SAN, ABS, ASA and MABS with other thermoplastics such as polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, PVC, polyolefins.
  • MABS acrylonitrile-butadiene-styrene polymers
  • 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, polyalkylacrylate rubbers in a copolymer matrix of, in particular, styrene and / or ⁇ -methylstyrene and acrylonitrile.
  • the rubber-elastic graft copolymer A ⁇ of component A is composed of
  • a1 1 to 99% by weight preferably 55 to 80% by weight, in particular 55 to 65% by weight, of a particulate grafting base A1 having a glass transition temperature below 0 ° C.
  • a2 1 to 99% by weight preferably 20-45% by weight, in particular 35-45% by weight, of a graft A2 from the monomers, based on A2, a21 40-100% by weight, preferably 65-85% by weight, of styrene units , a substituted styrene or a (meth) acrylic ester or mixtures thereof, in particular of styrene and / or ⁇ -methylstyrene as component A21 and a22 to 60 wt.%, preferably 15-35 wt.%, of units of acrylonitrile or methacrylonitrile, in particular of the acrylonitrile as component A22.
  • the graft A2 consists of at least one graft.
  • Component A1 consists of the monomers
  • the average particle size of the component A ⁇ is 50-1000 nm and is distributed monomodally.
  • the particle size distribution of component A is ⁇ bimodal, wherein 60-90% by weight has an average particle size of 50-200 nm and 10-40% by weight has an average particle size of 50-400 nm, based on the total weight of the 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 deduced 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.
  • the d-io or dgo value of the integral mass distribution is defined according to the dso 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 -S-alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, especially 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.
  • 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 favorable crosslinking monomer (see DE-PC 12 60 135).
  • the component A ⁇ is a graft copolymer.
  • the graft copolymers A merisate ⁇ 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 - 800 nm , preferably used of 50-500 nm and more preferably of 50-250 nm.
  • the graft copolymer A K is generally one or more stages, ie a polymer composed of a core and one or more shells.
  • the polymer consists of a base step (graft core) A1 and one or preferably several grafted steps A2 (grafting layer), the so-called grafting stages or graft shells.
  • one or more graft sheaths can be applied to the rubber particles, each graft shell having a different composition.
  • polyfunctional monomers containing crosslinking groups or reactive groups can also be grafted on (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 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, ⁇ -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, in particular below -3O 0 C possess.
  • 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 A2 would have a glass transition temperature of more than 80 0 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 0 C - 90 0 C using water-soluble or oil-soluble initiators such as peroxodisulfate or benzoyl peroxide, or by means of redox initiators. Redox initiators are also suitable for polymerization below 20 0 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.
  • Emulgatoren such as alkali metal salts of alkyl or alkylarylsuiflic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin 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. Generally, a weight ratio of water to monomers of 2: 1 to 0.7: 1 is used.
  • the polymerization initiators used are, in particular, the customary persulfates, for example 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 Position of the graft A1 used monomers used.
  • As further polymerization auxiliaries it is possible to use the customary buffer substances which bring about 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 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 d ⁇ o 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.
  • a monomer mixture of styrene and acrylonitrile 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, 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 grafting degree of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, is obtained 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, 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 ⁇ 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.
  • Proportion of the graft copolymer A ⁇ in the polymerization product obtained in the graft copolymerization is determined by the method indicated above.
  • reproducible changes in the particle size are also possible, for example by at least partial agglomeration of the particles into larger particles.
  • 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 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 ⁇ -methylstyrene and acrylonitrile.
