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WO2025021810A1 - Procédé pour munir des corps moulés en matière plastique d'un revêtement et moyen pour réaliser une surface microstructurée desdits corps moulés en matière plastique - Google Patents

Procédé pour munir des corps moulés en matière plastique d'un revêtement et moyen pour réaliser une surface microstructurée desdits corps moulés en matière plastique Download PDF

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Publication number
WO2025021810A1
WO2025021810A1 PCT/EP2024/070866 EP2024070866W WO2025021810A1 WO 2025021810 A1 WO2025021810 A1 WO 2025021810A1 EP 2024070866 W EP2024070866 W EP 2024070866W WO 2025021810 A1 WO2025021810 A1 WO 2025021810A1
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WIPO (PCT)
Prior art keywords
acid
plastic moldings
pretreatment
plastic
treatment
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PCT/EP2024/070866
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German (de)
English (en)
Inventor
Steffen Roos
Tobias Günther
Anika MAFFERT
Jürgen HOFINGER
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Biconex GmbH
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Biconex GmbH
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Publication of WO2025021810A1 publication Critical patent/WO2025021810A1/fr
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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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/14—Chemical modification with acids, their salts or anhydrides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers

Definitions

  • the invention relates to the fields of chemistry and mechanical engineering and relates to a method for coating plastic moldings which, for example, can be coated with various metals and used for various technical applications, such as in automobile construction, in the electronics industry, for example for high-frequency filters or high-frequency antennas, or in the jewelry industry, and a means for realizing a microstructured surface of the plastic moldings.
  • the metallization of plastic surfaces is usually carried out electrochemically in industry by immersing the plastic molded body in a bath of a salt solution of the metal to be applied after the molding process.
  • the bath also contains an anode made of the metal to be applied or an inert anode.
  • the metal is oxidized at the anode and passes into solution.
  • galvanic deposition the metal ions are reduced on the plastic molded part to be coated, which is connected as a cathode. This creates a metallic deposit. deposited on the plastic molded part to be coated.
  • several layers of different or identical metals are applied. Reduction and oxidation reactions are made possible by providing an electric current.
  • the prerequisite for this process is that the plastic molded part is electrically conductive.
  • the electrical conductivity of the plastic molded parts for metallization is achieved after the molding process by applying metal salts that are reduced to metal nuclei or metal colloids. A first metal layer is then often applied to the surface, on which the metallization then takes place.
  • plastic surfaces require good adhesion of the nuclei and the first chemically applied metal layer to the surface of the plastic molded part in question.
  • the hydrophobic surface of the plastic molded part must first be chemically modified to enable good wetting with the electrolyte.
  • DE 39 01 029 A1 describes a process for metallizing molded bodies made of polyarylene sulfides, in which a glass non-corrosive oxidizing agent acts on the molded bodies before activation.
  • Polyarylene sulfides containing 3-40% polycarbonate or polyarylene ester, 2.5-15% polyamide or polyester and 2-20% of a rubber elastomer are used, with the exception of TiO2 and MgCO3 as fillers for polycarbonates, polyarylene esters, polyamide and polyester.
  • Bromine solutions, concentrated sulfuric acid or chromic sulfuric acid or mixtures thereof with phosphoric acid or organic peracids are used as oxidizing agents.
  • WO 2009/133751 A1 also discloses a metallized molded body and a method for its production.
  • the metallized molded body has a coating layer of conductive polymer particles with a binder, which is deposited on the surface of the molded body to be metallized, on which a metal layer is formed by electroless coating through adsorption of a catalyst metal.
  • EP 3 414 364 B1 is a method for pretreating surfaces of plastic parts for electroplating, in which a plastic pretreatment dip solution is prepared with at least undissociated peroxomonosulfuric acid and undissociated sulfuric acid and the plastic parts to be coated are dipped into the plastic pretreatment dip solution.
  • the plastics are modified at least on the surface.
  • ABS plastics are strongly swollen by the acids in the pretreatment agent in a layer of approx. 1 pm on the surface.
  • the oxidizing agents in the pretreatment agent can then penetrate into the swollen plastic and oxidize the butadiene contained therein.
  • the oxidation of the butadiene causes the butadiene to foam due to the gas evolution and the inorganic acid present in the pretreatment agent can penetrate into the foamed surface. This creates a microstructured surface on the ABS plastics.
  • a comparable microstructured surface can also be achieved with molded bodies made of filled polyphenylene sulfide (PPS).
