WO1994001599A1 - Metallisierung von kunststoffen - Google Patents
Metallisierung von kunststoffen Download PDFInfo
- Publication number
- WO1994001599A1 WO1994001599A1 PCT/DE1993/000599 DE9300599W WO9401599A1 WO 1994001599 A1 WO1994001599 A1 WO 1994001599A1 DE 9300599 W DE9300599 W DE 9300599W WO 9401599 A1 WO9401599 A1 WO 9401599A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- nickel
- metal layer
- swelling
- plastic
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/26—Roughening, e.g. by etching using organic liquids
Definitions
- the invention relates to a method for metallizing plastics.
- Polymers have been coated with metal for many years.
- the applications of the metal-coated polymers can be divided into two groups: a decorative and a functional one.
- the requirements for the applied metal layers also differ according to these applications.
- a plastic that is metallized for decorative purposes should look like solid metal if possible: have a glossy or semi-gloss surface and be corrosion-resistant.
- Functional layers on polymers are required in very different areas of application: for example as circuit carriers (printed circuit boards) or for shielding against electromagnetic radiation.
- the metal can be applied by spraying, vapor deposition or other vacuum techniques (sputtering) or by painting or flame spraying.
- the electroplating of plastics is carried out by various processes.
- the substrate to be coated is roughened by a chemical pretreatment process in order to achieve sufficient adhesive strength of the metal layer.
- treatment solutions that are adapted to certain materials and do not contain any chemicals that are used are also used Roughen the polymer surface visibly. In the event of thermal or corrosion stress, the adhesion of the substrate surfaces pretreated in this way is generally insufficient.
- aqueous chromic acid, chromium / sulfuric acid solutions or mixtures thereof with phosphoric acid, sulfuric acid and permanganate solutions are typically used as etching solutions.
- Chromium / sulfuric acid solutions in particular have been used for some time for the metalization of acrylonitrile / butadiene / styrene polymer (ABS) substrates (K. Stoeckert, in: Kunststoffe 55. (1965) 857).
- glycol ethers such as diethylene glycol dimethyl ether (DE-39 22 477 AI, US Pat. No. 4,775,557), ethylene glycol monomethyl ether (FR-22 22 459), N-methylpyrrolidone, dimethylformamide (DE-38 07 618 AI), dimethyl sulfoxide and Propylene carbonate (DE-AS 22 22 941).
- Epoxy resin material but not satisfactory for surface treatment when used for shielding against electromagnetic radiation, using plastics that are difficult to metallize, for example polycarbonates, ABS copolymers with polycarbonates or polyphenylene oxide.
- the method most commonly used makes use of catalytic nucleation on the plastic surface, which consists, for example, in depositing palladium particles from a palladium colloid on the polymer surface. Then a firmly adhering metal layer can be produced from electrolessly depositing copper or nickel baths. In most cases, only small layer thicknesses are formed, which are then electrolytically reinforced to the desired layer thickness with suitable metal baths to produce the actual functional layer.
- plastics that are mostly metallized with this method are the already mentioned ABS material, polypropylene, polyphenylene oxide, epoxy resins, polyimide, polyamide and others.
- polycarbonate resins or their mixtures with other polymers are also used.
- Metals which have a high electrical conductivity are naturally particularly suitable for shielding electromagnetic radiation.
- copper also combines some other preferred ones Characteristics. Therefore, many electroless copper deposition systems are well known. A sufficient shielding effect of more than 40dB can already be achieved with a copper layer thickness of one to a few micrometers.
- copper is not very stable against oxidation or corrosion and oxidized copper or copper salts have no shielding effect: the copper surface must therefore be protected against corrosion. This can be done, for example, with a suitable paint, but it is safer to protect against corrosion with a correspondingly resistant metal, especially since this contributes to an increase in the electrical conductivity.
- the plastic parts have an inner and an outer surface, a pore-free, electrolessly deposited copper layer with a layer thickness of at least 0.125 ⁇ m and an electrolessly deposited nickel layer with a layer thickness of at least 0.125 ⁇ m being applied to at least one of the surfaces .
- the toxic chromium / sulfuric acid process is specified for the pretreatment of the plastics to be metallized.
- the adhesive strength of the metal coating is in most cases after the so-called tape test judged.
- one-sided self-adhesive tape is pressed onto the metallized surface of the plastic part and then torn off again with a strong pull. If the metal layer has sufficient adhesive strength, no metal particles may adhere to the adhesive tape.
- a major disadvantage of the described methods is to use solutions containing chromic acid as the etching medium, since these solutions are carcinogenic as aerosols.
- these solutions are carcinogenic as aerosols.
