EP1989341A2

EP1989341A2 - Metallized composite material

Info

Publication number: EP1989341A2
Application number: EP07704100A
Authority: EP
Inventors: Hartmut Sauer
Original assignee: AHC Oberflaechenechnik GmbH
Current assignee: Aalberts Surface Technologies GmbH Kerpen
Priority date: 2006-01-23
Filing date: 2007-01-23
Publication date: 2008-11-12
Also published as: DE102006003331A1; WO2007082961A3; WO2007082961A2

Abstract

Disclosed is a multilayer compound which is composed of a composite material and a metal layer or metal dispersion layer that is electrolessly applied thereto. The composite material contains 10 to 70 percent by volume of one or several inorganic materials and 30 to 90 percent by volume of one or several polymers or comprises a high temperature-resistant polymer while the surface of the composite material is plasma-modified in the presence of oxygen, and an electrolessly applied metal layer, metal alloy layer, metal dispersion layer, or metal alloy dispersion layer is deposited on the plasma-modified surface of the substrate. Also disclosed are a method for producing said multilayer compound as well as the use thereof.

Description

M e t a l l i s e r t e r V e r b u n d w e r k s t o f f

The present invention relates to a multilayer composite composed of a composite material and a metal layer applied with no external current, a process for its production and its use

The electroless metallization of plastics on their surface for decorative purposes but also for functional purposes has long been known

It has been found that due to the very different properties of the plastics on the one hand and the applied metal layer on the other hand, only a slight adhesion of the metallization can be achieved. To improve adhesion, numerous approaches have been developed to the positive effects of metallized plastics such as for example weight reduction at the same To achieve strength and improved corrosion resistance for the components. Among other things, adhesion promoters are used or the plastic surfaces are pretreated by wet-chemical methods

Adhesion promoters (primers) are substances that improve the adhesion between two phases, eg a substrate and a coating. The effect of adhesion promoters is based on the fact that they build with both phases sufficiently strong non-polar, polar or covalent bonds that are stronger than the ones Bonds of the two phases to each other Die

Use of primers in combination with a plasma cleaning or plasma

Activation method offers optimal possibilities for the connection of two phases, in particular for the permanent activation of a surface

The surface treatment of plastics (polymers, thermosets, thermoplastics, elastomers, thermoplastic elastomers, silicone, rubber, rubber) with the help of low-pressure plasmas also significantly improves the adhesion of liquids, solvents and adhesives to the surface of these materials more adherent surfaces, so that without adhesion promoters adhesion improvement occurs

A surface is cleaned by the ion bombardment physically and depending on the type of gas, also by chemical reactions The pollution is converted into the gas phase and sucked off (plasma cleaning) The etching effect (chemical and physical etching) refers to the fact that during plasma cleaning the surface of the treated workpiece is removed. Impurities and contaminations on the surface are thus removed. However, this plasma etching is effective only at the outermost surface layer (a few atomic layers). With a longer duration of treatment, a larger part of the boundary layer can be removed successively. In many cases, plasmas can replace wet-chemical etching, so plasma systems can be used as etchers. When used together with an etching mask, the etching can also lead to the (micro) structuring of surfaces.

In most cases, the plasma treatment is a pre-treatment for subsequent processes such as painting, gluing, soldering, etc.

It is known from the article "Adhesion Promotion of Metals Electrolessly Deposited on Inorganic Materials" by E. Touchais-Papet et al., Proceedings of the 22 ^nd Annual Meeting of the Adhesion Society, p. 48 - 51 (1999), glass or carbon The plasma modification of the glass surfaces is performed using methane and ammonia to deposit an amorphous hydrogenated carbon film on the glass surface, then these special surfaces are activated with palladium and de-energized by known techniques coated with a nickel / phosphorus alloy The resulting coatings have a bond strength of at most 4 N / mm ² .

The following scientific publications also report the performance of activation experiments using a plasma treatment for specific plastics materials and show their results:

Although in the publication "Interests of NH ₃ and N ₂ plasma for Polymers Surface Treatment Before Electroless Metallization" plasma and Polymers, Vol. 1, No. 2, 1996, pages 1 13-126, M. ALAMI, M. CHARBONNIER, and M. ROMAND proposes to use a plasma treatment as described for other polymers as well, the practical examples remain limited to the amorphous polystryroles, polycarbonates and polyamides. However, these polymers are of little interest to the electronics industry, for example, since they do not show sufficient temperature resistance and, in the case of polyamides, a high tendency to absorb water (ie to swell).