  • the rubber-elastic graft copolymer A ⁇ 'of 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% by weight of at least one crosslinking monomer, preferably divinylbenzene, diallyl maleate, allyl ester of (meth) acrylic acid, dihydrodicyclopentadienyl acrylate, dinvinyl ester of dicarboxylic acids, such as amber and adipic acid and also diallyl and divinyl ethers of bifunctional alcohols, such as ethylene glycol or butane-1,4-diol,
  • crosslinking monomer preferably divinylbenzene, diallyl maleate, allyl ester of (meth) acrylic acid, dihydrodicyclopentadienyl acrylate, dinvinyl ester of dicarboxylic acids, such as amber and adipic acid and also diallyl and divinyl ethers of 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,
  • a11 from 70 to 100, preferably from 75 to 100,% by weight of at least one conjugated diene, in particular butadiene and / or isoprene,
  • a2 "from 10 to 60, preferably from 15 to 55,% by weight of a grafting pad A2", based on A2 '
  • the hard matrix A M of component A is at least one hard copolymer containing units derived from vinyl aromatic monomers, and wherein to the total weight of units derived from vinylaromatic monomers, 0-100% by weight, preferably 40-100% by weight, particularly preferably 60-100% by weight of ⁇ -methylstyrene and 0-100% by weight, preferably from 0 to 60% by weight, particularly preferably from 0 to 40% by weight, of styrene-derived units are contained, 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 vinyl aromatic monomers and wherein, based on the total weight of vinylaromatic monomer-derived units, 0 - 100 wt .-%, preferably 40 - 100 wt .-%, particularly preferably 60 to 100 wt .-% of ⁇ -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 '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 having a viscosity number VN (determined according to DIN 53726 at 25 0 C in 0.5 wt .- 'is at least one hard copolymer% solution in dimethylformamide) of 50 to 120 ml / g, which contains units which are derived from vinylaromatic monomers, and wherein, based on the total weight of vinylaromatic monomers derived units, 0 - 100 wt .-%, preferably 40 - 100th Wt .-%, particularly preferably 60 to 100 wt .-% of ⁇ -methyl styrene and 0 - 100 wt .-%, preferably 0 - 60 wt .-%, particularly preferably 0-40 wt .-% of styrene derived Units are included, from, related to A M ' From 69 to 81, preferably 70 to 78 wt
  • 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 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.
  • ABS polymers may contain other 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 or A M ' of component A are preferably amorphous polymers. According to one embodiment of the invention, 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 ( ⁇ -grafted ) resulting from the graft copolymerization for the preparation of component A ⁇ or A ⁇ ' .
  • Methyl) styrene / acrylonitrile copolymers are examples of the graft copolymerization for the preparation of the graft copolymers 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.
  • 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 ⁇ (or A ⁇ ') 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 blending of these components is carried out by coextruding, kneading or rolling the components, wherein the components, if necessary, have previously been isolated from the solution or aqueous dispersion obtained in the polymerization.
  • the products of the graft copolymerization obtained in aqueous dispersion can also be only partially dewatered and mixed as a moist crumb with the hard matrix, in which case the complete drying of the graft copolymers takes place during the mixing.
  • Thermoplastic elastomers based on styrene 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 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
  • the total butadiene content is preferably in the range from 15 to 50% by weight, more preferably in the range from 25 to 40% by weight, the total styrene content is preferably in the range from 50 to 85% by weight, more preferably in the range 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 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 .-%.
  • Linear styrene-butadiene block copolymers are particularly preferred of the general structure S- (S / B) -S 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 mean 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 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.
  • 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 are, according to the invention, 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, 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.
  • 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 an 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 powder 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), if 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; spherical and plate-shaped are preferred.
  • Such metal powders are common commercial goods or can be easily prepared by known methods, such as by electrolytic deposition or chemical reduction from solutions of metal salts or by reduction of an oxidic powder, for example by hydrogen, by spraying or atomizing a molten metal, especially in cooling media, for example gases or water.
  • 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 bands, heating wires or from a heating medium flowed through by a heating jacket, is surrounded.
  • the average particle diameter of the separating carbonyl iron powder can be controlled by the process parameters and reaction in the decomposition in wide ranges and are generally from 0.01 to 100 .mu.m, preferably from 0.1 to 50 .mu.m, more preferably from 1 to 10 microns ,
  • 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 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.
  • 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, for example sodium dodecyl sulfate or potassium dodecyl sulfate, and alkali metal salts of C 12 -C 16 -paraffinic sulfonic acids.
  • sodium dodecylbenzenesulfonate and sodium dioctylsulfone succinate are suitable.
  • 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 such as e.g. Hexadecyltrimethylammonium 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 and / or po- lypropylenoxidbasêt substances such as Pluronic ®, Tetronic ® Pluriol ® or 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.
  • the polyalkylene glycols are known per se or can be prepared by processes known per se, for example by anionic polymerization with alkali metal hydroxides, such as sodium or potassium hydroxide or alkali metal, such as sodium, sodium or potassium or potassium isopropoxide, as catalysts and with the addition of at least one starter molecule, the 2nd to 8, preferably 2 to 6, bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids such as antimony pentachloride, borofluoride etherate or bleaching earth, are prepared as catalysts of one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
  • alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal, such as sodium, sodium or potassium or potassium isopropoxide
  • Lewis acids such as antimony pentachloride, borofluoride etherate or bleaching earth
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1, 2 or 2,3-
  • the Alkylene oxides can be used individually, alternately in succession or as mixtures.
