EP1618228A1 - Utilisation d'un objet comme element decoratif - Google Patents

Utilisation d'un objet comme element decoratif

Info

Publication number
EP1618228A1
EP1618228A1 EP04727647A EP04727647A EP1618228A1 EP 1618228 A1 EP1618228 A1 EP 1618228A1 EP 04727647 A EP04727647 A EP 04727647A EP 04727647 A EP04727647 A EP 04727647A EP 1618228 A1 EP1618228 A1 EP 1618228A1
Authority
EP
European Patent Office
Prior art keywords
use according
metallic
layer
metallic substrate
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04727647A
Other languages
German (de)
English (en)
Inventor
Hartmut Sauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aalberts Surface Technologies GmbH Kerpen
Original Assignee
AHC Oberflaechenechnik GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10317798A external-priority patent/DE10317798B4/de
Priority claimed from DE102004001613A external-priority patent/DE102004001613A1/de
Application filed by AHC Oberflaechenechnik GmbH filed Critical AHC Oberflaechenechnik GmbH
Publication of EP1618228A1 publication Critical patent/EP1618228A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2013—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by mechanical pretreatment, e.g. grinding, sanding
    • 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • 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
    • C23C18/16—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 by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942—Fibers are aligned substantially parallel
    • Y10T428/249945—Carbon or carbonaceous fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942—Fibers are aligned substantially parallel
    • Y10T428/249946—Glass fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition polymer is perhalogenated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to the use of an object, the surface of which comprises, in whole or in part, a composite material consisting of a polymer and a metallic layer thereon as a decorative component.
  • Effects are to be achieved, such as a stainless steel look, an aluminum look or the appearance of a matt metal surface.
  • Plastic films for example for food packaging.
  • DE 198 49 661 A1 discloses steaming a special polyester film with aluminum, so that it is high Oxygen barrier, has a good gloss and a low coefficient of friction.
  • the adhesive strengths of up to 3 N / mm specified there are, however, too low to be able to exist in a mechanically stressed, functional application of the metallized film.
  • DE 42 11 712 A1 also describes irradiating the surface of a substrate to improve the adhesive strength with an Eximer laser.
  • a PET (polyethylene terephthalate) film is irradiated with this special laser so that it can subsequently be vapor-coated with a ferromagnetic metal layer using a PVD process.
  • Such films are used inter alia as an audio or video recording medium.
  • a major disadvantage of this process is the considerable environmental pollution caused by the two chemical treatment agents, so that this process can no longer be used from an environmental point of view.
  • a further developed process for the metallization of polyamides which is based on the above-described principle of swelling the surface of the plastic substrate but does not provide for pickling with chromosulfuric acid, is described in an article by G.D. Wolf and F. Funger "Metallized polyamide injection molded parts", Kunststoffe, 1989, pp. 442-447.
  • the surface of the amorphous polyamide is treated with an organometallic activator solution. This is followed by a conventional deposition process for a chemical nickel layer.
  • the object of the present invention is to provide a decorative component, the surface of which is wholly or partly a composite material made of a plastic and one
  • Has metal layer that overcomes the disadvantages of the prior art described above and can be produced on an industrial scale.
  • the object is achieved according to the invention by the use of an object, the surface of which has a composite material in whole or in part, the composite material comprising a non-metallic substrate containing at least one polymer and a metal layer deposited thereon without external current and having an adhesive strength of at least 4 N / mm 2 exists as a decorative component.
  • the object used as a decorative component the surface of which comprises a composite material in whole or in part, this composite material having a first non-metallic layer and a second metallic layer applied thereon, and wherein a) the surface of the object is not chemically pretreated before the metallic layer is applied; and b) the metallic layer is not applied by thermal spraying, CVD, PVD or laser treatment.
