EP1618228A1 - Use of an object as a decorative component - Google Patents

Use of an object as a decorative component

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Publication number
EP1618228A1
EP1618228A1 EP20040727647 EP04727647A EP1618228A1 EP 1618228 A1 EP1618228 A1 EP 1618228A1 EP 20040727647 EP20040727647 EP 20040727647 EP 04727647 A EP04727647 A EP 04727647A EP 1618228 A1 EP1618228 A1 EP 1618228A1
Authority
EP
European Patent Office
Prior art keywords
use according
characterized
non
metallic
layer
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Withdrawn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
EP20040727647
Other languages
German (de)
French (fr)
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.)
Ahc-Oberflaechentechnik & Co oHG GmbH
AHC OBERFLAECHENTECHNIK GmbH
Ahc-Oberflachentechnik & Co oHG GmbH
Original Assignee
Ahc-Oberflaechentechnik & Co oHG GmbH
AHC OBERFLAECHENTECHNIK GmbH
Ahc-Oberflachentechnik & Co oHG 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 to DE2003117798 priority Critical patent/DE10317798B4/en
Priority to DE102004001613A priority patent/DE102004001613A1/en
Application filed by Ahc-Oberflaechentechnik & Co oHG GmbH, AHC OBERFLAECHENTECHNIK GmbH, Ahc-Oberflachentechnik & Co oHG GmbH filed Critical Ahc-Oberflaechentechnik & Co oHG GmbH
Priority to PCT/IB2004/050460 priority patent/WO2004092445A1/en
Publication of EP1618228A1 publication Critical patent/EP1618228A1/en
Application status is Withdrawn legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained
    • C23C18/165Multilayered product
    • C23C18/1653Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1655Process features
    • C23C18/1662Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2013Pretreatment 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22Roughening, e.g. by etching
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/285Sensitising or activating with tin based compound or composition
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/30Activating or accelerating or sensitising with palladium or other noble metal
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14Electroplating 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
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942Fibers are aligned substantially parallel
    • Y10T428/249945Carbon or carbonaceous fiber
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942Fibers are aligned substantially parallel
    • Y10T428/249946Glass fiber
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544Addition polymer is perhalogenated
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31678Of metal
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31938Polymer of monoethylenically unsaturated hydrocarbon

Abstract

The use of an object is disclosed, the surface of which entirely or partially comprises a composite material made of a non-metallic substrate which contains at least one polymer, and of a metallic layer deposited thereon without an external current supply, and having an adherence of at least 4 N/mm2.

Description

V G erwendungeines egenstandsalsdekorati ves B Auteil

The present invention relates to the use of an object whose surface comprises all or part of a composite material consisting of a polymer having thereon a metallic layer, as a decorative component.

Objects me a surface, comprising a composite material consisting of a polymer having thereon a metallic layer, are known.

In general, there are two different types of such items:

Firstly, those in which at least one metal layer is deposited by an electroless chemical process directly onto the plastic surface. The field of application of such objects is severely limited due to the low adhesion strength of the electrolessly deposited metal layer and is located almost exclusively in the decorative area, such as chrome-plated articles of ABS (acrylic / butadiene / styrene plastics) or polymer blends, in particular as trim, shower heads, grille of automobiles and coffee pots. A further disadvantage is that only a very limited choice of materials is possible, especially as regards the choice of the polymer when certain optical

Effects are to be achieved, such as a stainless steel look, an aluminum look or appearance of a frosted metal surface.

On the other hand, the use of such composites for decorative components, such as casings of mobile telephones, are known in which the metal layer on the plastic surface by vapor deposition of metal on plastic in a vacuum (CVD / PVD method) is prepared. Hereby be closed metallic coatings on non-metallic substrates, such as plastics, applied. Due to the principle of this method has the disadvantage that, firstly, there are no objects with larger dimensions can be manufactured economically on an industrial scale and on the other hand, the metal layers have a maximum thickness of 3 microns. In addition, articles with recesses or cavities are not completely metallised and the metal layer has a very low adhesion strength, so that their use for mechanically stressed objects is not possible. A widespread application of these physical vapor deposition techniques is the coating of

Plastic films, for example for food packaging. As disclosed in DE 198 49 661 A1 to dampen a specific polyester film with aluminum, so that it has a high oxygen barrier, a good gloss and a low coefficient of friction. However, the adhesive strengths of up to 3 N / mm given there should be low, in order to survive in a mechanically stressed, functional application of the metallized film.