The documents "Plasma Chemical Modification of Polycarbonate Surfaces for Electroless Plating", J. Adhesion, Vol. 57, Pages 77-90, M. ALAMI, M. CHARBONNIER, and M. ROMAND; "Surface plasma functionalization of polycarbonate: Application to electroless nickel and copper plating "M. Charbonnier, M. Romand, E. Harry, M. Alami; Journal of applied electrochemistry, January 2001, Volume 31, No. 1, pp. 57-63;" Electroless Plating of polymers: XPS study of the initiation mechanisms, "M. CHARBONNIER, M. ALAMI and M. ROMAND, Journal of Applied Electrochemistry, April 1998, Volume 28, No. 4, pages 449-453, include studies on the details and mechanisms of plasma treatment of polycarbonates and however, these materials have not been significantly used in the fields of electronics and functional components because of their poor heat resistance, electrical insulation performance, industrial processability and mechanical strength properties.

On the other hand, in the electronics industry for electronic circuits and interconnections, preferred are plastics exhibiting high heat stability, such as semi-crystalline or liquid-crystalline polymers, especially polyesters, polybutyl terephthalate (PBT), polyphenylene sulfide (PPS) or syndiotactic polystyrenes.

However, these plastics are known for their great indifference to chemical treatments in preparation for subsequent metallization. This indifference is even greater in semi-crystalline plastics, so that the attempts to metallize these high-temperature resistant materials were very limited.

The investigations in "Plasma Treatment Process for Palladium Chemisorption onto Polymers before Electroless Deposition", Charbonnier, M .; Alami, M .; Romand, M., Journal of the Electrochemical Society, 1996, Vol. 143, no. 2, pp. 472-480, for amorphous polystyrene describe the same results as before for polycarbonate. In addition, the authors report for the metallization of this material that the maximum achievable thickness of the deposited metal layer is less than 2 microns. An employment of these metallized plastics in industrial environment is excluded against this background, since metal layers with a thickness of 20 microns and more are often needed there.

Furthermore, the experiments presented in the publications on the plasma activation of plastics transferred to the industrially applicable high-temperature-resistant polymers already on a laboratory scale bad or at least not reproducible results. Thus, the use of industrial electrolyte baths little or no deposition on the method according to the presented method plasma-pretreated polymers. In addition, the fact that the industrially used plastics are often mixed with additives such as fillers and (glass) fibers, their indifference to the different activation methods is still increasing This also makes the low transferability of studies and experiments from the cited scientific Explain articles

Based on these studies, further adjustments have been proposed for the pretreatment of the surfaces of high temperature plastics

WO Publications WO 03/105548 A1 and WO 03/104526 A1 disclose a process or the product obtainable therefrom for the electronics industry, in which a high-temperature-stable polymer is coated with a conventional electrolessly deposited metal layer after a plasma pretreatment with a nitrogen-containing gas after palladium activation the necessary for electrochemical metallization palladium we bonded through a PdN _x -Bιndung to the polymer surface

A plasma activation with an oxygen-containing gas is not required for this purpose. A significant problem with the plasma-activated surfaces is the electroless metal deposition. The resulting coatings have partial areas where a smaller metal layer deposited without electroless has been deposited Therefore, this process is not suitable for industrially produced large numbers of pieces of work, especially not for workpieces with a large surface, such as rollers in the printing industry Moreover, it is not without further not possible, an industrially introduced

To use the metalization process In order for the metallization process to lead to a visually appealing coating, it is necessary to sensitize the electrolyte specifically by adding additives or by using metal sheets (eg nickel sheets in electroless copper plating). However, the stability of the bath is reduced, resulting in a In addition, this increased sensitization involves the risk that the bath will decompose spontaneously