  • chemical pretreatment is to be understood as a differentiation from mechanical treatments to any treatment of a substrate surface which is carried out by pickling, etching, swelling, vapor deposition, plasma treatment or similar methods and in which a change in the surfaces is brought about by a chemical reaction ,
  • the articles used according to the present invention have a rough, sharp-edged boundary layer between the non-metallic layer and the metal layer applied without external current. These sharp-edged bulges and undercuts in the boundary layer are clearly recognizable as angular surface contours, for example in a cross-section analysis, the
  • the adhesive strengths (specified in N / mm 2 ) of the composite materials according to the invention are determined exclusively on the basis of the front tensile test according to DIN 50160: the front tensile test (vertical tensile test) according to DIN 50160 has been used for years to test semiconductors, to determine the adhesive tensile strength of thermally sprayed layers and used in various coating technologies.
  • the layer / substrate composite to be tested is glued between two test stamps and subjected to uniaxial brisk force until it breaks (see Figure 1). If the adhesive strength is greater than that of the coating and if there is a break between the layer and the substrate, you can:
  • the standard deviation of the adhesive strength at six different measured values distributed over the surface of the composite material is at most 25% of the arithmetic mean.
  • the specified uniformity of adhesive strength enables the use according to the invention of objects with a composite material as decorative components in a special way. The items are more suitable for everyday use and are so wear-resistant that completely new areas of application can be opened up.
  • an object is used whose composite material has a non-metallic substrate, which is also the surface of the object.
  • These surfaces are preferably based on a polymeric material. Fiber-reinforced plastics, thermoplastics and other industrially used polymers are particularly preferred.
  • the object used can consist of a metallic or ceramic material that is coated with a non-metallic substrate that contains at least one polymer. Examples of this are a painted emblem made of aluminum, which is selectively metallized, or a metal housing, which is coated with a powder coating and is partially metallized.
  • an object with a composite material is used as the decorative component, which has a boundary between the non-metallic substrate and the metallic layer with a roughness whose R z value does not exceed 35 ⁇ m.
  • the R z value is a measure of the average vertical surface fracture.
  • objects with a composite material are used as decorative components which have a boundary between the non-metallic substrate and the metallic layer with a roughness, expressed by an R a value of at most 5 ⁇ m.
  • the R a value is a measurement-reproducible measure of the roughness of surfaces, whereby profile outliers (ie extreme valleys or hills) are largely ignored due to the area integration.
  • the sample to be examined is placed in a transparent investment material (Epofix putty, available from Struer).
  • the embedded sample is ground on a table grinding machine from Struer, type KNUTH-ROTOR-2.
  • Different sanding papers with silicon carbide and different grain sizes are used. The exact order is as follows:
  • Water is used during the grinding process to remove the abrasive particles.
  • the tangential force that occurs on the cross-section and arises from friction is directed so that the metallic layer is pressed against the non-metallic substrate. This effectively prevents the metallic layer from detaching from the non-metallic substrate during the grinding process.
  • the sample treated in this way is then polished using a motor-operated preparation device of the DAP-A type from Struer.
  • the usual sample winder is not used, rather the sample is only polished by hand.
  • a speed between 40 and 60 rpm and a contact pressure between 5 and 10 N are used.
  • the cross section is then subjected to an SEM image.
  • the boundary line of the layer between the non-metallic substrate and the metallic surface is determined at a magnification of 10,000 times.
  • the OPTIMAS program from Wilhelm Mikroelektronik is used for evaluation.
  • X-Y value pairs are determined that describe the boundary line between the substrate and the layer.
  • a distance of at least 100 ⁇ m is required to determine the enlargement of the boundary line in the sense of the present invention.
  • the course of the boundary line must be determined with at least 10 measuring points per ⁇ m.
  • the enlargement of the boundary line is determined from the quotient of true length by geometric length.