In DE 43 12 926 A1 a method for improving the adhesion of dental metal-plastic composite layers is described. For this purpose, a metallic substrate on which a polymer has been applied is irradiated using a special Te-C0 2 laser. If necessary, a coupling agent is also used. fabric substrates metallization of art is not described here.

Also the DE 42 11 712 A1 discloses an irradiation of the surface of a substrate to improve the adhesive strength with an eximer laser. A PET (Polyethylenterephtha- lat) film is then irradiated with this particular laser, to be subsequently vapor-coated with a ferromagnetic metal layer in the context of a PVD process. Such films are among others as an audio or video recording medium use.

For special plastics there is also a method in which the articles to be coated initially swollen with suitable substances and subsequently etched chemically. The adhesive strengths of the applied metal layer on the plastic achieved are not greater than 2 N / mm 2.

A major disadvantage of this process is the significant environmental impact of the two chemical treatment, so that this method can not be used long from an environmental perspective.

A further developed method for the metallization of polyamides, which is based on the principle described above the sources of the surface of the plastic substrate but does not provide for pickling with chrome sulfuric acid, in an article by GD Wolf and F. Fünger "metallized polyamide injection-molded parts", Plastics, 1989, S. 442-447, unveiled. The surface of the amorphous polyamide is treated with an organometallic activator solution. This is followed by a conventional deposition process of a chemical nickel layer.

in this type of surface treatment based on a chemical reaction of the treating solution to the substrate, it is disadvantageous that the swollen surfaces against environmental influences, such as dust inclusions are very sensitive. Furthermore, the polyamide to be treated must be amorphous since partially crystalline or crystalline polyamides are not affected by the proposed method. Thus, this method an expensive and limited usable method is to adhering

to achieve composite layers between the polymeric substrate and metallic layer.

>

The object of the present invention is to provide a decorative member whose surface is wholly or partially a composite material of a plastic and a

comprising metal layer, which overcomes the above-described disadvantages of the prior art and can be produced in an industrial scale.

The object is solved by the use of an object whose surface comprises all or part of a composite material, said composite material consisting of a non-metallic substrate containing at least one polymer, and thereon a metallic layer deposited with an adhesive strength of at least 4 N / mm 2 is composed, as a decorative component.

In a particularly preferred embodiment of the present invention, a

Object as a decorative component used, the surface of which a composite material wholly or partly, said composite material comprising a first non-metallic layer and applied thereto a second metallic layer, and wherein a) is not chemically pre-treated, the surface of the article prior to applying the metallic layer; and b) is not applied, the metallic layer by thermal spraying, CVD, PVD or laser treatment.

Chemical pretreatment is understood here and below as distinct from mechanical treatments any treatment of a substrate surface, which is performed by pickling, etching, sources of vapor deposition, plasma treatment, or similar methods, and in which a change in the surface caused by a chemical reaction ,

The articles used in the present invention, in contrast to the metallized after chemical pre-treatment articles of the prior art in a rough, sharp-edged boundary layer between the non-metallic layer and the electrolessly deposited metallic layer. These sharp-edged projections and undercuts of the boundary layer are clearly recognizable as edged surface contours, for example, in a cross section analysis, the

Embodiment will be described below. Thus, they are from the more round, but in any case rounded to distinguish contours resulting from a chemical pre-treatment (Figure 2). The bond strengths (expressed in N / mm 2) of the novel composite materials based only on the Stirnzugversuchs DIN 50160 provides: The Stirnzugversuch (vertical tensile test) according to DIN 50160 is for years for testing of semiconductors, the determination of the adhesive tensile strength of thermally sprayed coatings and used in various coating technologies.

