WO2013135862A2 - Process for metallizing nonconductive plastic surfaces - Google Patents
Process for metallizing nonconductive plastic surfaces Download PDFInfo
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- WO2013135862A2 WO2013135862A2 PCT/EP2013/055356 EP2013055356W WO2013135862A2 WO 2013135862 A2 WO2013135862 A2 WO 2013135862A2 EP 2013055356 W EP2013055356 W EP 2013055356W WO 2013135862 A2 WO2013135862 A2 WO 2013135862A2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1621—Protection of inner surfaces of the apparatus
- C23C18/1625—Protection of inner surfaces of the apparatus through chemical processes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1628—Specific elements or parts of the apparatus
- C23C18/163—Supporting devices for articles to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
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- 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
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- 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
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- 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
- C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
Definitions
- the present invention relates to a process for metallizing electrically nonconductive plastic surfaces of articles.
- the rack in which the said articles are fastened is treated with an iodate ion-containing solution in order to prevent metallization of the rack.
- the articles can be metallized by means of known processes. In the course of these, the rack remains free of metal.
- Articles made from electrically nonconductive plastic can be metallized by an electroless metallization process.
- the article is first cleaned and etched, then treated with a noble metal and finally metallized.
- the etching is typically undertaken by means of chromosulphuric acid. The etching serves to make the surface of the article receptive to the subsequent metallization, such that the surfaces of the articles are well-wetted with the respective solutions in the subsequent treatment steps and the deposited metal ultimately has sufficiently firm adhesion on the surface.
- the surface of articles for example made from acrylonitrile-butadiene-styrene copolymer (ABS copolymer), is etched using chromosulphuric acid, so as to form surface microcaverns in which metal is deposited and subsequently adheres there firmly.
- the plastic is activated for the electroless metallization by means of an activator comprising a noble metal, and then metallized electrolessly. Subsequently, a thicker metal layer can also be applied electrolytically.
- Etching solutions based on chromosulphuric acid are toxic and should therefore be replaced as possible.
- the literature describes attempts to replace etching solutions based on chromosulphuric acid with those comprising permanganate salts.
- permanganates in an alkaline medium for metallization of circuit boards as a carrier of electronic circuits has long been established. Since the hexavalent state (manganate) which arises in the oxidation is water-soluble and has sufficient stability under alkaline conditions, the manganate, similarly to trivalent chromium, can be oxidized electrolytically back to the original oxidizing agent, in this case the permanganate.
- the document DE 196 1 1 137 A1 describes the use of the permanganate also for metallization of other plastics as circuit board material.
- EP 1 0010 52 discloses an acidic permanganate solution which is said to be suitable for use in plastic galvanization. EP 1 0010 52 does not report the adhesion strengths achievable by this pretreatment. In-house experiments have shown that the adhesion strengths are below a value of 0.4 N/mm. Moreover, the solutions described in EP 1 0010 52 are unstable. A constant quality of the metallization therefore cannot be achieved.
- WO 2009/023628 A2 proposes strongly acidic solutions comprising an alkali metal permanganate salt. The solution contains about 20 g/l alkali metal permanganate salt in 40 - 85% by weight phosphoric acid. Such solutions form colloidal manganese(IV) species which are difficult to remove.
- WO 2009/023628 A2 proposes using manganese(VII) sources which do not contain any alkali metal or alkaline earth metal ions.
- manganese(VII) sources which do not contain any alkali metal or alkaline earth metal ions.
- the preparation of such manganese(VII) sources is costly and inconvenient. Therefore, toxic chromosulphuric acid is still being used for etching treatment of plastics.
- the articles are usually fastened to racks.
- racks These are metal carrier systems which allow the simultaneous treatment of a large number of articles with the successive solutions for the individual process steps, and last steps for electrolytic deposition of one or more metal layers.
- the racks are generally themselves coated with plastic. Therefore, the racks in principle likewise constitute a substrate for metallization processes on plastic surfaces.
- the additional metallization of the racks is undesirable, since the metal layers have to be removed again from the racks after the coating of the articles. This means additional cost and inconvenience for the removal, combined with additional consumption of chemicals.
- the productivity of the metallization plant in this case is lower, since the racks first have to be demetallized prior to reloading with articles. If the demetallization has to take place using semi-concentrated hydrochloric acid and/or using nitric acid, vapours and aerosols are produced, and these lead to corrosion in the environment.
- a further problem is that, when rack metallization occurs, it is no longer possible to achieve a defined current density in a reproducible manner because the extent of the rack coverage is usually unknown, and the exact surface area of the rack is likewise unknown. The consequence is then usually that the metal layer applied to the galvanized plastic articles is too thin.
- Patent DE 195 10 855 C2 describes a process for selective or partial electrolytic metallization of nonconductive materials. In this case, the simultaneous metallization of the racks is prevented by omitting treatment steps with adsorption-promoting solutions, called conditioners. However, it is emphasized that the process for metallizing nonconductive materials in DE 195 10 855 C2 is suitable only for direct metallization.
- Figure 1 Influence of the iodate treatment on rack metallization.
- Figure 2A Rack after metallization process without iodate treatment.
- Figure 2B Rack after metallization process with iodate treatment.
- Figure 3 Influence of the treatment time of articles made from an ABS/PC mixture with glycol compounds on adhesion strength.