  • the geometric length corresponds to the distance of the measuring section, i.e. between the first and last measuring point.
  • the true length is the length of the line that runs through all recorded measurement points.
  • the surface roughness value R a is determined according to the DIN 4768 / ISO 4287/1 standard, also using the XY value pairs previously recorded.
  • the non-metallic substrate contains at least one fiber-reinforced polymer, in particular a carbon fiber-reinforced polymer, and the diameter of the fiber is less than 10 ⁇ m.
  • the non-metallic substrate in a further form of the present invention may contain at least one fiber-reinforced polymer, in particular a glass fiber-reinforced polymer, the diameter of the fiber being more than 10 ⁇ m.
  • CFRP carbon fiber reinforced plastics
  • GTK glass fiber reinforced plastics
  • plastics reinforced by aramid fibers or plastics reinforced by mineral fibers are particularly preferably used, in particular carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GFK), plastics reinforced by aramid fibers or plastics reinforced by mineral fibers.
  • Components achieved with low weight which are particularly interesting due to their low cost for industrial use, such as components for the cabin area of aircraft.
  • glass fiber-reinforced polymers as part of the non-metallic substrate which have fibers with a diameter greater than 10 ⁇ m, are very inexpensive and easy to process.
  • the fiber diameter has a great influence on the roughness, so that in such materials the present invention is achieved a roughness value R a of at most 10 microns in accordance with.
  • R a of at most 10 microns in accordance with.
  • the objects used according to the invention have high uniformity of adhesion. This makes it possible for the first time to significantly increase the service life for the decorative component.
  • the advantage is particularly serious in the case of components with a surface covered by the layer composite of more than 10 dm 2 , that is to say in the case of large components or components with a large surface.
  • the object described above has a boundary between the non-metallic substrate and the metallic layer, which has a roughness with an R z value of at most 100 ⁇ m.
  • the object described above has a boundary between the non-metallic substrate and the metallic layer, which has a roughness with an R z value of at most 100 ⁇ m.
  • the polymer of the non-metallic substrate is selected from the group of polyamide, polyvinyl chloride, polystyrene, epoxy resins, polyether ether ketone, polyoxymethylene, polyformaldehyde, polyacetal, polyurethane, Polyetherimide, polyphenyl sulfone, polyphenylene sulfide, polyarylamide, polycarbonate and polyimide.
  • the metallic layer can have an adhesive strength of at least 12 N / mm 2 .
  • the polymer of the non-metallic substrate can also be selected from polypropylene or polytetrafluoroethylene.
  • Embodiments according to the invention are particularly preferred which have a standard deviation of the adhesive strength of six different measured values distributed over the surface of the layer composite of at most 25%, in particular at most 15%, of the arithmetic mean. In this way, the resulting components can be subjected to even greater mechanical stress.
  • the metal layer deposited without external current is a metal alloy or metal dispersion layer.
  • objects with a composite material can be used for the first time as decorative components which have excellent adhesion of the metallic layer to the non-metallic substrate.
  • the uniformity of the adhesion of the metallic layer also plays an important role in the suitability of these objects as highly stressed components.
  • a targeted selection of the non-metallic substrate and the metallic layer on it enables an exact adaptation of the property profile to the conditions of the area of application.
  • a copper layer is deposited on the non-metallic substrate of the object used according to the invention as a metal layer deposited without external current.
  • Nickel or gold layer applied.
  • a metal alloy or metal dispersion layer deposited without external current can also be applied, preferably a copper, nickel or gold layer with embedded non-metallic particles.
  • the non-metallic particles can have a hardness of more than 1,500 HV and can be selected from the group of silicon carbide, corundum, diamond and tetraborarbide.
  • these dispersion layers thus have further functions, for example the wear resistance or surface wetting of the objects used can be improved.
  • the non-metallic particles can also preferably have friction-reducing properties and be selected from the group of polytetrafluoroethylene, molybdenum sulfide, cubic boron nitride and tin sulfide.