- chromium (VI) ions because of the high toxicity of the chromium (VI) ions, very low limit values in wastewater are required. Therefore, a very high effort must be made in the treatment of wastewater. This enables considerably less effort for occupational safety and waste water treatment.
- chromic acid Another disadvantage of chromic acid is its property of acting as a strong catalyst poison in electroless metallization. Even traces of chromium (VI) ions that get into the activation solution or the electroless baths lead to a marked deterioration in the coating of the plastic surface with metal. For this reason, the chromium (VI) residues must be rinsed off completely from the polymer surfaces. On the one hand, this leads to a very high need for rinsing water and, on the other hand, too long Procedural consequences, since many rinsing steps have to be integrated into the process. For these reasons, there is a desire to replace chromic acid with less toxic substances.
- the invention is therefore based on the problem of avoiding these known disadvantages of the methods according to the prior art and of optimizing the metallization method.
- the organic compounds of the invention are as
- Swelling agents preferably in aqueous swelling solution, are used in a treatment step before an etching treatment in order to prepare the polymer surface for the etching attack.
- the compounds are represented by the general formula
- the substrate is subjected to the etching process in a permanganate solution.
- a permanganate solution which contain toxic chromic acid, less toxic etching media, such as permanganate, which do not interfere with the metallization process, are used.
- Another advantage of the method according to the invention is the more uniform roughening of the substrate than in the conventional methods.
- individual polymer regions are not detached from the polymer composite by the etching process. Rather, the method according to the invention results in a more uniform roughening of the polymer surface with less etching depth. This gives the surface a smoother appearance.
- organic compounds such as, for example, lower alcohols or glycol ethers
- other organic compounds such as, for example, lower alcohols or glycol ethers
- Possible compounds are methanol, ethanol, n- and i-propanol, ethylene glycol, propylene glycol and diethylene glycol monoethyl and butyl ether.
- the swelling attack can be intensified by alkali hydroxide, ammonia or quaternary ammonium bases.
- alkali hydroxide, ammonia or quaternary ammonium bases it should be noted that this results in a faster aging of the solution by increased absorption of carbon dioxide from the air with the formation of the corresponding carbonate, so that there is gradually a salting-up of the swelling solution. The higher the working temperature, the faster this is done.
- wetting agents or other surface-active compounds can also be added to these treatment solutions.
- the temperature of the treatment solution can take any values between room temperature and the boiling point of the solution. In any case, it is necessary to set a temperature which is matched to the special composition of the swelling solution, the process parameters of the subsequent process stages and the substrate to be coated. Usually, however, a temperature above room temperature is selected, preferably 40 to 75 * C. In the same way, the treatment time is selected depending on the parameters mentioned in such a way that sufficient adhesion of the metal coating to the polymer surface is achieved.
- the swelling agent treatment is usually carried out in the immersion process. However, it is also possible to use other methods with which the plastic surfaces are brought into contact with the swelling solution. This includes spraying, gushing, spraying the solution or other types of application.
- the swelling agent treatment After the swelling agent treatment, it is usually rinsed with water.
- the etching process is then carried out with a solution containing permanganate, the solution also usually being brought into contact with the plastic surface by dipping, but other types of contacting, such as spraying, gushing or spraying, are also possible.
- the most commonly used solutions contain potassium and / or sodium permanganate.
- Sodium permanganate is used when concentrations of permanganate are to be set which are higher than about 70 g / l. In this case the concentration of the potassium salt exceeds its solubility at room temperature.
- other permanganate salts are used. Most of these salts are used in alkaline solution.
- the pH of these solutions can, for example, be adjusted to a value greater than 13 using sodium or potassium hydroxide solution.
- the practical area for the above Permanganate concentrations range up to about 250 g / l.
- manganate compounds are formed in these solutions when standing, but especially when processing the plastic parts by converting or decomposing the permanganate.
- the manganate formed has to be reoxidized to permanganate. This can be done by adding strong oxidizing agents such as sodium peroxodisulfate, sodium hypochlorite or other salts or, much more elegantly, by electrolytic regeneration, in which the manganate ions are oxidized to permanganate on an inert anode.
- salts are added to the etching solutions to stabilize the pH of the solution, such as, for example, phosphates and to improve the wetting of the plastic surface, surface-active substances.
- fluorosurfactants are mostly used because of their higher chemical resistance to oxidation.
- the temperature of these solutions is preferably selected EN ⁇ semi-60 * C, but can vary depending on the other process parameters and the selected plastic lower temperatures can be set. Treatment times are usually set between 1 and 20 minutes. In this case, too, the optimal treatment time depends on the process parameters of the entire process and the type of polymer. Usually times between 2 and 6 minutes are preferred.