- the present invention is therefore based on the problem that it has not been possible to date to avoid the metallization of the racks and simultaneously to achieve metallization of articles made from electrically nonconductive plastic with sufficient process reliability and adhesion strength of the metal layers applied subsequently.
- the rack is treated with a solution comprising iodate ions.
- Articles in the context of this invention are understood to mean articles which have been manufactured from at least one electrically nonconductive plastic or which have been covered with at least one layer of at least one electrically nonconductive plastic.
- the articles thus have surfaces of at least one electrically nonconductive plastic.
- Plastic surfaces are understood in the context of this invention to mean these said surfaces of the articles.
- process steps of the present invention are performed in the sequence specified, but not necessarily in immediate succession. It is possible for further process steps and additionally rinse steps in each case, preferably with water, to be performed between the steps.
- the inventive treatment of the rack with a solution comprising iodate ions prevents the metallization of the rack, while the electrically nonconductive plastic surfaces of articles are coated with metal.
- the rack thus remains free of metal during the process according to the invention. With the process according to the invention, it is unnecessary to free the racks of metal again after use, since the racks are not metallized as a result of the inventive treatment with iodate ions and thus remain free of metal.
- the racks can be returned immediately back to the production cycle without further treatment and used for metallization of further articles.
- the plastic surfaces have been manufactured from at least one electrically nonconductive plastic.
- the at least one electrically nonconductive plastic is selected from the group comprising an acrylonitrile-butadiene- styrene copolymer (ABS copolymer), a polyamide (PA), a polycarbonate (PC) and a mixture of an ABS copolymer with at least one further polymer.
- the electrically nonconductive plastic is an ABS copolymer or a mixture of an ABS copolymer with at least one further polymer.
- the at least one further polymer is more preferably polycarbonate (PC), which means that particular preference is given to ABS/PC mixtures.
- the inventive treatment of the rack with a solution comprising iodate ions is also referred to hereinafter as protection of the rack.
- the protection of the rack can take place at various times during the process according to the invention.
- the treatment of the rack with a solution comprising iodate ions takes place prior to process step A).
- the articles are not yet fastened to the rack.
- the rack is thus treated alone, without the articles, with the solution comprising iodate ions.
- Step A) of the process according to the invention is the fastening of the articles to racks which enable the simultaneous treatment of a large number of articles with the successive solutions for the individual process steps, and the establishment of electrical contact connection during the last steps for electrolytic deposition of one or more metal layers.
- the treatment of the articles by the process according to the invention is preferably performed in a conventional dipping process, by dipping the articles successively into solutions in vessels in which the respective treatment takes place. In this case, the articles may be dipped into the solutions either fastened to racks or accommodated in drums. Fastening to racks is preferred.
- the racks are generally themselves coated with plastic.
- the plastic is usually polyvinyl chloride (PVC).
- the further process step A i) is also referred to as pretreatment step.
- This pretreatment step increases the adhesion strength between the plastic of the article and the metal layer.
- a glycol compound is understood to mean compounds of the following general formula (I):
- n is an integer from 1 to 4.
- R 1 and R 2 are each independently -H, -CH 3 , -CH 2 -CH 3 ,
- the glycol compounds include the glycols themselves and glycol derivatives.
- the glycol derivatives include the glycol ethers, the glycol esters and the glycol ether esters.
- the glycol compounds are solvents.
- Preferred glycol compounds are ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, butyl glycol, ethylene glycol monobutyl ether, ethylene glycol diacetate and mixtures thereof.
- Particular preference is given to diethylene glycol monoethyl ether acetate, ethylene glycol acetate, ethylene glycol diacetate, butyl glycol and mixtures thereof.
- glycol esters and glycol ether esters it is advisable to keep the pH of the aqueous solution of the glycol compound within the neutral range by suitable measures, in order to as far as possible suppress the hydrolysis to give the alcohol and carboxylic acid.
- suitable measures in order to as far as possible suppress the hydrolysis to give the alcohol and carboxylic acid.
- hydrolysis of the diethylene glycol monoethyl ether acetate is the hydrolysis of the diethylene glycol monoethyl ether acetate:
- the water concentration of the solution comprising a glycol compound likewise has an influence on the hydrolysis of the glycol esters and glycol ether esters.
- the solution has to contain water for two reasons: firstly to obtain a noncombustible treatment solution and secondly to be able to adjust the strength of the attack on the plastic surface.
- a pure solvent, i.e. 100% of a glycol compound, would dissolve most uncrosslinked polymers or at least leave an unacceptable surface.
- a phosphate buffer mixture has been found to be sufficiently suitable for this purpose.
- the readily soluble potassium phosphates allow sufficiently high concentrations with good buffer capacity at solvent concentrations up to 40% by vol.
- the optimal treatment time for the plastic surface depends on the plastic used, the temperature, and the nature and concentration of the glycol compound.
- the treatment parameters have an influence on the adhesion between the treated plastic surface and the metal layer applied in downstream process steps. Higher temperatures or concentrations of the glycol compounds also influence the texture of the plastic surface.
- the downstream etching step B) it should be possible for the downstream etching step B) to remove the solvent from the plastic matrix again, because the subsequent steps in the process, more particularly the activation in process step C), are otherwise disrupted.
- the process according to the invention gives adhesion strengths of at least 0.8 N/mm, which is well above the required minimum value of 0.4 N/mm.
- the treatment time in process step A i) is between 1 and 30 minutes, preferably between 5 and 20 minutes and more preferably between 7 and 15 minutes.