Furthermore, the resulting metal layers have an adhesive strength generally between 1 to 2, but not more than 4 N / mm ^2. In view of the increased requirements, for example in the aerospace industry, such adhesive strengths are inadequate, especially for functional workpieces The plasma-etched surfaces were examined by the XPS measurement method to determine the change in the chemical composition on the surface. The results show a marked change in the concentration of the chemical elements on the surface. After the plasma cleavage, a decrease in the carbon and oxygen content and an increase The increase in nitrogen content at the surface is due to the incorporation of the plasma gas nitrogen, in accordance with the results of M Charbonnier and A Fares-Karam

The object of the present invention is to provide a multi-layer composite with an electrolessly deposited metal layer on a composite material, in which the metal layer has an adhesive strength of more than 8 N / mm ² , without the surface being mechanically or wet-chemically altered, without being interposed between the surface Furthermore, the multi-layer composite should have the property that the metal layer deposited externally in the zone to be metallized is closed

A further object is to provide a method for producing such a multi-layer composite, which also ensures a reproducible and stable process on an industrial scale in terms of size and quantity of the products

The first object of the present invention is achieved by a multilayer composite composed of a composite material and a metal or metal dispersion layer applied thereon without external current, wherein

The composite contains 10 to 70% by volume of one or more inorganic materials and 30 to 90% by volume of one or more polymers, or comprises a high-temperature-resistant polymer,

• the surface of the composite is plasma-modified in the presence of oxygen, and

An electrolessly deposited metal, metal alloy, metal dispersion or metal alloy dispersion layer is deposited on the plasma-modified surface of the substrate

A composite material is a construction material that consists of two or more different materials, eg fibers, plastic, metal, ceramics. At least one component (eg fibers) is embedded in the basic structure (matrix) tries to combine the different advantages of the individual materials in the final material and to exclude their disadvantages

The term hochtemperaturbestandiges polymer such thermosetting plastics are understood herein, which have a use temperature of a larger 150 ⁰ C and thermoplastics which have a melting point greater than 1 50 ° C have are preferably those polymers which melt at a temperature of great 200 ⁰ C. Particular preference is given to using PBT (polybutylene terephthalate), LCP (liquid crystalne polymer), PPS (polyphenylene sulfide) and syndiotactic polystyrenes (SPS)

The generic term fillers are, for example, reinforcing and non-reinforcing

Fillers, inorganic (minerals and silicas) and organic fillers and carbon black summarized

Preferred examples of inorganic or organic material which may be present in a composite material of the present invention are carbon blacks, aluminum hydroxide (hydrate), aluminum silicate kaolin, antimony oxide, calcium sulfate, calcium silicate, silicic acid, calcium sulfate clays, calcium carbonate chalk, calcium oxide, Mg alumina. Sιlkat talc, titanium dioxide, lead oxides and fibers

As plasma is called in physics an ionized gas differences are high and low pressure plasmas high-pressure or high temperature plasmas - known for example from plasma welding - reach temperatures of several thousand degrees 100 ⁰ C The surface cleaning in low-pressure plasma plants takes place at a negative pressure of 0.1 to 2 mbar The vacuum chamber of corresponding plants is filled with a process gas For this noble gases, fluorine-containing gases and especially oxygen are used An electric field in the form of high-frequency voltages in kHz, MHz - (radio frequency) or GHz range (microwave) transfers energy into the system and accelerates free charge carriers, which ionize gas particles by collision. As process gas, mostly oxygen (oxidative processes) is used such as O ₂ -Radιkale that are able to break up hydrocarbon chains and to oxidize carbon dioxide and water vapor on this chemical reaction based the cleaning effect of the plasma Organic impurities are converted into volatile (gaseous) reaction products In addition to oxygen are preferably argon, helium, hydrogen , Nitrogen and tetrafluoromethane used as process gases In the multi-layer composite according to the invention, such excellent adhesion of the metallic layer to the surface of the composite is achieved that functional and mechanically stressed components can now also have a multi-layer composite according to the invention. The observed jump in the adhesion of the multi-layer composite according to the invention over the previously known electrolessly metallized plastic materials is thereby so great that only a surprising synergistic effect can be responsible for the strong increase in the adhesion of the metal layer. However, it has not yet been possible to clarify the binding effect on which this above-average increase can be attributed