For the determination of the adhesive strength in the test Stirnzugversuch layer / substrate composite between two test stamps and is glued under uniaxial spacious force until breaking load (see. Figure 1). If the adhesiveness of the adhesive is greater than that of the coating occurs and the breakage between the coating and substrate, it is possible to

equation

F H σ exp - A

Α G

(with σπ exp: experimentally determinable adhesive strength, F max: maximum force at break of the composite and A G: geometric fracture surface), the adhesive strength can be calculated.

In a preferred embodiment, the standard deviation of the adhesive strength at six different points distributed over the surface of the composite measured values ​​of maximum 25% of the arithmetic mean. The specified uniformity of adhesion strength allows the use according to the invention of objects with a composite material as decorative elements in a particular manner. Thus, the articles have an increased suitability for daily use and are so resistant to wear that can be opened up completely new areas of application.

According to another preferred embodiment, an article is used, the composite material has a non-metallic substrate, which is simultaneously the surface of the article. Preferably, these surfaces are based on a polymeric material. As a particularly preferred fiber-reinforced plastics, thermoplastics and other polymers used in industry are to be mentioned.

But equally, it is also possible to use objects whose non-metallic substrate is not the surface of the object. Thus, the object used from a metallic or ceramic material can be made which is coated with a non-metallic substrate containing at least one polymer. Examples include a painted emblem made of aluminum, which is selectively metallized, or a metal casing, which is coated and partially metallized with a powder coating. In a further embodiment of the present invention, an article with a composite material as a decorative component is used which has a boundary present between non-metallic substrate and the metallic layer having a roughness, R z value which does not exceed 35 microns.

The R z value is a measure of the average vertical Oberflächenzerklüflung.

According to a particularly preferred embodiment of the present invention, articles to be used with a composite material as decorative components having a boundary present between the non-metallic substrate and the metallic layer with a roughness expressed by an R a value of at most 5 microns.

The R a value is a measurement technology reproducible measure of the roughness of surfaces, said profile outliers (ie extreme valleys and hills) by the area of integration are largely ignored.

To determine roughness values R a and R z, a sample is taken from an article of the invention and there is made a cross-cut according to the reasonable subsequently led method.

When the cross cut made there is the special problem that the interface between the substrate and the surface can be by machining very quickly destroyed or peeled off. To avoid this, a new cut-off wheel of the company Struer type 33TRE DSA no. 2493 is used at every cross-cut production. In addition, care must be taken that the contact pressure, which is transmitted from the cutting wheel on the substrate coating, is directed such that the force proceeds from the coating in the direction of substrate. In the separation, make sure that the pressure is kept as low as possible.

The test sample (available Epofixkitt, by the company Struer) in a transparent encapsulant. The embedded sample is ground to a grinding table of the company Struer type Knuth-ROTOR-2. Various sandpaper with different grits and silicon carbide are used. The exact sequence is as follows:

During the grinding process, water is used in order to transport the abrasive particles. The tangential force, which occurs at the cross section and is caused by friction, is directed such that the metallic layer is pressed against the non-metallic substrate. Thus, it is effectively prevented that the metallic layer comes off during the grinding process of the nichtmelallischen substrate.

Subsequently, the thus treated sample is polished with a motor-driven preparation machine of the type DAP-A from Struer. In this case, not the usual specimen mover used, but the sample is entirely polished by hand. Depending be polished substrate, a rotational speed between 40 to 60 U / min and a pressing force of 5 to 10 N is applied.

The transverse cut is subsequently subjected to an SEM image. For determining the boundary magnification, the boundary line between the layer of non-metallic substrate and the metallic surface at 10,000-fold magnification is determined. To evaluate the program is used OPTIMAS the company Wilhelm microelectronics. As a result, XY value pairs are determined that describe the boundary line between the substrate and layer. To determine the boundary magnification according to the present invention, a distance of at least 100 microns is required. Here, the course of the boundary line is to determine with at least 10 measurement points per micron. The boundary line magnification determined from the ratio of true length by geometric length. The geometrical length corresponding to the distance of the measurement path, ie between the first and the last measuring point. The true length is the length of the line that passes through all of the recorded measurement points.