- the treatment temperature is between 20°C and 70°C, depending on the nature of the solvent or solvent mixture used. Preference is given to a treatment temperature between 20°C and 50°C, particular preference to a treatment temperature between 20°C and 45°C.
- the treatment of the plastic surfaces in process step A i) can be performed in an aqueous solution comprising one glycol compound or in an aqueous solution comprising two or more different glycol compounds.
- the total concentration of glycol compounds in the aqueous solution is 5% by vol. - 50% by vol., preferably 10% by vol. - 40% by vol. and more preferably 20% by vol. - 40% by vol. If said solution contains one glycol compound, the overall concentration corresponds to the concentration of this one glycol compound. If said solution contains two or more different glycol compounds, the total concentration corresponds to the sum total of the concentrations of all glycol compounds present.
- the concentration figures for the glycol compound/glycol compounds in % are always understood to mean a concentration in % by vol.
- concentration in % by vol. For instance, for pretreatment of ABS plastic surfaces, a solution of 15% by vol. of diethylene glycol monoethyl ether acetate in a mixture with 10% by vol. of butyl glycol at 45°C has been found to be advantageous (see Example 4).
- the first solvent therein serves to generate the adhesion strength, while the second, as a nonionic surfactant, increases wettability and helps to remove any soiling present from the plastic surface.
- the treatment of the rack with a solution comprising iodate ions takes place between process steps A) and B).
- the treatment of the rack with a solution comprising iodate ions can take place between process steps A) and A i) or between process steps A i) and B).
- the rack is thus treated together with the articles with the solution comprising iodate ions.
- the wordings "the rack is treated with a solution comprising iodate ions" and "treatment of the rack with a solution comprising iodate ions” in the context of this invention mean that the protection of the rack can take place alone, without the articles (for example when the protection of the rack takes place prior to process step A)), or that the protection of the rack can take place together with the articles (for example when the protection of the rack takes place at some time after process step A)).
- the etching treatment in process step B) is performed in an etching solution.
- the etching solution comprises a source for permanganate ions.
- the source for permanganate ions is selected from alkali metal permanganates.
- the alkali metal permanganates are selected from the group comprising potassium permanganate and sodium permanganate.
- the source for permanganate ions is present in the etching solution in a concentration between 30 g/l and 250 g/l, preferably between 30 g/l and 180 g/l, further preferably between 90 g/l and 180 g/l, more preferably between 90 g/l and 1 10 g/l and even more preferably between 70 g/l and 100 g/l.
- potassium permanganate may be present in the etching solution in a concentration of up to 70 g/l.
- Sodium permanganate may be present in the etching solution in a concentration of up to 250 g/l.
- the lower concentration limit for each of these two salts is typically 30 g/l.
- the content of sodium permanganate is preferably between 90 g/l and 180 g/l.
- the etching solution is preferably acidic, meaning that it preferably contains an acid.
- alkaline permanganate solutions as used routinely in the circuit board industry as an etching solution, are unsuitable for the present invention, since they do not give sufficient adhesion strength between plastic surface and metal layer.
- Acids which are used in the etching solution are preferably inorganic acids.
- the inorganic acid in the etching solution in process step B) is selected from the group comprising sulphuric acid, nitric acid and phosphoric acid.
- the acid concentration must not be too high, since the etching solution is otherwise not stable.
- the acid concentration is between 0.02 - 0.6 mol/l based on a monobasic acid. It is preferably between 0.06 and 0.45 mol/l, more preferably between 0.07 and 0.30 mol/l, based in each case on a monobasic acid.
- Preference is given to using sulphuric acid in a concentration between 0.035 and 0.15 mol/l, corresponding to an acid concentration between 0.07 and 0.30 mol/l based on a monobasic acid.
- the etching solution does only contain a source for permanganate ions as described above and an acid as described above. In this embodiment the etching solution does not contain any further ingredients.
- the etching solution can be employed at temperatures between 30°C and 90°C, preferably between 55°C and 75°C. It has been found that sufficiently high adhesion strengths between metal layers and plastic surfaces can also be achieved at low temperatures between 30°C and 55°C. In that case, however, it is not possible to ensure that all solvent from the treatment with glycol compound in process step A i) has been removed from the plastic surface. This is particularly true of pure ABS.
- the temperatures in the downstream process step B) should be selected at a higher level, namely within the range from 55°C to 90°C, preferably within the range from 55°C to 75°C.
- the optimal treatment time depends on the plastic surface being treated and the selected temperature of the etching solution.
- the best adhesion strength between plastic surface and subsequently applied metal layer is achieved at a treatment time between 5 and 30 minutes, preferably between 10 and 25 minutes and more preferably between 10 and 15 minutes.
- a longer treatment time than 30 minutes generally leads to no further improvement in the adhesion strengths.
- manganese dioxide An acidic permanganate solution is very reactive at elevated temperatures, for example at 70°C. The oxidation reaction with the plastic surface then forms many manganese(IV) species which precipitate out. These manganese(IV) species are predominantly manganese(IV) oxides or oxide hydrates and are referred to hereinafter simply as manganese dioxide.
- the manganese dioxide precipitate has a disruptive effect on the subsequent metallization if it remains on the plastic surface. During the activation in process step C), it ensures that regions of the plastic surface are not covered with metal colloid or gives rise to unacceptable roughness of the metal layer to be applied in later process steps.
- the etching solution does not contain any chromium or chromium compounds; the etching solution contains neither chromium(lll) ions nor chromium(VI) ions.