At present, therefore, further investigations and analyzes are carried out in order to find a scientific explanation for the observed properties. Printed in absolute numbers, the systems of metallized amorphous polymers presented by the Charbonnier working group have an adhesion of about 1-2 N / mm ² , measured with the so-called Stirnzugversuch, which in the einschlagigen

Literature describe well, however, such low bond strengths were found for some of the featured metallization, the metal layer is reapplied already taped (see Scotch ^® -Tape tests) For the hochtemperaturbestandigen systems in the international patent applications WO 03/105548 A1 and WO 03/104526 A1 describes adhesion values of greater than 1 N / mm ² and greater than 2 N / mm ²

In contrast, the multi-layer composite according to the invention achieves adhesion strengths of more than 8 N / mm ^2. A detachment of the metal layer from the composite material is not observed

As already explained above, the mechanisms underlying the surprising increase in the adhesion of the metallic layer are not yet understood. First, the plasma activation process is based on many parameters interacting with each other. Thus, it has already been found that the energy input into and to the activates In this regard, the volume flow of the process gas, the performance of the plasma furnace and the duration of treatment are of particular importance and must be strictly controlled and coordinated depending on the amount of parts to be treated

Related to the use of a plasma furnace of the type "NANO" Diener with a

Maximum performance of 300 W, the following parameters have been found to be particularly advantageous 1 Sample Plättchen the large 60 x 40 x 2 mm from a filled with 65% by weight mineral plastic is at a working pressure of oxygen process gas of 0.2 mbar for 20 minutes treated Here, the sample is heated to a temperature above 60 ⁰ C, preferably about 75 ⁰ C and especially above 80 ⁰ C. With this arrangement shows that a shortening of the treatment tent degraded results leads as well as a greater change in oxygen pressure

According to a preferred embodiment of the invention, the composite material contains 20-65% by volume of one or more inorganic materials

The electrolessly deposited metal may be copper, nickel, silver or gold

By choosing different metals that can be applied in an electroless process, opens up a very wide range of applications for erfmdungsgemaßen multilayer composite Certainly, the metals copper and nickel will be of particular interest in the electronics industry to selectively produce printed circuits and traces on the other hand but according to the invention but also the much more expensive metals silver or gold can be applied directly to the surface to be metallized without external power and firmly adhering, which can be used, for example, in medical technology or for shielding electromagnetic waves

According to a further preferred embodiment of the present invention, the polymer in the multi-layer composite according to the invention is a sprayable polymer

This characteristic makes it clear that the invention is also suitable for components which are industrially manufactured on a large scale and in high numbers. As already noted in the light of the above assessment of the scientific work of the M Charbonnier working group, this aspect is surprising. If the known plasma methods are considered, it is precisely the active and heat-resistant polymers, which moreover can also be mixed with fillers and fibers, that have hitherto caused the greatest difficulties in the production of a multi-layer composite

Only with the multi-layer composite according to the invention is it possible to achieve a sufficiently high adhesion of the metal layer to the composite material that even functional components which are exposed to a certain mechanical stress can be constructed from such a multilayer composite

The polymer may be selected from the group of PPS (polyphenylsulfone), PES (polyethersulfone), PEI (Polyetheπmid) PA (Polyamιd), PE (polyester), polyethylene, PS (polystyrene), PU (Polyurethane), PC (Polycarbonate), PTFE (Polytetrafluoroethylene), Epoxy resins, Phenolic resins and LCP (liquid crystal polymers)

Depending on the field of application, the polymer which best meets the requirements is selected. For example, if only polymers which have a high temperature resistance can be used, the person skilled in the art will certainly use a PPS or a syndiotactic polystyrene or an LCP. Conversely, the use of epoxy resins can also be used be beneficial for another area

The inorganic material, which forms the composite material in the multilayer composite according to the invention in admixture with the polymer, may be in the form of a fiber and / or sphere

Preferred fillers for composite materials in the inventive multi-layer construction are, in particular glass fibers and inorganic fillers such as rock dust, mica, zeolites, gypsum, natural silicates, such as quartz, kaolin, talc, precipitated and fumed silicas (Ultrasil ^®, Vulkasil ^®, Aerosil ^®), corundum, aluminum hydroxide , Carbonates, oxides and carbides

These fillers are very widespread in industrial use because they give the composites in a cost effective manner high flexural strength and resistance to mechanical deformation. In addition, they offer further advantages such as flame retardancy