  • Water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid or terephthalic acid, aliphatic or aromatic, optionally N-mono-, N 1 N- or N 1 N'-dialkyl-substituted diamines having 1 to 4 carbon atoms:
  • Suitable starter molecules are, for example, in consideration in the alkyl radical, such as optionally 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.
  • 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 can be produced in a known manner.
  • organic acids preferably adipic acid or terephthalic acid
  • polyethylene glycol adipate or polyethylene glycol terephthalate is preferred.
  • nonionic surfactants are obtained by alkoxylation of compounds containing active hydrogen atoms substances produced, for example, adducts of ethylene oxide with fatty alcohols, oxo alcohols or alkyl phenols, for example those which are sold under the brand name Lutensol ® from BASF Aktiengesellschaft or Emulan ®. Ethylene oxide or 1,2-propylene oxide are preferably used for the alkoxylation.
  • 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. loading 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, carbon 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.
  • alkoxylated sugar ethers and sugar esters which are obtained by alkoxylation of the cited sugar ethers and sugar esters.
  • Preferred alkoxylating agents are ethylene oxide and 1,2-propylene oxide.
  • the degree of alkoxylation is generally between 1 and 20, preferably 2 and 10, particularly preferably 2 and 6.
  • Particularly preferred alkoxylated sugar esters are polysorbates which are obtained by ethoxylation of the sorbitan esters described above, for example described in CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995, keyword "Polysorbate”.
  • 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 extruded films or sheets contain stabilizers which are typical and customary as such for plastic mixtures.
  • stabilizers serve, for example, to improve the thermal stability, to increase the light or UV stability, to increase the resistance to hydrolysis or the resistance to chemicals.
  • Preferred stabilizers are heat stabilizers or antioxidants, for example 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).
  • Preferred heat stabilizers or antioxidants are vitamin E or compounds of analogous construction, as are HALS stabilizers (hindered amine light stabilizers), benzophenones, resorcinols, salicylates, benzotriazoles such as TinuvinRP (UV absorber 2 - (2H-benzotriazol-2-yl 4-methylphenol of CIBA).
  • Preferred heat stabilizers or oxidation are, in particular hindered phenols, such as 2,6-dimethyl-4-tert-butyl-phenol, Irganox ® 1076 and chemically related products, Irganox ® 3052 and chemically related products and phosphites, such as tris (nonylphenyl) phosphite (for example, Irgafos ® TNPP) or Irgafos ® 168th
  • the extruded films or sheets 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 woliastonite may be added.
  • plastic mixture on which the extruded films or plates according to the invention are based can also contain further additives which are typical and customary for plastic mixtures.
  • additives examples include: dyes, pigments, colorants, antistatic agents, antioxidants, and in particular lubricants / lubricants, which are useful for the production of moldings or moldings.
  • the metering in of these further additives can take place at any stage of the production process, but preferably at an early stage, to take advantage of the desired effects or special effects of the additives at an early stage.
  • 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, colorants such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium suifides, derivatives of perylenetetracarboxylic acid are also useful.
  • Processing aids such as lubricants and antistatic agents are usually used in amounts of 0.01-5 wt .-%.
  • thermoplastic molding compositions for producing the inventive extruded films or sheets of the components A, B, C, D and, if present, E is carried out by methods known in the art, for example by mixing the components in the melt known to those skilled Devices at temperatures which are usually in the range of 150 to 300 0 C 1, in particular at 200 to 28O 0 C, depending on the type of polymer A used.
  • the components can be supplied in each case pure form the mixing devices.
  • 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, D and E.
  • a concentrate for example the components B 1 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 be processed into granules by methods known to the person skilled in the art in order to be extruded at a later time into the films or sheets according to the invention. However, they can also be extruded directly after the mixing process or in one working step with the mixing process (ie simultaneous melt mixing and extrusion), preferably by means of a screw extruder, to the films or sheets according to the invention.