- the etching solution is thus free of chromium or chromium compounds; the etching solution is free of chromium(lll) ions and chromium(VI) ions.
- the articles, after the permanganate treatment in process step B), are cleaned by rinsing off excess permanganate solution. The rinsing is effected in one or more, preferably three, rinsing steps with water.
- the further process step B i) is also referred to as reduction treatment.
- This reduction treatment reduces manganese dioxide adhering to the plastic surfaces to water-soluble manganese(ll) ions.
- the reduction treatment is conducted after the permanganate treatment in process step B) and optionally after the rinsing.
- an acidic solution of a reducing agent is used.
- the reducing agent is selected from the group comprising hydroxylammonium sulphate, hydroxylammonium chloride and hydrogen peroxide. Preference is given to an acidic solution of hydrogen peroxide because hydrogen peroxide is neither toxic nor complex-forming.
- the content of hydrogen peroxide in the solution of the reduction treatment is between 25 ml/1 and 35 ml/1 of a 30% hydrogen peroxide solution (% by weight), preferably 30 ml/1 of a 30% hydrogen peroxide solution (% by weight).
- the acid used in the reduction solution is an inorganic acid, preferably sulphuric acid.
- the acid concentration is 0.5 mol/l to 5.0 mol/l, preferably 1 .0 mol/l to 3.0 mol/l, more preferably 1.0 mol/l to 2.0 mol/l, based in each case on a monobasic acid.
- concentrations of 50 g/l 96% sulphuric acid to 100 g/l 96% sulphuric acid corresponding to an acid concentration of 1 .0 mol/l to 2.0 mol/l based on a monobasic acid.
- the reduction treatment removes the manganese dioxide precipitate which disrupts the metallization of the articles.
- the reduction treatment of process step B i) promotes the homogeneous and continuous coverage of the articles with the desired metal layer and promotes the adhesion strength and smoothness of the metal layer applied to the articles.
- the reduction treatment in process step B i) likewise has an advantageous effect on the metallization of the plastic casing of the rack.
- the unwanted coverage of the plastic casing with palladium during process step C) is suppressed. This effect is particularly pronounced when the reduction solution comprises a strong inorganic acid, preferably sulphuric acid. Hydrogen peroxide is preferred over hydroxylammonium sulphate or chloride in the reduction solution also because it better suppresses rack metallization.
- the reduction treatment in process step B i) is performed at a temperature between 30°C and 50°C, preferably at 40°C to 45°C.
- the reduction treatment is performed for a period between 1 and 10 minutes, preferably between 3 and 6 minutes.
- the hydrogen peroxide reducing agent used has to be replenished from time to time.
- the consumption of hydrogen peroxide can be calculated from the amount of manganese dioxide bound to the plastic surfaces.
- the treatment of the rack with a solution comprising iodate ions takes place between process steps B) and C), preferably between process steps B i) and B ii).
- the treatment of the rack with a solution comprising iodate ions is perfomed prior to process step C).
- the treatment of the rack with a solution comprising iodate ions is perfomed prior to process step B ii). If the treatment of the rack with a solution comprising iodate ions is performed at a time later than step C) during the inventive metallizing process, or simultaneously with step C), the effect of protection of the plastic casing of the racks against metal deposition is not achieved (see Example 6).
- Figure 2A shows part of a rack after a plastic surface of an article in the form of a plate which has been fastened in the rack has been copper-plated.
- the process for applying the copper layer corresponded to the metallization process according to the invention, except that the protection of the rack was not carried out.
- the part of the rack which came into contact with the various treatment solutions in the metallization process is completely coated by a copper layer.
- Figure 2B shows a corresponding part of a rack after a plastic surface of an article in the form of a plate which has been fastened in the rack has been copper-plated with inclusion of the protection of the rack.
- the plastic surface of the article bears a homogeneous copper layer, while the plastic casing of the rack has not been copper-plated.
- the plastic casing of the rack additionally bears a black- green colour which is caused by long use of the rack.
- Treatment with iodate ions is particularly advantageous when process step C ii), in one embodiment of the invention, consists of electroless metallizing of the articles in a metallization solution.
- the iodate ions are of sufficient stability in aqueous solution and are consumed only through drag-out.
- the effect of the protection of the rack increases with rising concentration of the iodate ions and with rising operating temperature. Finding of the optimum concentration is described in working example 1.
- the protection of the rack is executed at a temperature of 20°C to 70°C, more preferably of 45°C to 55°C.
- the iodate ions are in the form of metal iodates.
- the metal iodates are selected from the group comprising sodium iodate, potassium iodate, magnesium iodate, calcium iodate and the hydrates thereof.
- the concentration of the metal iodates is between 5 g/l and 50 g/l, preferably from 15 g/l to 25 g/l.
- the duration of the treatment of the rack with iodate ions is between 1 and 20 minutes, preferably between 2 and 15 minutes and more preferably between 5 and 10 minutes.
- the solution comprising iodate ions may further comprise an acid.
- Inorganic acids are preferred.
- the inorganic acids are selected from the group comprising sulphuric acid and phosphoric acid, preferably sulphuric acid.
- the acid concentration is 0.02 mol/l to 2.0 mol/l, preferably 0.06 mol/l to 1.5 mol/l, more preferably 0.1 mol/l to 1 .0 mol/l, based in each case on a monobasic acid.