- the substrate is generally treated with a reducing agent in order to remove residues of the oxidizing solution and adhering reaction products, such as manganese dioxide, from the surface. Acidic solutions are used for this. Solutions containing hydrogen peroxide, hydrazine or hydrazinium salt, hydroxylammonium salts, glyoxal, oxalic acid or other compounds are mostly used.
- a further treatment in aqueous solutions of conditioning agents can then be carried out, which allow sufficient adsorption of the catalytic nuclei subsequently produced on the plastic surface.
- Polymeric quaternary compounds are mostly used for this.
- the plastic surface is activated with precious metal seeds.
- Palladium is used as the catalytic metal in the commonly used solutions.
- Either a hydrochloric acid palladium colloid or a complex compound of palladium can be used.
- other possibilities are also known, such as a two-stage procedure in which the plastic is first treated in a hydrochloric acid tin (II) chloride solution and then in a palladium chloride solution which is also hydrochloric acid.
- palladium chloride with tin (II) chloride is used, the protective colloid is removed again in a commercially available accelerator solution; if a palladium complex compound is used, the palladium complexes adsorbed on the substrate surface are reduced to palladium nuclei with boron water. connections made.
- the first metal deposition can be carried out on the surface from any electroless metal baths, for example with precious metals, copper, nickel or cobalt or their alloys. However, an easy-to-use and inexpensive electroless copper or nickel bath is mostly used.
- a very advantageous embodiment of the invention consists in that the metal layers applied to the substrate consist of at least three layers, the first layer being a metal layer of the metals nickel, cobalt, palladium, and gold, if appropriate after pretreatment with the swelling and etching solutions described above or their alloys and the metals are deposited from an electroless plating bath, the second layer consists of electrolessly deposited copper and the third layer is a metal layer of the metals nickel, cobalt, palladium, gold or their alloys and the metals from an electroless plating bath be deposited.
- the advantage of the method according to the invention is that a very high adhesion of the deposited metal layers is achieved even immediately after the metallization.
- the method can also be used without problems for plastics such as polycarbonate or its mixtures with other plastics, such as ABS, or other polymers which are difficult to metallize.
- the first metal layer can be formed as a thin, highly adhesive layer onto which thicker metal layers are deposited in an economical process with a higher deposition rate.
- Critical problems in the metallization of polymer surfaces are the adhesive strength of the metal layer on the surface, the environmental friendliness of the process (type of chemicals used and chemical consumption) and the cost of the process. Compromises can be found between these parameters: an environmentally friendly and less aggressive pretreatment of the polymer surface often results in a longer residence time in the treatment baths or worsens it
- Quality of the products for example the adhesive strength of the metal on the surface.
- the exchange of chromic acid or chromosulphuric acid in the first pretreatment step of a plastic surface for pretreatment with a swelling system and alkaline permanganate solution can considerably expand the range of the process with regard to the types of plastic to be metallized.
- This exchange also avoids the use of solution with chromium compounds in oxidation state + VI, which is not harmless, and replaces this with the harmless permanganate solutions.
- the higher bandwidth results in a lower adhesive strength of the electrolessly deposited metal on the plastic surface.
- Electrolytes with the copper layer drastically increases the adhesive strength of the metal layers on the plastic surface and allows one
- the metallization processes are explained in more detail in the examples for this invention.
- the peel tests are carried out with an Instron tensile testing machine.
- nickel layers with phosphorus or boron as an alloy component have proven to be suitable.
- electroless copper is applied to such a base metallization in a layer thickness necessary to achieve a sufficient shielding effect.
- the shielding effect should be at least 20 dB in the frequency range to be shielded (10 kHz to 1 GHz) exceed.
- the copper layer is then protected against corrosion with a further electrolessly deposited metal layer (nickel, cobalt, palladium, gold or alloys thereof). So the whole process is, first, the
- Pretreat the plastic surface for the metallization then activate it for electroless metal deposition and then electrolessly deposit a layer of nickel, cobalt, palladium, gold or an alloy of these metals, then copper in a thickness necessary to achieve the shielding effect and then preferably the same electrolessly depositing bath as in the first metallization step to deposit another metal layer as corrosion protection.
- BAYBLEND plastic a trademark of Bayer AG, (polycarbonate / ABS blend) was metallized in accordance with the following procedure:
- Rinsing was carried out between all successive process stages, except between 2nd and 3rd, 3rd and 4th and 5th and 6th.
- the swelling agent contained 70 vol Diethylene glycol ethyl ether acetate in water.