The surface roughness value R a is also determined according to the standard DIN 4768 / ISO 4287/1 using the previously recorded XY-value pairs.

According to a further, likewise preferred embodiment of the present invention, 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 microns. In addition, the non-metallic substrate may contain in a further form of the present invention at least one fiber-reinforced polymer, in particular a glass fiber-reinforced polymer, wherein the diameter of the fiber is more than 10 microns.

Provided that the composites are subject to not only thermal stresses but also mechanical be particularly preferably reinforced plastic, in particular carbon fiber reinforced plastics (CFRP), glass fiber reinforced plastics (GRP), also by aramid-reinforced plastics or mineral fiber reinforced plastics. With the use of these items is a high rigidity of the resulting

made components with low weight, which are particularly interesting due to their low cost for industrial applications such as components for cabins of aircraft. In particular, glass fiber reinforced polymers comprise as a component of the non-metallic substrate, the fibers having a diameter greater than 10 microns are very inexpensive and easy to process. The fiber diameter has a great influence on the roughness, so that is achieved with such materials in accordance with the present invention, a roughness value R a of at most 10 microns. At the same time, it is inventively possible to achieve excellent values ​​for adhesion. Moreover, the objects used in the invention to a high uniformity of adhesion. This allows for the first time, to significantly increase the service life of the decorative member. Because even a local delamination of the layered composite leads to a failure of the entire component. Particularly serious is the advantage for components with a surface covered by the laminate surface area of more than 10 dm 2, eg for large components or components with a large surface area.

In a further embodiment, the article described above has a boundary between a non-metallic substrate and the metallic layer having a roughness with an R z value of at most 100 microns. Especially for the use of fiber-reinforced polymers, the fiber thickness is more than 10 .mu.m, it is important to achieve as low as possible, R z values. With this combination it is possible, surprisingly, high bond strength at - in relation to the large fiber diameters used - to achieve low R z values.

The polymer of the non-metallic substrate in a preferred embodiment of the invention selected from the group of polyamide, polyvinyl chloride, polystyrene, epoxy resins, polyether ether ketone, polyoxymethylene, polyformaldehyde, polyacetal, polyurethane, polyether imide, polyphenyl sulphone, polyphenylene sulphide, polyarylamide, polycarbonate and polyimide.

In this embodiment, the metallic layer may have an adhesive strength of at least 12 N / mm 2.

Likewise, the polymer of the non-metallic substrate in another embodiment of the present invention may be made of polypropylene or polytetrafluoroethylene but also selected.

In cases in which the non-metallic layer is either polypropylene and / or polytetrafluoroethylene, adhesive strengths of at least 4 N / mm 2 can be achieved. This represents an excellent value, especially when combined with the high uniformity of adhesion, which previously could not be achieved.

Particularly preferred embodiments of the invention which have a standard deviation of the adhesive strength of six different points distributed over the surface of the layered composite of measured values ​​of at most 25%, in particular more than 15% of the arithmetic mean is. In this way, an even higher mechanical strength of the resulting components is ensured.

According to a further, likewise preferred embodiment of the present invention, the electrolessly deposited metal layer is a metal alloy or metal dispersion layer.

In these ways, articles may be used as decorative components for the first time with a composite material having an excellent adhesion of the metallic layer on the non-metallic substrate. The uniformity of the adhesion of the metallic layer plays an essential role for the suitability of such items as highly stressed components. A targeted selection of the non-metallic substrate and the metallic layer thereon enables a precise adjustment of the property profile of the conditions of the application.

Particular preference is given to the non-metallic substrate of the present invention comparable applied article as electrolessly deposited metal layer is a copper,

Nickel or gold layer is applied. but it can also be a deposited without external metal alloy or metal dispersion layer may be applied, preferably a copper, nickel or gold layer with embedded non-metallic particles. The non-metal particles can have a hardness of more than 1,500 HV and be selected from the group consisting of silicon carbide, corundum, diamond and tetracarbide.

This dispersion layers thus have in addition to the above-described characteristics to other functions, such as wear resistance or surface may wetting of the items used are improved.