- sulphuric acid In the case of use of sulphuric acid, particular preference is given to concentrations of 5 g/l 96% sulphuric acid to 50 g/l 96% sulphuric acid, corresponding to an acid concentration of 0.1 mol/l to 1.0 mol/l based on a monobasic acid.
- composition of the solution comprising iodate ions and temperature and duration for the treatment of the rack are independent of the juncture in the process according to the invention at which the protection of the rack takes place.
- a metallization cycle in the context of this invention is understood to mean a metallization process which includes process steps A) to D) already described, but not the treatment of the rack with a solution comprising iodate ions.
- unmetallized articles are fastened to the racks and used to produce metallized articles.
- the process according to the invention comprising the treatment of the rack with a solution comprising iodate ions is performed, and then one to four metallization cycles are performed.
- articles are metallized.
- the rack is metallized neither during the process according to the invention nor during the subsequent metallization cycles, even though the metallization cycles do not include the treatment of the rack with a solution comprising iodate ions.
- the treatment of the rack with a solution comprising iodate ions during the process according to the invention is sufficient to avoid metallization of the racks even during one to four subsequent metallization cycles.
- the process of the present invention further comprises process step C), in which a plastic surface is treated with a solution of a metal colloid or of a compound of a metal.
- the metal of the metal colloid or of the metal compound is selected from the group comprising the metals of transition group I of the Periodic Table of the Elements (PTE) and transition group VIII of the PTE.
- the metal of transition group VIII of the PTE is selected from the group comprising palladium, platinum, iridium, rhodium and a mixture of two or more of these metals.
- the metal of transition group I of the PTE is selected from the group comprising gold, silver and a mixture of these metals.
- a preferred metal in the metal colloid is palladium.
- the metal colloid is stabilized with the protective colloid.
- the protective colloid is selected from the group comprising metallic protective colloids, organic protective colloids and other protective colloids.
- metallic protective colloid preference is given to tin ions.
- the organic protective colloid is selected from the group comprising polyvinyl alcohol, polyvinylpyrrolidone and gelatine, preferably polyvinyl alcohol.
- the solution of the metal colloid in process step C) is an activator solution with a palladium/tin colloid.
- This colloid solution is obtained from a palladium salt, a tin(ll) salt and an inorganic acid.
- a preferred palladium salt is palladium chloride.
- a preferred tin(ll) salt is tin(ll) chloride.
- the inorganic acid may consist in hydrochloric acid or sulphuric acid, preferably hydrochloric acid.
- the colloid solution forms through reduction of the palladium chloride to palladium with the aid of the tin(ll) chloride.
- the conversion of the palladium chloride to the colloid is complete; therefore, the colloid solution no longer contains any palladium chloride.
- the concentration of palladium is 5 mg/l - 100 mg/l, preferably 20 mg/l - 50 mg/l and more preferably 30 mg/l - 45 mg/l, based on Pd 2+ .
- the concentration of tin(ll) chloride is 0.5 g/l - 10 g/l, preferably 1 g/l - 5 g/l and more preferably 2 g/l - 4 g/l, based on Sn 2+ .
- the concentration of hydrochloric acid is 100 ml/l - 300 ml/l (37% by weight of HCI).
- a palladium/tin colloid solution additionally comprises tin(IV) ions which form through oxidation of the tin(ll) ions.
- the temperature of the colloid solution during process step C) is 20°C - 50°C and preferably 35°C - 45°C.
- the treatment time with the activator solution is 0.5 min - 10 min, preferably 2 min - 5 min and more preferably 3 min - 5 min.
- the solution of a compound of a metal is used in place of the metal colloid.
- the solution of a metal compound used is a solution comprising an acid and a metal salt.
- the metal in the metal salt consists in one or more of the above-listed metals of transition groups I and VIII of the PTE.
- the metal salt may be a palladium salt, preferably palladium chloride, palladium sulphate or palladium acetate, or a silver salt, preferably silver acetate.
- the acid is preferably hydrochloric acid.
- it is also possible to use a metal complex for example a palladium complex salt, such as a salt of a palladium-aminopyridine complex.
- the metal compound in process step C) is present in a concentration of 40 mg/l to 80 mg/l, based on the metal.
- the solution of the metal compound can be employed at a temperature of 25°C to 70°C, preferably at 25°C.
- the treatment time with the solution of a metal compound is 0.5 min - 10 min, preferably 2 min - 6 min and more preferably 3 min - 5 min.
- process step B ii) is more preferably performed between the protection of the racks and process step C).
- the treatment of the plastic surfaces in process step B ii) is also referred to as preliminary dipping, and the aqueous acidic solution used as a preliminary dipping solution.
- the preliminary dipping solution has the same composition as the colloid solution in process step C), without the presence of the metal in the colloid and the protective colloid thereof.
- the preliminary dipping solution in the case of use of a palladium/tin colloid solution in process step C), comprises exclusively hydrochloric acid if the colloid solution likewise comprises hydrochloric acid.
- brief immersion into the preliminary dipping solution at ambient temperature is sufficient. Without rinsing the plastic surfaces, they are treated further directly with the colloid solution of process step C) after the treatment in the preliminary dipping solution.
- Process step B ii) is preferably performed when process step C) involves the treatment of a plastic surface with a solution of a metal colloid.
- Process step B ii) can also be performed when process step C) involves the treatment of a plastic surface with a solution of a compound of a metal.