  • PPS polyphenylene sulfide
  • the plastic matrix and sometimes also the fillers are oxidized or displaced at different rates by the oxidizing agents.
  • EP 0 435 212 A1 discloses a process for pretreating the metal coating of a molded body made of a resin which contains as main components a polyphenylene sulfide resin, reinforcing fillers made of glass and optionally one or more other thermoplastic resins.
  • the molded body made of the resin is first dipped into an oxidative acid solution, then into a liquid containing an organic polar solvent and then into a solvent which dissolves the reinforcing fillers made of glass and the thermoplastic resin.
  • Hydrogen peroxide and sulfuric acid can be used as the oxidative acid solution
  • N-methylpyrrolidone or dimethylacetamide can be used as the organic polar solvent and sulfuric acid and/or an aqueous alkali solution can be used as the solvent.
  • the disadvantage of the known solutions is that the adhesive strength of the coatings on plastic moldings is still insufficient, or that numerous and/or complex process steps have to be carried out before coating the plastic moldings in order to improve the adhesive strength.
  • Another disadvantage is the high surface roughness of the plastic moldings after coating.
  • the object of the present invention is to provide a method for coating plastic moldings which is simpler and more cost-effective and achieves good adhesion and/or low surface roughness of the coating on the plastic moldings, as well as to provide a means for achieving a microstructured surface of the plastic moldings, which achieves a hydrophilic and microstructured surface of the plastic moldings before chemical and/or galvanic coating.
  • plastic moldings which consist at least partially of a thermoplastic filled to at least 10 percent by mass and which have been subjected to a pretreatment in a liquid comprising at least one acid and an oxidizing agent and, directly after the pretreatment of the plastic moldings and before coating, the at least pretreated plastic moldings are subjected to a treatment in at least one acid which has a maximum of 5 millimoles of an oxidizing agent per liter of at least one acid for at least 1 minute and then the plastic moldings treated in this way are rinsed and/or cleaned and chemically and/or galvanically coated.
  • plastic moldings which consist of one or more thermoplastics filled to 20 to 80% by mass.
  • Polyphenylene sulfide, polyoxymethylene or polyetheretherketone are also advantageously used as thermoplastics.
  • plastic moldings are advantageously used which contain inorganic fillers, advantageously inorganic salts such as carbonates and/or sulfates and/or chlorides. It is also advantageous to use plastic moldings which consist at least partially of polyphenylene sulfide or polyoxymethylene or polyetheretherketone filled with calcium carbonate, calcium sulfate, magnesium carbonate or dolomite.
  • plastic molded bodies are used whose fillers are in the form of particles, fibers, spheres and/or geometrically shaped bodies.
  • the inorganic acid or acid mixture used during the pretreatment is used for the treatment of the pretreated plastic moldings, whereby it is even more advantageous to use an inorganic acid for the pretreatment of the plastic moldings and the treatment with an acid, which is again advantageously a concentrated sulfuric acid.
  • pretreated plastic moldings are subjected to treatment in at least one acid for between 1 and 30 minutes.
  • plastic molded bodies are rinsed and/or cleaned in at least one acid one to five times after treatment.
  • the plastic molded bodies are chemically or galvanically coated after treatment in at least one acid with or without rinsing and/or cleaning steps. It is also advantageous if, during the pretreatment of the plastic moldings, a mechanical stress on the pretreatment liquid is realized, advantageously by means of ultrasound, stirring, realization of a flow, turbulence, or the plastic moldings are moved in the pretreatment liquid.
  • the agent according to the invention for realizing a microstructured surface of plastic moldings for the coating of plastic moldings after a pretreatment and a directly subsequent treatment before the coating of plastic moldings consists of at least one acid with the exclusion of oxidizing agents, wherein the exclusion of oxidizing agents means that a maximum of 5 millimoles of an oxidizing agent are present per liter of acid.
  • the present invention provides for the first time a simple and cost-effective method for coating plastic moldings, which realizes good adhesion and/or low surface roughness of the coating on the plastic moldings, as well as a means for realizing a microstructured surface of the plastic moldings, which realizes a hydrophilic and microstructured surface of the plastic moldings.
  • plastic moldings This is achieved by the method according to the invention for coating plastic moldings. This makes it possible to coat plastic moldings that consist at least partially of a thermoplastic filled to at least 10% by mass.
  • thermoplastic(s) 20 to 80 mass% filled thermoplastic(s).
  • Polyphenylene sulfide, polyoxymethylene or polyetheretherketone are advantageously used as thermoplastics.