  • the objects of the present invention are particularly preferably obtained using a special method which comprises the following steps: i. the surface of the non-metallic layer is not chemically pretreated before the metallic layer is applied; ii. the surface of the non-metallic layer is microstructured in a first step by means of a blasting agent; iii. the metallic layer is then applied by electroless metal deposition.
  • the objects to be used as decorative components according to the present invention initially have a non-metallic substrate as a composite material which contains at least one polymer. To produce the composite material according to the
  • the surface of the non-metallic substrate is microstructured in a first step by means of a beam treatment.
  • the method used is described for example in DE 197 29 891 A1.
  • Particularly wear-resistant, inorganic particles are used as blasting media. It is preferably copper-aluminum oxide or silicon carbide. It has proven to be advantageous that the blasting agent has a particle size between 30 and 300 ⁇ m. It is further described there that a metal layer can be applied to the roughened surfaces by means of a metal deposition without external current.
  • the substrate surface is activated in two steps.
  • the component is immersed in a colloidal solution (activator bath).
  • the palladium nuclei required for metallization which are already present in the activator solution, are adsorbed on the plastic surface.
  • the tin-II or tin-IV oxide hydrate which is additionally formed when immersed in the colloidal solution is dissolved by rinsing in an alkaline, aqueous solution (conditioning), thereby exposing the palladium seed.
  • chemical reduction baths can be nickel-plated or copper-plated.
  • the baths for the nickel or copper deposition have the property of reducing the metal ions dissolved in them at the nuclei and of depositing elementary nickel or copper.
  • the two reactants have to approach the noble metal nuclei on the plastic surface.
  • the resulting redox reaction creates the conductive layer, the noble metal nuclei taking up the electrons of the reducing agent and releasing them again when a metal ion approaches. This reaction releases hydrogen.
  • the applied layer takes on the catalytic effect. This means that the layer grows together from the palladium seeds until it is completely closed.
  • the deposition of nickel is dealt with here as an example.
  • the germinated and conditioned plastic surface is immersed in a nickel metal salt bath, which is in a temperature range between 82 ° C and
  • the electrolyte is generally a weak acid with a pH between 4.4 and 4.9.
  • the thin nickel coatings applied can be reinforced with an electrolytically deposited metal layer.
  • Coating components with layer thicknesses> 25 ⁇ m is not economical due to the low deposition rate of chemical coating processes.
  • the chemical coating pro only a few coating materials are deposited, so that it is advantageous to use electrolytic processes for other technically important coating materials.
  • Another important point is the different properties of chemically and electrolytically deposited layers with layer thicknesses> 25 ⁇ m, for example leveling, hardness and gloss.
  • the basics of electrolytic metal deposition can be found in B. Gaida, "Introduction to electroplating", EG Leuze-Verlag, Saulgau, 1988 or in H. Simon, M. Thoma, "Applied surface technology for metallic materials", C.
  • Plastic cables that have an electrically conductive layer due to an electroless coating process differ only insignificantly from those of the metals in terms of electrolytic metallization. Nevertheless, some points should not be neglected in the electrolytic metallization of metallized plastics. Due to the mostly low conductive layer thickness, the current density must be reduced at the beginning of the electrolytic deposition. If this point is not observed, the conductive layer may peel off and burn. Furthermore, care should be taken to ensure that annoying tarnish layers are removed using specially designed paper baths. Furthermore, residual stresses can destroy the layer. When nickel layers are deposited from an ammoniacal bath, tensile stresses of the order of 400 to 500 MPa, for example, can occur.
  • a change in the structure of the nickel coatings in the form of a changed grain size and the formation of micro-deformations can promote the reduction of internal stresses, which can have a positive effect on a possible premature coating failure.
  • One or more layers in particular metallic, ceramic, as well as crosslinked or hardened polymer layers, can also be arranged on the metallic layer.