Also preferably, the non-metallic particles exhibit friction-reducing properties and may be selected from the group of polytetrafluoroethylene, molybdenum sulphide, cubic boron nitride and tin sulphide.

The objects of the present invention are particularly preferably obtained by using a special method, comprising the steps of: i. the surface of the non-metallic layer is not chemically pretreated before applying the metallic layer; ii. the surface of the non-metallic layer is microstructured in a first step by a blasting agent; iii. the metallic layer is subsequently applied by electroless metal deposition.

To be used as decorative components articles according to the present invention, as a composite material, first a non-metallic substrate containing at least a polymer. For the preparation of the composite material according to the

Invention, the surface of the nonmetallic substrate is microstructured in a first step by a blasting treatment. The method used is described for example in DE 197 29 891 A1. As an abrasive particularly wear-resistant, inorganic particles are used. It is preferable to copper-aluminum oxide or silicon carbide. It has proved advantageous that the blasting agent has a particle size between 30 and 300 microns. There is also described that on the thus roughened surfaces, a metal layer can be applied by means of an electroless metal deposition.

As already expresses the method name is supplied in an electroless metal deposition during the coating process no electric power from the outside but the metal layer is deposited exclusively by a chemical relation. The metallization of non-conductive plastics in a chemically reductive working metal salt solution requires a catalyst at the surface to disturb this metastable equilibrium of the reducing metal bath and deposit on the surface of the catalyst metal. This catalyst consists of noble metal nuclei such as palladium, silver, gold and isolated copper, which are deposited on the plastic surface of an activator. But activation with palladium nuclei is preferred process engineering reasons.

In essence, the activation of the substrate surface takes place in two steps. In a first step, the component is immersed in a colloidal solution (activator). The necessary for metallization, repent ts present in the activator palladium nuclei on the plastic surface are rt adsorbi egg. After the seeding is (tioning Konditu) by rinsing in an alkaline aqueous solution, the dissolved when immersed in the colloidal solution additionally formed Il- tin or tin-IV-oxide hydrate and thereby exposed the palladium seed. After rinsing can be plated with chemical reducing baths or copper-plated.

This is done in a held by a stabilizer in the metastable equilibrium bath containing both the metal salt and the reducing agent. The baths for the nickel or copper deposition have to reduce the metal ions dissolved in them the germs and deposit elemental nickel or copper the property. In the coating, the two reactants must approach the precious germs to the plastic surface. By thus held redox reaction, the conductive layer, wherein the noble metal nuclei thereby absorb the electrons of the reducing agent and they give off when approaching a metal ion again arises. In this reaction, hydrogen is released. After the palladium seeds were coated with nickel or copper, the applied layer takes on the catalytic action. This means that the layer is growing together of the palladium seeds, until it is completely closed.

An example will be discussed at this point to the deposition of nickel. When coating with nickel The seeded and conditioned plastic surface is immersed in a Nickelmetallsalzbad which in a temperature range between 82 ° C and

94 ° C permits a chemical reaction. The electrolyte is generally a weak acid with a pH value that is 4.4 to 4.9.

The deposited thin nickel coatings can be strengthened with an electrolytically deposited metal layer. A coating of components with layer thicknesses> 25 microns due to the low deposition rate of chemical coating processes not economical. Furthermore, only a few coating materials can be deposited with the chemical Beschichtungspro- processes, so it is advantageous to use for other commercially important coating materials in electrolytic processes. Another key point is the different properties of chemically and electrolytically deposited layers with thicknesses> 25 .mu.m, for example, leveling, hardness and gloss. The basics of electrolytic metal deposition are in B. Gaida, "Introduction to Electroplating", EC Leuze-Verlag, SAUL gau, 1988 or H. Simon, M. Thoma, "Applied Surface Technology for metallic materials" C. Hanser-Verlag, Munich (1985). Kunststoffleile having by a electroless coating process an electrically conductive layer, differ only slightly from those of the metals with respect to the electrolytic metallization. Nevertheless, some points in the electrolytic metallization of metallized plastics should not be disregarded. Due to the mostly low Leitschichtstärke the current density at the beginning of electrolytic deposition must be reduced. If this point is not observed, it may become detached and burning the conductive layer. Furthermore, care should be taken that interfering annealing layers are removed with specially suitable for Dekapierbädern. Furthermore, residual stresses can lead to the destruction of the layer. In the deposition of layers of nickel from an ammoniacal bath, for example, tensile stresses in the order of 400 to 500 MPa can occur. By additives such as saccharin and butynediol, a change in the structure of the nickel coatings in the form of a change in grain size and formation of micro deformations may favor the elimination of internal stress, which can have a positive impact on a possible premature failure in the coating.