Most preferably, the inorganic material is a glass fiber

Glass fibers are long, thin fibers made of glass Glass fibers are used in glass fiber cables for data transmission, or as textile fibers for heat and sound insulation and for glass fiber reinforced plastics Glass reinforced plastics can be plasma-treated in such a way that the fibers are exposed

Glass fiber-reinforced plastics with an adhesive electroless metallization offer high rigidity and strength at low weight A very good corrosion resistance and insensitivity to weathering make these novel multilayer composites particularly suitable for applications in the automotive industry as an external attachment and in aerospace engineering

The inorganic material may also be a mineral fiber In this further embodiment can be addressed by the selection of mineral fibers as a filler in the composite material on very specific requirements (such as lesser distortion during cooling of the plastic parts in the injection mold)

Particularly preferred is the entire substrate of a glass fiber reinforced plastic as a composite material

In this way, a high property profile (based on high elasticity, low weight, corrosion resistance, Chemikahenbe steadiness, good heat and noise insulation etc) can be awarded to the entire composite material

The inorganic material can be selected in a further preferred embodiment of the present invention from the group of silica, Banumsulfat, glass, clay, titanium dioxide and layered Hats Depending on the application, the various fillers are selected to the lent advantages of the individual materials in the final material combine and vice versa to exclude their disadvantages

In a preferred embodiment, the composite material in a multi-layer composite according to the invention can be composed of various metallic or non-metallic layers and the electroless metallized surface contains 10% to 70% by volume of one or more inorganic materials and 30% to 90% by volume of one or more polymers Thus, complex components of the invention are also accessible, as long as they have on their surface completely or partially a composite material having the stated characteristics, the invention plasma-etched and then metallized to form a multi-layer composite

The second object of the present invention is achieved by a process for producing a multilayer composite composed of a composite material and a metal or metal dispersion layer applied thereon without external current, the composite material comprising 10 to 70% by volume of one or more inorganic materials and 30 to 90% by volume of a or more polymers or comprises a high-temperature-resistant polymer, and characterized by the steps a) plasma etching of the composite in the presence of oxygen, b) immersion of the workpiece in a palladium-containing solution c) immersion of the workpiece in an electrolytic solution for electroless metallization For the first time with the method according to the invention, it is also possible to work in large metallizing tanks. This achieves a breakthrough towards an industrially applicable method with which even large numbers of pieces can be produced in a short time.

In contrast to the previously known methods for plasma activation of plastic surfaces of the type defined above, the process of the invention surprisingly achieves a very high degree of nucleation in the palladium nucleation following the plasma clot. Although the literature known achieve a certain, albeit small Bekeimung with palladium ions or palladium (0), it is still not sufficient to subsequently generate a closed and satisfactory metallization reproducible with conventionally used Metallisierungsbadern. Rather, it has hitherto required metallizing baths which had to be highly sensitized, for example by suspending a metal sheet or sharpening the copper deposition bath immediately before the actual deposition process.

The particularly high degree of nucleation with palladium ions or palladium (0) according to the method according to the invention makes it possible for the first time to use industrial and normally stabilized metallization baths which have a large volume and a long service life associated with a high piece throughput.

In a particularly preferred form of the present inventive method, the plasma etching is carried out with an oxygen-containing process gas volume flow for the production of the plasma of at least 20 sccm and at most of 400 sccm. With a lower flow rate of the process gas than 20 sccm, there are no longer enough gas particles in the plasma chamber to allow a sufficient number of plasma

Ions can be generated. Thus, plasma etching of the composite would fail and not enough reaction sites could be formed to ensure good palladium nucleation. On the other hand, the optimum range is also limited to the top. If the volume of process gas is too high, the individual ionized particles no longer receive enough energy to optimally attack and etch the surface of the composite material.