  • the screw extruder is designed as a single-screw extruder with at least one distributively mixing screw element. In a further preferred embodiment of the method according to the invention, the screw extruder is designed as a twin-screw extruder with at least one distributively mixing screw element.
  • the type and amount of the other components are selected such that the plastic mixtures comprising the components A, B, C, D and, if present, E have tear strengths within the following ranges:
  • extruded films or sheets according to the invention are suitable in particular as a cover layer (3) of multilayer composite laminate sheets or films which, in addition to the cover layer, have at least one further substrate layer (1) 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 made of the impact-modified vinylaromatic copolymers described above, in connection with the extruded films or plates, thermoplastic elastomers based on styrene, polyols finen, polycarbonates and thermoplastic polyurethanes or mixtures thereof, particularly preferably 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) may 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).
  • One embodiment of the invention relates to a composite layered sheet or film of a substrate layer (1), covering layer (3) and an intervening intermediate layer (2) consisting of aliphatic thermoplastic polyurethane, impact-modified polymethyl methacrylate (PMMA), 1 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.
  • a substrate layer (1), covering layer (3) and an intervening intermediate layer (2) consisting of aliphatic thermoplastic polyurethane, impact-modified polymethyl methacrylate (PMMA), 1 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.
  • 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 foils 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 laminate sheets or sheets according to the invention may, in addition to the mentioned layers, also have further layers, preferably an adhesion promoter layer, on the side of the substrate layer (1) facing away from the cover layer (3), which results in improved adhesion of the composite layer boards or foils to that described below serve as described carrier layer.
  • adhesive layers made of a material compatible with polyolefins, such as SEBS are preferred (styrene-ethylene-butadiene-styrene copolymer, for example sold under the trademark crater-ton ®) manufactured. 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 in such a way that the composite layer plates or foils 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 of the invention can be prepared 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. The desired layer sequence is then produced by appropriate overlapping of the foils or plates, whereupon these are applied, for example, by be performed a heatable nip and be connected under pressure and heat to form a composite layer plate or film.
  • extruded films or plates and the laminated sheets or films comprehensive 'send extruded films or plates according to the invention can be used for the production of moldings.
  • 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 comprising the extruded foils or sheets according to the invention and a back-injected, back-foamed, back-poured or back-pressed carrier layer made of plastic.
  • the production of molded parts according to the invention from the extruded films or plates or the composite layer plates or films can be carried out according to known and, for example, in WO 04/00935 described method (hereinafter, the methods for the further processing of composite layer plates or films are described, but these methods are also can be used for the further processing of the extruded films or plates according to the invention).
  • the composite laminates or foils can be back-injected, backfoamed, back-poured or back-pressed without further processing.
  • the use of the described composite layer plates or foils makes it possible to produce easily three-dimensional components without prior thermoforming.
  • the composite sheets or films may also be subjected to a previous thermoforming process.
  • composite layer plates or sheets having the three-layer structure of substrate layer, intermediate layer and cover layer or the two-layer structure of substrate layer and cover layer can 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 foils are stretched in the thermoforming process. Since the surface quality and metallizability of the composite layer plates or films at high draw ratios, for example up to 1: 5 does not decrease with the stretching, the thermoforming processes are almost no restrictions on the possible stretching exposed.
  • the composite layer plates or films may be subjected to further shaping steps, for example contour cutting.
  • the molded parts according to the invention can be produced, if appropriate after the described thermoforming processes, by insert molding, backfoaming, back-casting or rear-pressing. 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.
  • thermoplastic molding compositions based on ASA or ABS are preferred.
  • SAN polymers poly (meth) acrylates, polyethersulfones, polybutylene terephthalate, polycarbonates, polypropylene (PP) or polyethylene (PE) and blends of ASA or ABS polymers and polycarbonates or polybutylene terephthalate and blends of polycarbonates and polybutylene terephthalate used, wherein it is useful when using PP and / or PE to provide the substrate layer previously with a primer layer.
  • Particularly suitable are amorphous thermoplastics or their blends.
  • thermoset molding compounds known to those skilled in the art are used.
  • these plastic materials are glass fiber reinforced, suitable variants are described in particular in DE-A1 100 55 190.
  • 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, molded or pressed behind, or backfoamed or thermoset with molding compounds.
  • 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. Metallized polymer body
  • extruded films or sheets, composite layer films or sheets and moldings according to the invention are particularly suitable for producing metallized polymer bodies, without the need for any special pretreatment of the surface of the extruded films or sheets, composite layer films or sheets and moldings.