  • Thermoplastics can also be used that differ in the types of plastic or in the variants of identical types of plastic from different manufacturers, which usually result from minor differences in the manufacturing processes.
  • thermoplastic molded articles which contain inorganic fillers, even more advantageously inorganic salts as fillers, such as carbonates and/or sulfates and/or chlorides.
  • plastic moldings which consist at least partially of polyphenylene sulfide or polyoxymethylene or polyetheretherketone filled with calcium carbonate, calcium sulfate, magnesium carbonate or dolomite are used in the process according to the invention.
  • Fillers in the form of particles, fibers, spheres and/or geometrically shaped bodies are advantageously used in the thermoplastic molded bodies.
  • the plastic moldings used according to the invention are subjected to a pretreatment in a liquid comprising at least one acid and at least one oxidizing agent, wherein the oxidizing agent must be capable of at least oxidizing the plastic on the surface and in the region close to the surface and advantageously also of oxidizing the filler on the surface and in the region close to the surface.
  • the pretreatment parameters for the plastic moldings used can also be adapted to different types of plastic or to the variants of different manufacturers for identical types of plastic.
  • the acid used in the pretreatment must also be able to dissolve the oxidized plastic parts and, if applicable, the oxidized fillers at least from the surface.
  • An inorganic acid is advantageously used as the acid.
  • the fillers on the surface of the thermoplastics can be at least partially removed from the surface of the thermoplastics by the acid and/or the oxidizing agent but also by other means or by mechanical or thermal means.
  • the pretreatment of the plastic moldings can be carried out in a liquid that contains not only sulfuric acid but also oxidizing agents such as peroxomonosulfuric acid. Both the acid and the oxidizing agents can advantageously be used partially or completely in undissociated form.
  • a liquid consisting of concentrated sulfuric acid, water and peroxy compounds as oxidizing agents is used for the pretreatment of the plastic moldings.
  • the precursors of the peroxy compounds can also be used, and the formation of the peroxy compounds then takes place in situ during the pretreatment of the plastic moldings.
  • thermoplastic itself to be at least partially oxidized on the surface and in the near-surface area, usually to a depth of up to several micrometers.
  • the fillers can also be oxidized.
  • the fillers in the plastic molded part are and should in any case be dissolved out of the plastic composite at the surface and in the area close to the surface, creating depressions in the plastic surface that form the microstructured surface of the plastic molded body and contribute to the realization and/or improvement of the adhesion of the metallization.
  • the oxidized and/or dissolved fillers and plastics are only partially removed from the surface during the pretreatment of the plastic moldings. After the pretreatment of the plastic moldings, relatively irregular Large and irregularly distributed residues of oxidized plastic and filler on the surface of the plastic molded parts.
  • the pretreatment of the plastic molded parts is immediately followed by treatment in at least one acid for at least 1 minute.
  • this treatment must be carried out in at least one acid with the exclusion of an oxidizing agent.
  • exclusion of an oxidizing agent in the context of the present invention means that the amount of oxidizing agent in the at least one acid is a maximum of 5 millimoles per liter.
  • the amount of oxidizing agents in the at least one acid is 0 to 3 millimoles per liter, particularly advantageously between 0 and 1 millimole per liter.
  • oxidizing agents are neither added to the at least one acid by oxidizing agents nor introduced into the at least one acid as precursors for an oxidizing agent, so that an oxidizing agent cannot form in situ in the at least one acid in concentrations higher than a maximum of 5 millimoles per liter of the at least one acid.
  • oxidizing agents can be introduced due to the technical implementation and/or by the introduction of oxidizing agents from previous treatment steps.
  • acids which themselves have an oxidizing effect are used in a treatment step prior to coating, these are either not used or used in small quantities, or acids which have only a slight oxidizing effect on the plastic are used.
  • the relatively irregularly large and irregularly distributed residues of oxidized Plastic and possibly also oxidized filler on the surface of the plastic molded parts can be essentially completely removed and the cleaned and microstructured surface of the plastic molded parts can be provided with a well-adhering coating.
  • thermoplastics and/or the fillers it is advantageous if a mechanical stress on the pretreatment liquid is realized during the pretreatment of the plastic moldings, advantageously by means of ultrasound, stirring, realization of a flow, turbulence, or the plastic moldings are moved in the pretreatment liquid.
  • the pretreatment and the treatment according to the invention take place in at least one acid with the exclusion of an oxidizing agent, each using the same acid, advantageously an inorganic acid. This further excludes further contamination.
  • the pretreated plastic moldings are subjected to treatment in at least one acid for between 1 min and 30 min, excluding an oxidizing agent.