During the plasma etching, the pressure in the plasma chamber is preferably less than 0.25 mbar, preferably less than 0.2 mbar

In the method according to the invention, the chamber pressure in the plasma chamber during plasma etching in the presence of oxygen is an essential variable in the invention. Experiments have shown that at a pressure of 0.3 mbar no adequate Plasmaatzung takes place to the surface of the composite material for the subsequent external powerless

Prepare metallization so that a firm metallization is possible

Only from a pressure of 0.25 mbar and below is a erfmdungsgemaße

Plasma etching instead, which allows a sufficient pretreatment, followed by a good seeding with palladium ions or with Palladιum (O) -Partιkeln and thus closed, firmly adhering metal layers

At a pressure of 0.2 mbar and below, a particularly good plasma etching of the surface of the composite material and an associated excellent adhesion of the resulting metal layer can be determined according to the attempts of the applicants

In a further likewise preferred embodiment of the invention

Process reaches the temperature of the workpiece during the plasma etching at the

Surface at least 55 ° C

The temperature of the surface of the workpiece is an easy-to-determine control size to ensure that the plasma etching process step

Plasma is generated with sufficiently high energy, so that optimal etching of the

Surface is achieved

Below the threshold of 55 ° C for the temperature of the workpiece is an optimal

Plasma cats no longer guaranteed

The erfmdungsgemaße plasma etching process step lasts between 1 mm and 30

Mm, preferably between 15 μm and 20 μm

From a duration of 1 minute of plasma etching, a suitable surface activation is to be observed for small pieces to be individually etched in a small plasma chamber. Overall, the duration of the plasma etching depends on several factors, such as the total surface area to be etched, the size and geometry of the plasma chamber and the

Number of simultaneously struck pieces

In further experiments it was found that for a reasonable industrial application of the inventive method with many parts that are etched simultaneously, a duration of plasma etching of 10 minutes usually not sufficient

Metallization received only insufficient layers

Only from a duration of 15 mm are good results in the following

Achieved metallization that meet the industrial requirements

The Plasmaatzen is particularly preferably carried out at a power of 300 watts

In a further embodiment of the method according to the invention, a gas which contains at least 2% by volume of oxygen is used as the process gas in the plasama process Only the presence of oxygen in the process step of plasma etching in the process according to the invention results in closed and firmly adhering layers being deposited in the subsequent electroless metallization. The plasma-ionized oxygen molecules are responsible for the surprising effect of the excellent surface activation with respect to the subsequent palladium nucleation Responsible Because currently too little data could be collected, which allowed a scientific explanation of this effect, the exact role of the oxygen molecules in the inventive method can not be conclusively explained

The source of oxygen in the process gas used is not critical. In particular, it is also possible to work with air or with pure oxygen gas

The process gas can also be varied during the plasma etching. It is possible, for example, for a gas with a high oxygen content to be used as process gas at the beginning of the plasma etching and for a process gas with a lower oxygen content or no oxygen content to be used at the end of the plasma etching

In a further embodiment of the method according to the invention, no laser pretreatment of the surface of the composite material is performed. This avoids superficial imperfections in the composite material due to too long or too high-energy laser radiation

The surface of the composite is preferably not etched wet-chemically

In contrast to plasma etching, the etching of the surface in a wet-chemical method occurs by immersion in a liquid solution. Further steps are therefore necessary, which are aimed at removing the residues of this solution from the surface before the palladium is sealed Atzen the disadvantage that the partially highly reactive and therefore highly polluting chemicals may be handled only under great safety regulations and consuming complicated disposal after use Some of the previously preferred wet chemical substances are now also prohibited due to the stricter regulations completely Another aspect that speaks against a wet chemical etching is the danger that the

Composite material absorb water or solvent and swell uncontrollably on its surface An exact dimensional accuracy is thus no longer given The surface of the composite is preferably not roughened by radiation. Mechanical-abrasive methods always run the risk of damaging the surface of the workpiece more than intended.

Furthermore, the uniform removal and roughening in cavities and undercuts is difficult to achieve

In the method according to the invention, it is particularly preferred that no PVD or CVD layer is applied before step b).

Coating methods (PVD method) with which metals, alloys or chemical compounds are deposited by supplying thermal energy or by particle bombardment in a high vacuum, i. the Beschichtungsmateπal is transferred in various ways from a solid in the vapor phase and then condensed on a substrate surface to the PVD method count nor ion plating and sputtering (Sputteπng). For the realization of PVD systems vacuum systems are necessary for the production of high vacuum pressures <10-5 mbar.