  • the composite layer films or plates or moldings after the last molding process are electrolessly or galvanically brought into contact with an acidic metal salt solution, the metal of this metal salt solution having a more positive normal potential in acidic solution than component B.
  • Preferred metals having a more positive normal potential in acidic solution than component B are gold and silver (when component B is copper), or copper, nickel and silver, in particular copper (when 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.
  • galvanic deposition of layers Mg of aluminum is preferred.
  • Application by direct metallization by means of vacuum vapor deposition, irradiation / spraying or sputtering by methods known to the person 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 polymer bodies 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 polymer bodies for use in the decorative sector have a copper layer deposited electrolessly, on which a galvanically deposited nickel layer and a chromium, silver or gold layer deposited thereon.
  • extruded films or sheets, composite layer films or sheets and moldings comprising component B according to the invention are suitable as absorbers for electromagnetic radiation or oxygen scavengers without subsequent metallization.
  • the metallized polymer bodies according to the invention comprising an electrolessly depositable metal layer M s are suitable without further application of a deposited metal layer M 9 as electrically conductive components, in particular printed circuit boards, transponder antennas, switches, sensors and MID's absorbers for electromagnetic radiation or gas barriers.
  • the metallized polymer bodies comprising an electrolessly depositable metal layer Ms and at least one deposited metal layer M 9 are electrically conductive components, in particular printed circuit boards, transponder antennas, switches, sensors and MIDs, absorbers for electromagnetic radiation or gas barriers or decorative parts, in particular decorative parts in motor vehicle, sanitary , Toy, household and office area, suitable.
  • Examples of such applications are: computer cases, electronic component housings, military and non-military shields, shower and washbasin faucets, showerheads, shower rods and holders, metalized door handles and door knobs, toilet paper roll holders, bath tub handles, metallized trim on furniture and mirrors, frame for shower enclosures. Also to be mentioned: Metallized plastic surfaces in the automotive sector, such as trim strips, exterior mirrors, radiator grills, front-end metallization, wind deflectors, exterior body parts, door sill, tread plate replacement, wheel covers.
  • 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.
  • the metallised polymer bodies insofar as they comprise magnetisable 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 metallizable plastic parts according to the invention have improved mechanical properties, in particular improved toughness, flexural strength and deformability, as well as improved processing properties, for example in forming processes for producing complex shaped articles, with comparatively good application properties with respect to electroless metallization, absorption of electromagnetic radiation or oxygen absorption Components, and are metallizable without special pretreatment of the plastic surface.
  • Styroflex ® 2G66 a TPE-S from BASF Aktiengesellschaft with an elongation at break of 480%, wherein component D1 0.3 wt .-%, based on the total weight of A1, D1 and D2, 2-propanoic acid, 2- (1 , 1-dimethylethyl) -6 - [[3- (1, 1-dimethylethyI) -2-hydroxy-5-methylphenyl] methyl] -4 (Irganox ® 3052) and as compo- nent D2 0.3 wt .-% , based on the total weight of A1, D1 and D2,
  • Tris (nonylphenyl) phosphite Tris (nonylphenyl) phosphite.
  • plastic mixtures were each injection molded at 220 0 C to test specimens and tensile elongations and tensile strengths in the tensile test according to ISO 527-2: 1996 on specimens of type 1 BA (Appendix A of the said standard: "small specimens”) determined.
  • a pressed film with 100 microns thickness at 200 bar pressure and 200 0 C temperature were prepared.
  • 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: 34 0 C in the plastic mixture containing A2, or 45 0 C in the plastic mixture containing A1).
  • the component B1 and in each case a dispersing agent C were kneaded on a kneader (type IKAVISC MKD). Borkneter H60) at temperatures of 140-190 0 C plastic mixtures with different proportions by weight of components A and B produced. The plastic mixtures were each further processed to a pressed film with 100 microns thickness at 200 bar pressing pressure and 200 0 C temperature.