  • the plastic moldings treated in this way are rinsed and/or cleaned, can be activated with a catalyst, and chemically coated, i.e. without external current, and optionally also galvanically coated afterwards.
  • the number and length of the rinsing and cleaning steps correspond to those of the known state of the art.
  • Chemical and galvanic coating are also carried out using state-of-the-art processes.
  • the process according to the invention essentially completely removes the relatively irregularly large and irregularly distributed residues of oxidized material that have formed and remain during the pretreatment of the plastic moldings and that adhere more or less firmly to the plastic surface from the surface of the plastic moldings. For the subsequent chemical and/or galvanic coating, this means that a complete and well-adhering metallization of the plastic molding surface and a smooth surface of the metallization are achieved.
  • the object is achieved by a means for realizing a microstructured surface of the plastic moldings, which realizes a microstructured surface of the plastic moldings before coating.
  • a means for realizing a microstructured surface of the plastic moldings for the coating of plastic moldings after a pretreatment and a directly subsequent treatment before coating the surfaces of the plastic moldings which consists at least of at least one acid with exclusion of oxidizing agents, whereby the exclusion of oxidizing agents means that a maximum of 5 millimoles of an oxidizing agent are present per liter of acid.
  • At least one inorganic acid is present.
  • the exclusion of oxidizing agents also means that the amount of oxidizing agents in the at least one acid is a maximum of 5 millimoles per liter, advantageously between 0 and 3 millimoles per liter, particularly advantageously between 0 and 1 millimole per liter.
  • the agent can contain a maximum of 5 millimoles per litre due to the technical implementation of the process and/or due to the introduction of oxidising agents from previous treatment steps.
  • the means according to the invention for realizing a microstructured surface of the plastic moldings before coating removes the irregularly large and irregularly distributed residues of oxidized material on the surface and in the near-surface area of pretreated plastic moldings after pretreatment and before coating.
  • the filler still present on the surface and in the near-surface area of the plastic moldings is at least partially dissolved out and can also be at least partially oxidized and/or removed.
  • the at least partial removal of the fillers from the plastic composite creates a microstructured surface that significantly improves the adhesion of the subsequently applied coating.
  • the coating is applied to three plastic molded bodies in the form of injection-molded plates made of PPS from Toray (Torelina A310MB6) as a thermoplastic with a filler content of glass fibers and mineral particles of 65 mass%.
  • the dimensions of the plates were 80 mm by 80 mm and 3 mm thick.
  • the plates were first cleaned and degreased and then dried. A mixture of sulfuric acid and hydrogen peroxide was used as the etching solution for pretreatment as an oxidizing agent, resulting in 78% sulfuric acid with a total oxidizing agent content of 35 mM (millimoles). The plates were exposed to the etching solution for 2.5 minutes.
  • the copper layer on the plates was cut with a saw at a distance of one centimeter after drying and the resulting copper strip was detached from the component over a length of 1 cm and clamped into a Mecmesin Multitest 2.5i material testing machine to measure the peel strength in accordance with DIN EN 1464.
  • the strip was peeled off at a speed of 50 mm/s at an angle of 90°.
  • the measurements showed values between 2.9 N/cm and 3.7 N/cm for the peel force of the plates.
  • Example 2 The process was carried out up to the pretreatment as in Example 1 on three plastic moldings in the form of injection-molded sheets made of PPS from Toray (Torelina A310MB6) as a thermoplastic with a filler content of glass fibers and mineral particles of 65% by weight.
  • the dimensions of the sheets were again 80 mm by 80 mm with a thickness of 3 mm.
  • the plates were first cleaned and degreased and then dried. A mixture of sulfuric acid and hydrogen peroxide was used as the etching solution for the pretreatment as an oxidizing agent, resulting in 78% sulfuric acid with a total oxidizing agent content of 35 mM. The plates were exposed to the etching solution for 2.5 minutes.
  • the injection-molded PPS sheets as plastic moldings were completely immersed in an acid solution with the exclusion of an oxidizing agent, consisting of 78% sulfuric acid with an addition of 0.1 g/l of the surfactant sodium lauryl sulfate (SDS), directly after pretreatment.
  • an oxidizing agent consisting of 78% sulfuric acid with an addition of 0.1 g/l of the surfactant sodium lauryl sulfate (SDS), directly after pretreatment.
  • SDS sodium lauryl sulfate
  • the total content of oxidizing agents in the solution was determined by oxidizing an iron stock solution.