  • the objects of the present invention can have a copper layer as a metallic layer, to which a further copper layer can subsequently be applied. Then, for example, a gold layer is applied to the existing metal layers.
  • Such coatings can be used, for example, for the production of gold-plated fittings, for example in the sanitary or automotive sector.
  • the objects used according to the present invention can also have a nickel layer as the metallic layer, to which a further nickel layer is applied. In this way it is possible to achieve a high degree of rigidity of the resulting plastic parts and thus to ensure an application for components that are subject to high mechanical stress.
  • metallic layers can be applied not only electrolytically but also with the aid of other methods such as CVD / PVD to an object with a metallic layer of the present invention.
  • Another interesting example of an object according to the invention is a plastic which is initially provided with a nickel layer applied without external current. Layers of silver and gold are subsequently applied electrolytically to this nickel layer.
  • Objects can be used in a very wide range of technical applications.
  • An article according to the present invention can be used, for example, as a housing, container, handle, cover, emblem, holder and trim strip.
  • the blasting system is operated at a pressure of 4 bar.
  • a boron carbide nozzle with a diameter of 8 mm is used as the jet nozzle.
  • the beam duration is 4.6 s.
  • SiC with P80 grit with an average grain diameter of 200 to 300 ⁇ m is used as the abrasive.
  • 2 pressure circuits were installed, one each for the transport of the blasting medium and the actual acceleration process. This modification resulted in a very constant volume flow and a large pressure range.
  • a stream of compressed air transports the abrasive to the lowest possible pressure
  • the flow conditions ensure, caused by a high volume flow of the blasting medium and a low proportion of compressed air, a low wear of the system and the blasting medium.
  • the cross section is only reduced at the end of the transport hose in front of the mixing nozzle in order to set the desired volume flow.
  • a constant volume flow of 1 l / min was specified for all plastic pretreatments.
  • compressed air volume flow 1 flows up to the nozzle, which can be continuously adjusted within a pressure range of 0.2-7 bar.
  • the blasting medium which is conveyed into the mixing nozzle at a very low flow rate, is then accelerated by the high flow rate of the compressed air flow.
  • the roughened plate is treated in an ultrasonic bath with a mixture of deionized water and 3% by volume butyl glycol for five minutes.
  • the bath series used for the metal deposition of the conductive layer are based on the well-known colloidal palladium activation in connection with a final catalyzed metal reduction. All of the bath rows required for this were purchased from Max Schlötter. The diving sequences, treatment times and temperatures specified by the manufacturer were observed in all process steps of nickel deposition:
  • Conditioner 101 Conditioning the material surface by detaching annoying tin compounds from the surface. Diving time: 6 min, room temperature
  • the thickness of the nickel layer is sufficient for an electrolytic coating. All process steps that were necessary for the deposition of the conductive layer were carried out in 50 l plastic trays, with a nickel temperature of 90 ° ⁇ 0.5 ° C being maintained during the entire coating cycle by an additional heating plate with temperature control. In order to obtain a uniform and reproducible layer quality, the bath series were analyzed and supplemented after a throughput of 20 samples according to the Max Schlötter company. After the nickel conductive layer had been chemically applied, the sample was cooled from approx. 90 ° C. to approx. 60 ° C. in distilled water in order to then be electrolytically coated with nickel at 55 ° C. This intermediate step served the emergence of
  • the example according to the invention is repeated, but after the blasting treatment the
  • the plate is then treated in a further ultrasonic bath with pure, 96% ethanol for a further five minutes.
  • the cross section examination by SEM (1,500 times and 3,000 times) are in the following
  • the evaluation of the EDX analysis showed a residual amount of calcium of 0.91% by weight, which comes from the treatment of the CaC0 3 / ethanol suspension.
  • This difference for example when using polyamide automobile door handles, means that in addition to the optical properties of the component, the thermal resistance to temperature fluctuations for a period of more than