  • Pluronic ® PE 10400 a block copolymer of 80 mol% Ethlenoxidtechniken and 20 mol% propylene oxide units
  • Pluronic ® PE 6800 a block copolymer composed of 50 mol% Ethlenoxidtechniken and 50 mol% propylene oxide units
  • Pluriol ® P polypropylene glycol (number average trailing Mol weight M w)
  • Lutensol ® AO 11 largely linear Ci3-Ci5-oxo alcohol ethoxylate with 11 ethylene oxide units
  • Emulan® ® L 200 castor oil
  • the component A1 used the components D1 and D2 in amounts of 0.3 wt .-%, based on the total weight of the components A1, D1 and D2 contained.
  • Comparative Experiment 4-1 V of Table 3 by prior annealing of component A1, the detectable content of components D1 and D2 was in each case less than 0.02% by weight, based on the total weight of components A1, D1 and D2. gereichert. These plastic mixtures were stored for 30 min in a drying oven at 26O 0 C. The respective observations regarding discoloration and crosslinking during hot storage are shown in Table 3.

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Abstract

L'invention concerne des films ou des plaques extrudés métallisables produits à partir d'un mélange de matières plastiques comprenant, par rapport au poids total des constituants A, B, C, D et E qui correspond à 100 % en poids, a) comme constituant A, 5 à 49,45 % en poids d'un polymère thermoplastique, b) comme constituant B, 50 à 94,45 % en poids d'une poudre métallique à diamètre moyen de particules compris entre 0,01 et 100 µm (déterminé selon la méthode décrite dans la description), le métal présentant en solution acide un potentiel normal plus négatif que l'argent, c) comme constituant C, 0,5 à 10 % en poids d'un agent dispersant, d) comme constituant D, 0,05 à 5 % en poids d'un agent stabilisant et e) comme constituant E, 0 à 40 % en poids de matières de remplissage fibreuses ou particulaires ou leurs mélanges. L'invention concerne également des matières moulables thermoplastiques servant à produire de tels films ou plaques extrudés métallisables, des granulés comprenant de telles matières moulables thermoplastiques, des films ou plaques stratifiés composites et des pièces moulées comprenant de tels films ou plaques extrudés, des corps polymères métallisés comprenant ces films ou plaques extrudés, des films ou plaques stratifiés composites et des pièces moulées, des procédés servant à produire ces objets, l'utilisation de ces objets, ainsi que des absorbeurs pour le rayonnement électromagnétique, des désoxygénants, des composants électroconducteurs, des barrières contre les gaz et des pièces décoratives comprenant ces objets.
PCT/EP2006/061847 2005-04-27 2006-04-26 Objets en plastique pour la metallisation a proprietes de façonnage ameliorees WO2007039323A1 (fr)

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DE102005019923A DE102005019923A1 (de) 2005-04-27 2005-04-27 Kunststoffgegenstände zur Metallisierung mit verbesserten Formgebungseigenschaften
DE102005019923.2 2005-04-27
DE102005048122.1 2005-10-06
DE200510048122 DE102005048122A1 (de) 2005-10-06 2005-10-06 Kunststoffgegenstände zur Metallisierung mit verbesserten Formgebungseigenschaften

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110014492A1 (en) * 2008-03-13 2011-01-20 Basf Se Method and dispersion for applying a metal layer to a substrate and metallizable thermoplastic molding compound
WO2022226953A1 (fr) * 2021-04-30 2022-11-03 The Procter & Gamble Company Article moulé ayant un aspect métallique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI355220B (en) 2008-07-14 2011-12-21 Unimicron Technology Corp Circuit board structure
KR102658489B1 (ko) * 2017-12-28 2024-04-18 라이온 가부시키가이샤 안과용 제품 및 마스킹 방법

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Publication number Priority date Publication date Assignee Title
GB2171410A (en) * 1985-01-31 1986-08-28 Mitsubishi Petrochemical Co Polymer compositions containing metal powders
EP0265839A2 (fr) * 1986-10-28 1988-05-04 CALP Corporaton Composition à mouler à base d'une résine thermoplastique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2171410A (en) * 1985-01-31 1986-08-28 Mitsubishi Petrochemical Co Polymer compositions containing metal powders
EP0265839A2 (fr) * 1986-10-28 1988-05-04 CALP Corporaton Composition à mouler à base d'une résine thermoplastique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110014492A1 (en) * 2008-03-13 2011-01-20 Basf Se Method and dispersion for applying a metal layer to a substrate and metallizable thermoplastic molding compound
WO2022226953A1 (fr) * 2021-04-30 2022-11-03 The Procter & Gamble Company Article moulé ayant un aspect métallique

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