A multilayer composite according to the invention can be used in the electronics industry, as a decorative element of a component, in the automotive industry, or in the aerospace industry. A preferred example of a use is the use as high-gloss handles in an aircraft or automobile.

The following figures show a FORTRON 6165 A4 sample plasma etched and metallised under different conditions, whereby only the first three tests showed a surface temperature of more than 55 ° when removed from the plasma furnace (type NANO from Diener)

Figure 1 shows a sample plate made of glass and mineral fiber reinforced PPS (Fortron ^® 6165A4) with the dimensions 60 * 40 * 2 mm, chemical copper plating (5 microns), pre-treatment in a plasma furnace (NANO Fa. Servant) at a reactor pressure during the plasma treatment of 0.2 mbar for a period of 20 minutes using the reaction gas oxygen at 200 sccm

The deposited metal layer is closed. The picture shows the sample after a cross hatch test. Both on the tape and on the sample no detachment can be seen (Gt 0).

Figure 2 shows a sample plate made of glass and mineral fiber reinforced PPS (Fortron ^® 6165A4) with the dimensions 60 * 40 * 2 mm, chemical Nickeibeschichtung (5 microns), Pretreatment in a plasma oven (NANO Fa Diener) at a reactor pressure during the plasma treatment of 0.2 mbar for a period of 20 minutes using the reaction gas oxygen at 200 sccm

The deposited metal layer is closed. The picture shows the sample after a lattice cut test. No delamination is visible on the adhesive tape or on the sample (Gt 0)

Figure 3 shows a sample plate made of glass and mineralfaserverstarktem PPS (Fortron ^® 6165A4) with the dimensions 60 * 40 * 2 mm, chemical Nickeibeschichtung (5 microns), pre-treatment in a plasma furnace (NANO Fa servant) at a reactor pressure during the plasma treatment of 0.3 mbar for a period of 20 minutes using the reaction gas oxygen at 200 sccm

The deposited metal layer is closed The picture shows the sample after a lattice cut test Both the tape and the sample show complete detachment (Gt 5)

Figure 4 shows a sample plate of glass and mineralfaserverstarktem PPS (Fortron ^® 6165A4) with the dimensions 60 * 40 * 2 mm, chemical Nickeibeschichtung (5 microns), pretreatment in a plasma oven (NANO the Fa Diener) at a reactor pressure during the plasma treatment of 0.3 mbar for a period of 5 minutes using the reaction gas nitrogen at 200 sccm

The deposited metal layer is not closed The strips show that almost no metal deposition took place A crosshatch test could not be carried out

Figure 5 shows a sample plate made of glass and mineralfaserverstarktem PPS (Fortron ^® 6165A4) with the dimensions 60 * 40 * 2 mm, chemical Nickeibeschichtung (5 microns), pre-treatment in a plasma furnace (NANO Fa servant) at a reactor pressure during the plasma treatment of 0.3 mbar for a period of 5 minutes using the reaction gas oxygen at 200 sccm

The deposited metal layer is not closed The stripes show that almost no metal deposition took place. Em cross-cut test could not be carried out

Figure 6 shows a sample plate made of glass and mineralfaserverstarktem PPS (Fortron ^®

6165A4) with the dimensions 60 * 40 * 2 mm, chemical nickel coating (5 μm), pretreatment in a plasma oven (NANO from Diener) under a reactor pressure during the plasma treatment of 0.3 mbar for a period of 1 minute Use of the reaction gas oxygen at 200 sccm. The deposited metal layer is not closed A cross-hatch test showed extensive detachment (Gt 5).

Figure 7 shows a sample plate made of glass and mineral fiber reinforced PPS (Fortron ^® 6165A4) with the dimensions 60 * 40 * 2 mm, chemical Nickeibeschichtung (5 microns), pre-treatment in a plasma furnace (NANO Fa. Servant) at a reactor pressure during the plasma treatment of 0.3 mbar for a period of 1 minute using the reaction gas nitrogen at 200 sccm

The deposited metal layer is not closed. The picture shows the sample after a crosshatch test. A crosshatch test could not be performed

Claims

Patent claims

1.) Multilayer composite of a composite material and a powerless applied metal or metal dispersion layer, characterized in that

The composite contains 10 to 70% by volume of one or more inorganic materials and 30 to 90% by volume of one or more polymers or comprises a high-temperature-resistant polymer,

The surface of the composite is plasma etched in the presence of oxygen and

An electrolessly deposited metal, metal alloy, metal dispersion or metal alloy dispersion layer is deposited on the plasma-etched surface of the substrate.