- the plastic surfaces are treated in process step C i) with an accelerator solution in order to remove constituents of the colloid in the colloid solution, for example a protective colloid, from the plastic surfaces.
- the accelerator solution used is preferably an aqueous solution of an acid.
- the acid is selected, for example, from the group comprising sulphuric acid, hydrochloric acid, citric acid and tetrafluoroboric acid.
- the accelerator solution helps to remove the tin compounds which served as the protective colloid.
- a red uctor treatment is performed when, in process step C), a solution of a metal compound has been used in place of a metal colloid for the activation.
- the reductor solution used for this purpose then comprises, if the solution of the metal compound was a hydrochloric acid solution of palladium chloride or an acidic solution of a silver salt, hydrochloric acid and tin (I I ) chloride.
- the reductor solution may also comprise another reducing agent, such as NaH 2 P0 2 or else a borane or borohydride, such as an alkali metal borane or alkaline earth metal borane or dimethylaminoborane. Preference is given to using NaH 2 P0 2 in the reductor solution.
- Process step C i) and optionally one or more rinse steps are followed by process step C ii) in which the plastic surfaces are metallized electrolessly.
- Electroless nickel-plating is accomplished, for example, using a conventional nickel bath which comprises, inter alia, nickel sulphate, a hypophosphite, for example sodium hypophosphite, as a reducing agent, and also organic complexing agents and pH adjusters (for example a buffer).
- the reducing agent used may likewise be dimethylaminoborane or a mixture of hypophosphite and dimethylaminoborane.
- an electroless copper bath for electroless copper-plating typically comprising a copper salt, for example copper sulphate or copper hypophosphite, and also a reducing agent, such as formaldehyde or a hypophosphite salt, for example an alkali metal or ammonium salt, or hypophosphorous acid, and additionally one or more complexing agents such as tartaric acid, and also a pH adjuster such as sodium hydroxide.
- a copper salt for example copper sulphate or copper hypophosphite
- a reducing agent such as formaldehyde or a hypophosphite salt, for example an alkali metal or ammonium salt, or hypophosphorous acid
- complexing agents such as tartaric acid
- a pH adjuster such as sodium hydroxide
- the surface thus rendered conductive can subsequently be electrolytically further metallized in order to obtain a functional or decorative surface.
- Step D) of the process according to the invention is the metallization of the plastic surface with a metallization solution.
- the metallization in process step D) can be effected electrolytically.
- electrolytic metallization it is possible to use any desired metal deposition baths, for example for deposition of nickel, copper, silver, gold, tin, zinc, iron, lead or alloys thereof.
- deposition baths are familiar to those skilled in the art.
- a Watts nickel bath is typically used as a bright nickel bath, this comprising nickel sulphate, nickel chloride and boric acid, and also saccharine as an additive.
- composition used as a bright copper bath is one comprising copper sulphate, sulphuric acid, sodium chloride and organic sulphur compounds in which the sulphur is in a low oxidation state, for example organic sulphides or disulphides, as additives.
- the effect of the metallization of the plastic surface in process step D) is that the plastic surface is coated with metal, the metal being selected from the above-listed metals for the electrolytic deposition baths.
- the protection of the rack has the effect that the rack is not, or the racks are not, coated with metal and thus remain free from metal.
- the adhesion strength between metal and plastic substrate increases in the first period after the application of the metal layer. At room temperature, this process is complete after about three days. This can be accelerated considerably by storage at elevated temperature. The process is complete after about one hour at 80°C. It is assumed that the initially low adhesion strength is caused by a thin water layer which lies at the boundary between metal and nonconductive substrate and hinders the formation of electrostatic forces. The treatment of the metallized plastic surfaces at elevated temperature is thus advantageous.
- Such a step may involve treating a copper-metallized article made of ABS plastic at elevated temperature in the range from 50°C to 80°C for a period between 5 minutes and 60 minutes, preferably at a temperature of 70°C, in a water bath, in order that the water can be distributed at the metal-plastic interface in the plastic matrix.
- the effect of the treatment or storage of the metallized plastic surfaces at elevated temperature is that an initial, relatively low adhesion strength is enhanced further, such that, after process step D i), an adhesion strength of the metal layer applied to the plastic surface which is within the desired range of at least or greater than 0.8 N/mm is achieved.
- the process according to the invention thus enables metallization of the racks to be avoided, and simultaneously, with good process reliability and excellent adhesion strength of the subsequently applied metal layers, achievement of metallization of electrically nonconductive plastic surfaces of articles.
- the adhesion strength of the metal layers applied to plastic surfaces reaches values of 0.8 N/mm or higher.
- the adhesion strengths achieved are also well above those obtainable according to the prior art.
- the process according to the invention is suitable not just for metallizing planar plastic surfaces but also inhomogeneously shaped plastic surfaces, for example shower heads, with successful avoidance of the metallization of the racks.
- the treatment of the plastic surfaces by the process according to the invention is preferably performed in a conventional dipping process, by dipping the articles successively into solutions in vessels, in which the respective treatment takes place.
- the articles may be dipped into the solutions either fastened to racks or accommodated in drums. Fastening to racks is preferred.
- the articles can also be treated in what are called conveyor plants, by lying, for example, on trays and being conveyed continuously through the plants in horizontal direction.
- Example 1 inventive example
- An ABS moulding (shower head) was fastened to a PVC-coated holding rack (process step A)).
- a PVC-coated holding rack For this example, an old holding rack having a particularly strong tendency to rack metallization was selected.