- the permanganate solution had the following composition:
- the electroless copper bath contained formaldehyde as a reducing agent.
- Ethylene diamine tetrakis (propan-2-ol) was used as a comp lexbi lnner.
- the electrolessly deposited copper layer adhered well to the base material.
- Example 2 The same result as in Example 1 was obtained if, instead of the diethylene glycol ethyl ether acetate, a 50% by volume solution of ethylene glycol methyl ether acetate was used.
- the plastic PULSE trademark of Dow Chemicals, Inc., (also a blend of polycarbonate and ABS) could be metallized with adhesive.
- Example 2 The same result as in Example 1 was obtained when a 50 vol.% Or 70 vol.% Solution of di-ethylene glycol ethyl ether acetate and 5 vol.% N-propanol was used as swelling agent. In both cases, there was an adherent copper-plating of the plastics BAYBLEND, PULSE and LEXAN, trademark for a polycarbonate from General Electric Plastics, reached.
- the copper layer was detached from the plastic surface in all cases during the adhesive tape test.
- Rinsing is carried out between all process stages, except between 2nd and 3rd, 3rd and 4th and 5th and 6th.
- the permanganate solution had the following composition:
- the electroless nickel bath contained sodium hypophosphite as a reducing agent and worked at a pH of 8 to 8.5.
- the parts were subjected to alkaline degreasing before the metallization treatment.
- An alkaline wetting agent solution at 60 * C was used for this.
- the treatment time was 9 minutes.
- the pretreatment freed the plastic parts of contaminants such as release agents from the injection molding. Very good adhesion of the metal coating to the metal surface was found.
- a housing part which has been injection molded from the plastic acrylonitrile / butadiene / styrene (ABS) is pretreated for ten minutes in a solution of 360 g / l chromic acid and 360 g / 1 sulfuric acid, rinsed, detoxified with a solution of 80 g / 1 sodium sulfite ', then treated with a solution of 300 g / 1 sodium chloride and 10 g / 1 hydrochloric acid and in a solution of 8.8 g / 1 tin (II) chloride, 11.25 g / 1 hydrochloric acid and 0.15 g / 1 Palladium chloride activated.
- ABS plastic acrylonitrile / butadiene / styrene
- the mixture is metallically reductively metallized for five minutes at 40 ° C. from a commercially available bath which is an alloy deposits from nickel and phosphorus with a phosphorus content of 5% and a deposition rate of about 4 ⁇ m / h. Then copper is deposited from a reductive depositing bath based on Quadrol at 45 ° C.
- a commercially available bath which is an alloy deposits from nickel and phosphorus with a phosphorus content of 5% and a deposition rate of about 4 ⁇ m / h.
- This copper layer is coated with an approximately 1 ⁇ m thick nickel layer in the same nickel bath as previously described and thus protected against corrosion.
- a plastic molding made of Lexan BE2130 is at room temperature for five minutes in a sweller consisting of 15% of a diglycol ether in water and then after rinsing in a solution of 140 g / 1 permanganate and 50 g / 1 sodium hydroxide at 65 ° C in Pretreated for 10 minutes.
- the manganese oxide deposited on the surface is then removed by a solution of hydrogen peroxide and sulfuric acid.
- an ionic activator system with a palladium content of 70 ppm at 45 ° C.
- Example 26 The adhesive strengths of some such layer systems have been listed in the overview described above.