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
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  • Chemically Coating (AREA)

Abstract

L'invention concerne l'utilisation d'un objet comme élément décoratif, la surface de l'objet comprenant entièrement ou partiellement un matériau composite constitué d'un substrat non métallique qui contient au moins un polymère, et d'une couche métallique déposée sans apport de courant externe sur le substrat et ayant une adhérence d'au moins 4 N/mm<2>.
EP04727647A 2003-04-16 2004-04-15 Utilisation d'un objet comme element decoratif Withdrawn EP1618228A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10317798A DE10317798B4 (de) 2003-04-16 2003-04-16 Verfahren zur Herstellung eines dekorativen Bauteils
DE102004001613A DE102004001613A1 (de) 2004-01-09 2004-01-09 Gegenstand mit einem Schichtenverbund
PCT/IB2004/050460 WO2004092445A1 (fr) 2003-04-16 2004-04-15 Utilisation d'un objet comme element decoratif

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EP1618228A1 true EP1618228A1 (fr) 2006-01-25

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EP (1) EP1618228A1 (fr)
JP (1) JP2006523772A (fr)
CA (1) CA2522644A1 (fr)
WO (1) WO2004092445A1 (fr)

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WO2004091906A2 (fr) * 2003-04-16 2004-10-28 Ahc Oberflächentechnik Gmbh & Co. Ohg Utilisation d'un objet comme outil de façonnage
DE102005041375A1 (de) * 2005-08-29 2007-03-01 Hansgrohe Ag Verfahren zur Erzeugung dekorativer Oberflächenstrukturen
US9098263B2 (en) * 2007-04-30 2015-08-04 Microsoft Technology Licensing, Llc Database application assembly and preparation
US9153554B2 (en) * 2012-04-22 2015-10-06 Kulicke And Soffa Industries, Inc. Methods of adjusting ultrasonic bonding energy on wire bonding machines
EP2996817B1 (fr) * 2013-05-15 2019-07-03 SRG Global, Inc. Promoteurs d'adhérence organométalliques pour polymères chromés peints
DE102013107347A1 (de) 2013-07-11 2015-01-15 AHC-Oberflächentechnik GmbH Konstruktionselement
US11440270B2 (en) * 2014-04-24 2022-09-13 Teijin Limited Carbon fiber reinforced resin processed product having end surface and method of manufacturing the same
DE102015016495B4 (de) 2015-12-18 2020-11-19 Audi Ag Verfahren zum Herstellen eines Kunststoffbauteils
CN112276806B (zh) * 2020-10-26 2022-02-08 东莞金太阳研磨股份有限公司 一种干湿两用砂纸涂层胶料及其制备方法和应用

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CH1576467A4 (fr) * 1967-11-10 1970-03-13
US3607352A (en) * 1968-11-29 1971-09-21 Enthone Electroless metal plating
GB1313651A (en) * 1969-06-25 1973-04-18 Nat Res Dev Bearing component
US4093693A (en) * 1969-08-11 1978-06-06 Lemelson Jerome H Method for making composite articles
US4510208A (en) * 1983-07-01 1985-04-09 The Dow Chemical Company Duplex metal alloy/polymer compositions
US4643940A (en) * 1984-08-06 1987-02-17 The Dow Chemical Company Low density fiber-reinforced plastic composites
DE4406191A1 (de) * 1994-02-25 1995-09-07 Ks Aluminium Technologie Ag Gleitlagerung
DE19729891B4 (de) * 1997-07-12 2006-12-21 AHC-Oberflächentechnik GmbH & Co. OHG Verfahren zur gezielten Aufrauhung von Kunststoffoberflächen und Vorrichtung zur Ausführung des Verfahrens
DE10212304C1 (de) * 2002-03-20 2003-12-04 Bayer Ag Verfahren zur Herstellung von metallisierten Kunststoffformteilen und deren Verwendung

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WO2004092445A1 (fr) 2004-10-28
CA2522644A1 (fr) 2004-10-28
JP2006523772A (ja) 2006-10-19

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