- a treatment time of 10 minutes was again followed by rinsing under water and removal of adhering manganese dioxide in a solution of 50 g/l 96% sulphuric acid and 30 ml/1 30% hydrogen peroxide (process step B i), see Table 2).
- the rack with the ABS moulding was treated in a solution with various concentrations of potassium iodate (0, 5, 10, 20, 40 g/l) in 50 g/l 96% sulphuric acid at 50°C for 10 minutes (protection of the rack).
- process step B ii Subsequent rinsing and brief dipping into a solution of 300 ml/l 36% hydrochloric acid (process step B ii) was followed by activation in a colloidal activator based on a palladium colloid (Adhemax Activator PL from Atotech, 25 ppm of palladium) for three minutes (process step C), see Table 2). Subsequent rinsing was followed by removal of the protective shells of the palladium particles at 50°C for 5 minutes (Adhemax ACC1 accelerator from Atotech, process step C i), see Table 2). The ABS moulding was subsequently nickel-plated at 45°C without external current for 10 minutes (Adhemax LFS, from Atotech, process step C ii)) and then rinsed.
- Adhemax Activator PL from Atotech, 25 ppm of palladium
- hydrochloric acid approx. 10% by weight 1 min 20°C dipping
- Example 2 Inventive Example
- valve caps round mouldings of diameter of about 7 cm
- ABS plastic Novodur P2MC
- Electroless nickel-plating was additionally followed by electrolytic copper-plating for 70 minutes (Cupracid HT from Atotech, 3.5 A/dm 2 , room temperature, process step D)). After rinsing, the valve caps were stored at 80°C for 30 minutes (process step D i)). Subsequently, a tensile tester (from Instron) was used to pull the metal layer away from the plastic (ASTM B 533 1985 Reapproved 2009), and the adhesion strength was thus determined. Adhesion strengths of the metal layers to the plastic of the valve caps of 1.14 N/mm and 1 .17 N/mm were found.
- the coverage of the rack with metal was 4% of the rack surface area and was thus likewise negligible.
- a treatment time of ten minutes was again followed by rinsing under water for one minute, and the now dark brown panels were cleaned to remove deposited manganese dioxide in a solution of 50 g/l 96% sulphuric acid and 30 ml/l 30% hydrogen peroxide.
- the panels were activated in a colloidal activator based on a palladium colloid (Adhemax Aktivator PL from Atotech, 25 ppm of palladium) at 45°C for three minutes.
- the protective shells of the palladium particles were removed at 50°C for five minutes (Adhemax ACC1 accelerator from Atotech).
- the panels were subsequently nickel-plated at 45°C without external current for ten minutes (Adhemax LFS, from Atotech), rinsed and copper-plated at 3.5 A/dm 2 at room temperature for 70 minutes (Cupracid HT, from Atotech).
- the panels were stored at 80°C for 1 hour. Subsequently, a knife was used to cut out a strip of each metallized plastic panel of width about 1 cm, and a tensile tester (from Instron) was used to pull the metal layer away from the plastic (ASTM B 533 1985 Reapproved 2009).
- the adhesion strengths of the metal layers are shown in Figure 3 and summarized in Table 3.
- the residence time of the plastic surfaces in the solution of the glycol compounds has an influence on the adhesion strength of the metal layers applied. Without treatment with glycol compounds (residence time 0 min in Figure 3), only an adhesion strength of 0.25 N/mm was obtained. After treatment with glycol compounds for only 5 minutes, in contrast, a good adhesion strength of 0.92 N/mm was already achieved, and this rises further with longer treatment time.
- Panel 1 front side 1.09 N/mm.
- reverse side 1.27 N/mm
- Panel 2 front side 1.30 N/mm.
- reverse side 1.32 N/mm
- the panels were rinsed under running water for one minute and then treated in a bath of 100 g/l sodium permanganate and 10 g/l 96% sulphuric acid, which was kept at 70°C (process step B)).
- a treatment time of 10 minutes was again followed by rinsing under water and removal of adhering manganese dioxide in a solution of 25 ml/1 96% sulphuric acid and 30 ml/1 30% hydrogen peroxide (process step B i), see Table 6).
- both panels were rinsed and briefly dipped into a solution of 300 ml/1 36% hydrochloric acid (process step B ii). These steps were followed by activation in a colloidal activator based on a palladium colloid (Adhemax NA from Atotech, 25 ppm of palladium) for five minutes (process step C), see Table 6). Subsequent rinsing was followed by removal of the protective shells of the palladium particles at 50°C for 4 minutes (Adhemax ACC1 accelerator from Atotech, process step C i), see Table 6). The ABS panels were subsequently nickel-plated at 45°C without external current for 10 minutes (Adhemax Ni LFS, from Atotech, process step C ii)) and then rinsed.
- Adhemax NA from Atotech, 25 ppm of palladium
- panel 1 was electrolytically copper-plated for 60 minutes (Cupracid HT from Atotech, 3.5 A/dm 2 , room temperature, process step D)). After rinsing, the panel was stored at 75°C for 30 minutes (process step D i)). Subsequently, the adhesion strength was determined as described in Example 2. Results are summarized in Table 5 and the sequence of process steps in Example 6 is summarized in Table 6.
- Rack 1 About 25 % of rack area was coated with nickel.
- Panel 1 Complete area of panel was plated with nickel and copper.