Examples of electroless deposited metal layers are in the manual of the company

AHC Oberflächentechnik described in detail ( "The AHC surface" Handbook for, design and manufacturing, 4th edition, 1999).

On the metallic layer, one or more layers, in particular metallic, ceramic, and crosslinked or cured polymer layers may be disposed.

Thus, it is for example possible to apply a further electrolytically deposited nickel layer on an electroless deposited nickel layer as a metallic layer of the present invention and then depositing a chromium layer. The electrolytic deposition of the second nickel layer is made to be able to produce greater layer thicknesses inexpensive. Furthermore, the objects of the present invention may have a copper layer as a metallic layer, on which then a further layer of copper may be applied. Then, a gold layer is applied to the existing metal layers, for example. Such coatings may, for example, for the production gilt fittings, for example in plumbing or automotive industry, find their application.

Also, the articles used in the present invention may include a nickel layer as a metallic layer, is introduced listed on another nickel layer. In this way it is possible to achieve high rigidity of the resulting plastic parts, thus ensuring an application for mechanically highly stressed components.

Further metallic layers can be applied to an article with a metallic layer of the present invention, not only electrolytically but also by other methods such as CVD / PVD.

In this way, it is possible to apply aluminum or stainless steel to an article which consists for example of plastic and is provided with a nickel layer according to the present invention.

Another interesting embodiment of an inventive article is a plastic, which is first provided with an electrolessly deposited layer of nickel. In this nickel layer sequentially layers of silver and gold are applied electrolytically subsequently. Overall, the above examples show that the invention

Objects can be used in a very wide range of technical applications.

An object of the present invention may for example be used as housing, container, handle, cover, emblem, holders and trim strip.

Example (according to the invention)

A plate made of polyamide-6 having the dimensions 200 * 100 * 12 mm with a Ausgangsrauhigkeit of R a = 0.64 microns and R z = 7.5 microns was surface-treated: The surface pretreatment is with a modified pressure jet unit from.

Straallechnik International made. The blasting machine is operated at a pressure of 4 bar. As a jet nozzle Borcarbiddüse is used having a diameter of 8 mm. Radiation time is 4.6 s. As an abrasive grit SiC is the P80 having an average grain diameter of 200 to 300 microns. To adapt the blasting system specifically to the requirements of the plastics modification in reproducible surface topographies, two pressure circuits have been installed, one for the transport of the abrasive and the actual acceleration process. This modification resulted in a very constant flow rate and a wide pressure range. An air flow transports the blasting agent with a very small pressure for

Jet. ensure the flow conditions caused by a high volume flow of the blasting agent, and a small amount of compressed air, a low wear of the plant and of the blasting agent. Only at the end of the transport hose in front of the mixing nozzle, the cross section is reduced, to set the desired volume flow. In all plastic pretreatments, a constant flow rate of 1 l / min was given. In the second part of the system flows to the nozzle compressed air (flow 1), the bar can be adjusted continuously in a pressure range of 0.2-7. The blasting medium which is conveyed with a very small flow velocity into the mixing nozzle is then accelerated by the high flow velocity of the air stream.

The thus-roughened plate we .-% butyl glycol treated for five minutes in an ultrasonic bath with a mixture of deionized water and 3 vol.