- Example 26 The adhesive strengths of some such layer systems have been listed in the overview described above.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93914605A EP0650537B1 (de) | 1992-07-02 | 1993-07-02 | Metallisierung von kunststoffen |
AT93914605T ATE188261T1 (de) | 1992-07-02 | 1993-07-02 | Metallisierung von kunststoffen |
DE59309916T DE59309916D1 (de) | 1992-07-02 | 1993-07-02 | Metallisierung von kunststoffen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4221948A DE4221948C1 (de) | 1992-07-02 | 1992-07-02 | Verfahren zur Metallisierung von Kunststoffen und Verwendung |
DEP4221948.5 | 1992-07-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994001599A1 true WO1994001599A1 (de) | 1994-01-20 |
Family
ID=6462448
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE1993/000599 WO1994001599A1 (de) | 1992-07-02 | 1993-07-02 | Metallisierung von kunststoffen |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0650537B1 (de) |
AT (1) | ATE188261T1 (de) |
DE (2) | DE4221948C1 (de) |
ES (1) | ES2140461T3 (de) |
WO (1) | WO1994001599A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008043125A1 (de) * | 2008-10-23 | 2010-04-29 | BSH Bosch und Siemens Hausgeräte GmbH | Bedienelement für ein Haushaltsgerät |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102015201562A1 (de) | 2015-01-29 | 2016-08-04 | Helmholtz-Zentrum Dresden - Rossendorf E.V. | Verfahren zur Metallisierung von Kunststoffteilen sowie Lösung |
WO2017137584A1 (de) | 2016-02-12 | 2017-08-17 | Biconex Gmbh | Verfahren zur vorbehandlung von kunststoffteilen für die galvanische beschichtung |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4515829A (en) * | 1983-10-14 | 1985-05-07 | Shipley Company Inc. | Through-hole plating |
WO1985005755A1 (en) * | 1984-05-29 | 1985-12-19 | Enthone, Incorporated | Composition and process for conditioning the surface of plastic substrates prior to metal plating |
EP0207586A1 (de) * | 1985-05-31 | 1987-01-07 | Macdermid Incorporated | Natriumpermanganatlösung und ihre Anwendung beim Reinigen, Entgraten und/oder Ätzen von Kunststoffoberflächen |
EP0309243A1 (de) * | 1987-09-25 | 1989-03-29 | Engelhard Technologies Limited | Vorätzbehandlung eines Plastiksubstrats |
WO1989010431A1 (en) * | 1988-04-25 | 1989-11-02 | Macdermid, Incorporated | Process and composition for preparing printed circuit through-holes for metallization |
DE3922477A1 (de) * | 1989-07-06 | 1991-01-17 | Schering Ag | Quellmittel zur vorbehandlung von kunstharzen vor einer stromlosen metallisierung |
DE4108461C1 (de) * | 1991-03-13 | 1992-06-25 | Schering Ag Berlin Und Bergkamen, 1000 Berlin, De |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3769061A (en) * | 1971-06-14 | 1973-10-30 | Shipley Co | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating |
JPS5133833B2 (de) * | 1973-03-19 | 1976-09-22 | ||
US4775557A (en) * | 1987-11-09 | 1988-10-04 | Enthone, Incorporated | Composition and process for conditioning the surface of polycarbonate resins prior to metal plating |
DE3807618A1 (de) * | 1988-03-04 | 1989-09-14 | Schering Ag | Basismaterial aus epoxid-harz |
-
1992
- 1992-07-02 DE DE4221948A patent/DE4221948C1/de not_active Expired - Fee Related
-
1993
- 1993-07-02 DE DE59309916T patent/DE59309916D1/de not_active Expired - Lifetime
- 1993-07-02 ES ES93914605T patent/ES2140461T3/es not_active Expired - Lifetime
- 1993-07-02 WO PCT/DE1993/000599 patent/WO1994001599A1/de active IP Right Grant
- 1993-07-02 AT AT93914605T patent/ATE188261T1/de not_active IP Right Cessation
- 1993-07-02 EP EP93914605A patent/EP0650537B1/de not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4515829A (en) * | 1983-10-14 | 1985-05-07 | Shipley Company Inc. | Through-hole plating |
WO1985005755A1 (en) * | 1984-05-29 | 1985-12-19 | Enthone, Incorporated | Composition and process for conditioning the surface of plastic substrates prior to metal plating |
EP0207586A1 (de) * | 1985-05-31 | 1987-01-07 | Macdermid Incorporated | Natriumpermanganatlösung und ihre Anwendung beim Reinigen, Entgraten und/oder Ätzen von Kunststoffoberflächen |
EP0309243A1 (de) * | 1987-09-25 | 1989-03-29 | Engelhard Technologies Limited | Vorätzbehandlung eines Plastiksubstrats |
WO1989010431A1 (en) * | 1988-04-25 | 1989-11-02 | Macdermid, Incorporated | Process and composition for preparing printed circuit through-holes for metallization |
DE3922477A1 (de) * | 1989-07-06 | 1991-01-17 | Schering Ag | Quellmittel zur vorbehandlung von kunstharzen vor einer stromlosen metallisierung |
DE4108461C1 (de) * | 1991-03-13 | 1992-06-25 | Schering Ag Berlin Und Bergkamen, 1000 Berlin, De |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008043125A1 (de) * | 2008-10-23 | 2010-04-29 | BSH Bosch und Siemens Hausgeräte GmbH | Bedienelement für ein Haushaltsgerät |
Also Published As
Publication number | Publication date |
---|---|
EP0650537A1 (de) | 1995-05-03 |
ATE188261T1 (de) | 2000-01-15 |
ES2140461T3 (es) | 2000-03-01 |
DE59309916D1 (de) | 2000-02-03 |
DE4221948C1 (de) | 1993-10-21 |
EP0650537B1 (de) | 1999-12-29 |
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