- Adhesion strength of nickel-copper layers 1 .14 N/mm, 1.10 N/mm, 1.12 N/mm, mean value: 1 .12 ⁇ 0.02 N/mm
- Panel 2 Complete area of panel was plated with nickel.
- Example 7 An ABS panel (same dimensions as in Example 6) was treated as described in Example 6. In contrast to Example 6 the etching step (step B) and the reducing step (step B i) were omitted and replaced by the treatment with an iodate solution (step: rack protection). The sequence of process steps in Example 7 is summarized in Table 7.
- Panel Complete area of panel was plated with nickel. Nickel layer did not adhere to the panel surface.
- Example 6 An ABS panel (same dimensions as in Example 6) was treated as described in Exampli 6. In contrast to Example 6 the treatment with an iodate solution (step: rack protection) was performed after the activation step (step C). An overview of the sequence of process steps in Example 8 is given in Table 7.
- Example 6 An ABS panel (same dimensions as in Example 6) was treated as described in Example 6. In contrast to Example 6 the accelerating step (step C i) was omitted and replaced by the treatment with an iodate solution (step: rack protection). The sequence of process steps in Example 9 is summarized in Table 7.
- Table 7 Overview of the sequence of process steps in Examples 7 to 9.
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Abstract
Description
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Priority Applications (8)
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CA2866766A CA2866766C (en) | 2012-03-15 | 2013-03-15 | Process for metallizing nonconductive plastic surfaces |
US14/376,857 US9181622B2 (en) | 2012-03-15 | 2013-03-15 | Process for metallizing nonconductive plastic surfaces |
ES13712718.9T ES2587104T3 (en) | 2012-03-15 | 2013-03-15 | Process to metallize non-conductive plastic surfaces |
KR1020147028815A KR101872065B1 (en) | 2012-03-15 | 2013-03-15 | Process for metallizing nonconductive plastic surfaces |
JP2014561461A JP6150822B2 (en) | 2012-03-15 | 2013-03-15 | Method for metallizing non-conductive plastic surface |
CN201380014373.8A CN104254641B (en) | 2012-03-15 | 2013-03-15 | Non-electricity is led to the method for metallization of plastic surface |
EP13712718.9A EP2825690B1 (en) | 2012-03-15 | 2013-03-15 | Process for metallizing nonconductive plastic surfaces |
BR112014021995-8A BR112014021995B1 (en) | 2012-03-15 | 2013-03-15 | METALIZATION PROCESS FOR NON-CONDUCTIVE PLASTIC SURFACES |
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EP12159652.2 | 2012-03-15 | ||
EP12159652.2A EP2639332A1 (en) | 2012-03-15 | 2012-03-15 | Method for metallising non-conductive plastic surfaces |
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WO2013135862A3 WO2013135862A3 (en) | 2013-11-07 |
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US (1) | US9181622B2 (en) |
EP (2) | EP2639332A1 (en) |
JP (1) | JP6150822B2 (en) |
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CN (1) | CN104254641B (en) |
BR (1) | BR112014021995B1 (en) |
CA (1) | CA2866766C (en) |
ES (1) | ES2587104T3 (en) |
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EP3181726A1 (en) | 2015-12-18 | 2017-06-21 | ATOTECH Deutschland GmbH | Etching solution for treating nonconductive plastic surfaces and process for etching nonconductive plastic surfaces |
EP3228729A1 (en) | 2016-04-04 | 2017-10-11 | COVENTYA S.p.A. | Process for metallization of an article having a plastic surface avoiding the metallization of the rack which fixes the article within the plating bath |
EP3059277B1 (en) | 2015-02-23 | 2019-04-10 | MacDermid Enthone Inc. | Inhibitor composition for racks when using chrome free etches in a plating on plastics process |
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- 2013-03-15 CA CA2866766A patent/CA2866766C/en active Active
- 2013-03-15 KR KR1020147028815A patent/KR101872065B1/en active IP Right Grant
- 2013-03-15 WO PCT/EP2013/055356 patent/WO2013135862A2/en active Application Filing
- 2013-03-15 PT PT137127189T patent/PT2825690T/en unknown
- 2013-03-15 BR BR112014021995-8A patent/BR112014021995B1/en active IP Right Grant
- 2013-03-15 EP EP13712718.9A patent/EP2825690B1/en active Active
- 2013-03-15 ES ES13712718.9T patent/ES2587104T3/en active Active
- 2013-03-15 CN CN201380014373.8A patent/CN104254641B/en active Active
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CN104254641A (en) | 2014-12-31 |
CN104254641B (en) | 2016-05-18 |
JP6150822B2 (en) | 2017-06-21 |
ES2587104T3 (en) | 2016-10-20 |
KR20140138286A (en) | 2014-12-03 |
PT2825690T (en) | 2016-07-28 |
EP2825690A2 (en) | 2015-01-21 |
WO2013135862A3 (en) | 2013-11-07 |
JP2015513617A (en) | 2015-05-14 |
PL2825690T3 (en) | 2016-11-30 |
EP2639332A1 (en) | 2013-09-18 |
CA2866766A1 (en) | 2013-09-19 |
CA2866766C (en) | 2020-03-10 |
US20150001177A1 (en) | 2015-01-01 |
US9181622B2 (en) | 2015-11-10 |
KR101872065B1 (en) | 2018-06-27 |
BR112014021995B1 (en) | 2020-12-15 |
EP2825690B1 (en) | 2016-05-18 |
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