The Badreihen used for metal deposition of the conductive layer based on the known colloidal palladium activation in conjunction with a final catalysed metal reduction. All Badreihen needed for this were purchased from Max. Schlötter. Specified by the manufacturer diving sequences, treatment times and temperatures were maintained for all process steps of nickel deposition:

(1) Aktivatorvortauchlösung:

Serves to prevent the introduction of impurities and for the complete wetting of the sample prior to the actual activation of the surface. Immersion time: 2 min, room temperature

(2) activator GS 510:

Activation of the surface with tin / palladium colloid. Immersion time: 4 min, room temperature (3) of rinsing steps: deionized water

To avoid the entrainment of activator GS 510 components by rinsing in deionized water. Immersion time: 1 min, room temperature

(4) Conditioner 101: conditioning of the material surface by peeling interfering tin compounds from the surface. Immersion time: 6 min, room temperature

(5) rinsing baths: deionized water. Immersion time: 1 min, room temperature (6a) chemical nickel bath SH 490 LS:

Metallization of the plastics with a bright, semi-bright amorphous layer at a deposition temperature of 88-92 ° C. Dive time: 10 minutes

At the chosen immersion time in the nickel bath a layer thickness of 1, 4 microns resulted. These

Thickness of the nickel layer is sufficient for an electrolytic coating. All process steps which were necessary for the deposition of the conductive layer, were carried out in 50 I-making plastic trays, using a bath temperature of 90 ° ± 0.5 ° C was observed during the entire coating cycle in the nickel deposition by an additional hot plate with temperature control. To obtain a uniform and reproducible coating quality that Badreihen Max Schlötter were, according to the company after a throughput of 20 samples. Analyzed and completed. After the Nickelleitschicht was chemically deposited, the sample of about 90 ° C were cooled to about 60 ° C in distilled water, to be then further coated electrolytically at 55 ° C with nickel. This intermediate step served to the emergence of

To avoid reaction layers and ruled by rapid cooling induced residual stresses. The samples which were coated only with a Nickelleitschicht, cooled in a distilled water bath slowly to 25 ° C.

The cross-cut examination by SEM (1,500-fold and 3,000-fold) in the following

reproduced images (Figure 3). The results of the adhesion tests are shown in Table 1 below.

Table 1

Comparative Example (not of the invention)

The example of the invention is repeated but after blasting treatment

Plate weight in an ultrasonic bath in a suspension of 5 .-% CaC0 3 in 96% Ethanol 5

Minutes treated.

The plate is then treated in a further ultrasonic bath with pure 96% ethanol long for another five minutes. The cross-cut examination by SEM (1,500-fold and 3,000-fold) in the following

reproduced pictures (Figure 4). The evaluation of the EDX analysis showed a residual amount of 0.91 wt .-% of Caicium, the 3 / ethanol suspension comes from the treatment of CaC0.

The results of the adhesion tests are shown in Table 2 below.

The results clearly show a significant difference in the standard deviation of the adhesive strength of the various places distributed over the surface of the composite material

Readings.

This difference caused, for example in the use of door handles of automobiles made of polyamide that in addition to the optical property of the component and the ther- mal resistance to temperature fluctuations for a period of more than

15 years is ensured without locally occurring delamination. LIST OF REFERENCES Figure 1:

(1) Zugstempel

(2) Adhesive

(3) metal layer

(4) Substrate

Claims

P atentanspr ü che
1. Use of an object whose surface comprises all or part of a composite material, said composite material consisting of a non-metallic substrate containing at least one polymer having thereon a metallic layer deposited with an adhesive strength of at least 4 N / mm 2 is composed, as a decorative component.
2. Use according to claim 1, characterized in that said standard deviation of the adhesive strength at six different points distributed over the surface of the composite measured values ​​of maximum 25% of the arithmetic mean.
3. Use according to claim 1 or 2, characterized in that a) is not chemically pre-treated, the surface of the article prior to applying the metallic layer deposited; and b) is not applied, the metallic layer by thermal spraying, CVD, PVD or laser treatment.
4. Use according to any one of claims 1 to 3, characterized in that the non-metallic substrate is the surface of the article.
5. Use according to any one of claims 1 to 3, characterized in that the non-metallic substrate is not the surface of the article.
6. Use according to one of the preceding claims, characterized in that the boundary present between the non-metallic substrate and the metallic layer exhibits a roughness with an R z value of at most 35 microns.
7. Use according to one of the preceding claims, characterized in that the boundary present between the non-metallic substrate and the metallic layer exhibits a roughness with an R a value of maximum 5 microns.
8. Use according to one of the preceding claims, characterized in that the non-metallic substrate, at least one fiber-reinforced polymer, in particular a carbon fiber-reinforced polymer, and the diameter of the fiber is less than 10 microns.
9. Use according to any one of claims 1 to 5, characterized in that the non-metallic substrate, at least one fiber-reinforced polymer, in particular a glass fiber-reinforced polymer, and the diameter of the fiber is more than 10 microns.
10. Use according to claim 9, characterized in that the boundary present between the non-metallic substrate and the metallic layer exhibits a roughness with an R a value of maximum 10 microns.
11. Use according to one of claims 9 or 10, characterized in that the boundary present between the non-metallic substrate and the metallic layer exhibits a roughness with an R z value of at most 100 microns.
12. Use according to any one of the preceding claims, characterized in that the polymer is selected from the group of polyamide, polyvinyl chloride, polystyrene, epoxy resins, polyether ether ketone, polyoxymethylene, polyformaldehyde, polyacetal, polyurethane, polyether imide, polyphenyl sulphone, polyphenylene sulphide, polyarylamide, polycarbonate and polyimide ,
13. Use according to claim 12, characterized in that the metallic layer has an adhesive strength of at least 12 N / mm 2.
14. Use according to any one of claims 1 to 11, characterized in that the non-metallic substrate is polypropylene or polytetrafluoroethylene.
15. Use according to any one of the preceding claims, characterized in that the standard deviation of the adhesive strength is at most 25%, especially more than 15% of the arithmetic mean.
16. Use according to any one of the preceding claims, characterized in that the electrolessly deposited metal layer is a metal alloy or metal dispersion layer.
17. Use according to any one of the preceding claims, characterized in that the electrolessly deposited metal layer is a copper, nickel or gold layer.
18. Use according to any one of the preceding claims, characterized in that the electrolessly deposited metal dispersion layer is a copper, nickel or gold layer with embedded non-metallic particles.
19. Use according to claim 18, characterized in that the non-metallic particles exhibit a hardness of more than 1,500 HV and are selected from the group consisting of silicon carbide, corundum, diamond and tetracarbide.
20. Use according to claim 18 or 19, characterized in that the non-metallic particles exhibit friction-reducing properties and are selected from the group of polytetrafluoroethylene, molybdenum sulphide, cubic boron nitride and tin sulphide.
21. Use according to any one of the preceding claims as a housing, vessel, handle, cover, emblem, holders and trim strip.
EP20040727647 2003-04-16 2004-04-15 Use of an object as a decorative component Withdrawn EP1618228A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE2003117798 DE10317798B4 (en) 2003-04-16 2003-04-16 A process for producing a decorative structure
DE102004001613A DE102004001613A1 (en) 2004-01-09 2004-01-09 The use of an object as a shaping tool having a surface consisting in whole or in part of a composite material made of a nonmetallic substrate useful
PCT/IB2004/050460 WO2004092445A1 (en) 2003-04-16 2004-04-15 Use of an object as a decorative component

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DE102005041375A1 (en) * 2005-08-29 2007-03-01 Hansgrohe Ag Method of producing decorative surface structures or patterns on objects of decorative layer on sanitary involves metal layer, partial removal of this, e.g. by electromagnetic radiation, and deposition toned down surface structure
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
EP2996817A4 (en) * 2013-05-15 2017-10-18 SRG Global, Inc. Organometallic adhesion promoters for paint-over-chrome plated polymers
DE102013107347A1 (en) 2013-07-11 2015-01-15 AHC-Oberflächentechnik GmbH design element
DE102015016495A1 (en) 2015-12-18 2017-06-22 Audi Ag A method of manufacturing a plastic component

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CH1576467A4 (en) * 1967-11-10 1970-03-13
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GB1313651A (en) * 1969-06-25 1973-04-18 Nat Res Dev Bearing component
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