2.) multi-layer composite according to claim 1, characterized in that the composite material 20 - contains 65 vol .-% of one or more inorganic materials.

3.) multilayer composite according to one of claims 1 or 2, characterized in that the externally electroless deposited metal is Cu, Ni, Ag or Au.

4.) multilayer composite according to one of the preceding claims, characterized in that the polymer is a sprayable polymer.

5.) multilayer composite according to one of the preceding claims, characterized in that the polymer is selected from the group of PR3 (Rolyphenylsulfon), PES (Rolyethersulfon), PB (Rolyetherimid) PA (Rolyamide), PE (polyester), Rolyethylene, PS ( Polystyrene), PU (polyurethane), PC (rolycarbonate), PTFE (rolytetrafluoroethylene), epoxy resins, phenolic resins and LCP (liquid crystal polymers).

6.) multilayer composite according to one of the preceding claims, characterized in that the inorganic material is in the form of a fiber and / or ball.

7.) multilayer composite according to one of the preceding claims, characterized in that the inorganic material is a glass fiber.

8.) multilayer composite according to one of the preceding claims, characterized in that the inorganic material is a mineral fiber.

9.) multilayer composite according to one of the preceding claims, characterized in that the substrate is a glass fiber reinforced plastic.

10.) multilayer composite according to one of the preceding claims, characterized in that the inorganic material is selected from the group of silicon dioxide, barium sulfate, glass, clay, titanium dioxide and layer silicate.

1 1.) multi-layer composite according to one of the preceding claims, characterized in that the composite material of different metallic or non-metallic layers is constructed and electroless metallized surface 10 - 70 vol .-% of one or more inorganic materials and 30 - 90 vol. -% of one or more polymers.

12.) A process for producing a multilayer composite of a composite material and a metal or metal dispersion layer applied externally thereon, wherein the composite material contains 10 to 70% by volume of one or more inorganic materials and 30 to 90% by volume of one or more polymers a high temperature resistant polymer, characterized by the steps of: a) plasma etching the composite in the presence of oxygen, b) dipping the workpiece into a solution containing a precipitate c) dipping the workpiece into a electrolytic solution for electroless metallization.

13.) Process according to claim 12, characterized in that the plasma etching is carried out with an oxygen-containing stock gas volume flow for generating the plasma of at least 20 sccm and at most 400 sccm.

14.) Method according to one of the preceding claims 12 to 13, characterized in that the pressure in the plasma chamber during the plasma etching is less than 0.25 mbar, preferably less than 0.2 mbar.

15.) Method according to one of the preceding claims 12 to 14, characterized in that during the plasma etching, the temperature of the workpiece on the surface reaches at least 55 ⁰ C.

16) Method according to one of the preceding claims 12 to 15, characterized in that the plasma etching lasts between 1 min. And 30 min., Preferably between 15 min. And 20 min.

17) Method according to one of the preceding claims 12 to 16, characterized in that the plasma etching is carried out at a power of 300 watts.

18) Method according to one of the preceding claims 12 to 17, characterized in that the Rasmaätzen as the process gas, a gas is used which contains at least 2 vol. -% oxygen.

19.) Method according to one of the preceding claims 12 to 18, characterized in that the process gas is varied during the Rasmaätzens.

20.) Method according to one of the preceding claims 12 to 19, characterized in that no laser pretreatment of the surface of the composite material is carried out.

21) Method according to one of the preceding claims 12 to 20, characterized in that the surface of the composite material is not wet-chemically etched.

22.) Method according to one of the preceding claims 12 to 21, characterized in that the surface of the composite material is not roughened by blasting.

23.) Method according to one of the preceding claims 12 to 22, characterized in that no PVD or CVD layer is applied before step b).

24.) Use of a multilayer composite according to one of claims 1 to 1 in the electronics industry, as a decorative element of a component, in the automotive industry, in the aerospace industry, in particular as high-gloss handles in an aircraft or automobile or as an automobile grille.