  • an iron stock solution containing 19 g of iron(II) sulfate and 1.5 g of ammonium iron(II) sulfate was dissolved in 45 ml of deionized water and the concentration was then determined by titration with potassium permanganate. 2 ml of this iron stock solution were added to a mixture of 50 ml of deionized water and 1 ml of the solution to be determined and the concentration was again determined using a potassium permanganate titration.
  • the decrease in Fe2+ ions due to the addition of the solution to be examined corresponds to twice the value of the oxidizing agents contained.
  • the measurement resulted in a value of 0.8 millimoles per liter of oxidizing agents.
  • the solution with the plates was placed in a laboratory ultrasound device (Bandelin Sonorex RK100) filled with water and exposed to 80 watts of ultrasound during the exposure. The samples were then rinsed with water at room temperature (20 °C).
  • the coated panels already had a more homogeneous appearance over the entire surface and very little roughness.
  • a measurement of the surface roughness using the method in Example 1 was carried out before and after the treatment of the panels and yielded the following values:
  • the coating was applied to three plastic molded bodies in the form of injection-molded plates made of polyphenylene sulfide (PPS) from DSM (Xytron M5710T black) as a thermoplastic with a filler content of glass fibers and mineral particles of 57% by weight.
  • PPS polyphenylene sulfide
  • DSM Xytron M5710T black
  • the dimensions of the plates were 80 mm by 80 mm and 3 mm thick.
  • the plates were first cleaned and degreased and then dried.
  • a mixture of sulphuric acid and hydrogen peroxide was used as the etching solution for the pre-treatment as an oxidizing agent, so that 79.5% sulphuric acid was obtained with a total oxidizing agent content of 50 mM.
  • the pickling solution was brought to a temperature of 40°C and the plates were completely immersed in the pickling solution for 1.5 minutes.
  • the plates were completely immersed in a bath consisting of 80% sulfuric acid at a temperature of 40°C for acid treatment, excluding an oxidizing agent.
  • the process was interrupted three times for a few seconds after 2 minutes each and the plates were lifted out of the bath. After the plates had been exposed in the bath for a further four minutes, the plates were then rinsed in water at 60°C for 10 minutes.
  • step 3 The further process steps for metal coating were carried out again according to Example 1, but in step 3, with the same exposure time of 7.5 minutes, a particularly active nickel bath Enplate Ni-817 (MacDermid Enthone) at pH 4.7 and a temperature of 85°C was used.
  • a particularly active nickel bath Enplate Ni-817 MacDermid Enthone
  • the values show that the initial surface roughness of the plastic panels has been reduced by the treatment.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé permettant de munir des corps moulés en matière plastique d'un revêtement et un moyen permettant de réaliser une surface microstructurée desdits corps moulés en matière plastique. L'invention se rapporte au domaine de la chimie et concerne un procédé permettant d'utiliser lesdits corps moulés en matière plastique revêtus de différents métaux dans le domaine de la construction automobile. La présente invention vise à mettre au point un procédé de revêtement de corps moulés en matière plastique, plus simple et plus économique, permettant d'obtenir une bonne adhérence et/ou une faible rugosité de surface du revêtement sur les corps moulés en matière plastique. A cet effet, l'invention porte sur un procédé selon lequel les corps moulés en matière plastique se composent au moins en partie d'une matière thermoplastique chargée à au moins 10% en masse, lesdits corps moulés en matière plastique ont été soumis à un traitement préalable dans un liquide composé d'au moins un acide et d'un oxydant et les pièces moulées en matière plastique prétraitées sont soumises directement après le traitement préalable et avant le revêtement à un traitement dans au moins un acide, lequel comporte au maximum 5 millimoles d'un oxydant par litre d'au moins un acide, pendant au moins 1 mn et sont revêtues par voie galvanique.
PCT/EP2024/070866 2023-07-27 2024-07-23 Procédé pour munir des corps moulés en matière plastique d'un revêtement et moyen pour réaliser une surface microstructurée desdits corps moulés en matière plastique Pending WO2025021810A1 (fr)

Applications Claiming Priority (2)

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DE102023120007.0A DE102023120007A1 (de) 2023-07-27 2023-07-27 Verfahren zur Beschichtung von Kunststoffformkörpern und Mittel zur Realisierung einer mikrostrukturierten Oberfläche der Kunststoffformkörper
DE102023120007.0 2023-07-27

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US20230142233A1 (en) * 2020-04-28 2023-05-11 Kurita Water Industries Ltd. Etching method for resin molded article and etching process system for resin molded article

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