EP4341464A1 - Bâti destiné à être utilisé dans un procédé de décapage de pièces en plastique destinées à être revêtues de métal - Google Patents

Bâti destiné à être utilisé dans un procédé de décapage de pièces en plastique destinées à être revêtues de métal

Info

Publication number
EP4341464A1
EP4341464A1 EP22730434.2A EP22730434A EP4341464A1 EP 4341464 A1 EP4341464 A1 EP 4341464A1 EP 22730434 A EP22730434 A EP 22730434A EP 4341464 A1 EP4341464 A1 EP 4341464A1
Authority
EP
European Patent Office
Prior art keywords
plastic
frame
plasticizer
sulfonic acid
alkyl sulfonic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22730434.2A
Other languages
German (de)
English (en)
Inventor
Johannes DRESCHER
Sarah Schmitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Delta Engineering & Chemistry GmbH
Original Assignee
Delta Engineering & Chemistry GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Delta Engineering & Chemistry GmbH filed Critical Delta Engineering & Chemistry GmbH
Publication of EP4341464A1 publication Critical patent/EP4341464A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • 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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/2053—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 only one step pretreatment
    • C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/06—Suspending or supporting devices for articles to be coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/06—Suspending or supporting devices for articles to be coated
    • C25D17/08—Supporting racks, i.e. not for suspending
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron

Definitions

  • the present invention relates to a frame for receiving a plastic part to be metallized and a method for metallizing a plastic part.
  • plastic objects are provided with a suitable metal layer for decorative or technical reasons.
  • Decorative metalized plastic surfaces are widely used, particularly in the area of automotive production.
  • metallization is carried out, for example, in order to form electrically conductive structures on the plastic surfaces.
  • plastic parts are therefore treated prior to metal deposition.
  • the plastic parts are chemically etched in a first step. This creates pores on the surface of the plastic parts, which serve as appropriate anchoring for the later deposited metal layer.
  • the plastic parts are treated with a pickling solution containing sulfuric acid containing chromium(VI).
  • pickling solutions based on chromium-sulfuric acid can contain, for example, chromium(VI) oxide and sulfuric acid in a weight ratio of 1:1.
  • chromium(VI)-containing sulfuric acid pickling solutions are, for example, stains based on permanganates.
  • pickling solutions based on alkali metal permanganates, such as potassium permanganate, and a mineral acid, such as phosphoric acid are known.
  • Electroplating racks are commonly used to metalize many plastic parts at the same time.
  • Such frames conduct the electric current to the plastic part to be metallized, which is fixed in a favorable position for the metallization process by the contact wires of the frame. So that the metal to be deposited is deposited only on the plastic parts to be metallized and not on the frame itself, the frames are covered with a plastic that insulates them.
  • This plastic is usually polyvinyl chloride (PVC). Phthalic acid ester is usually included as a plasticizer.
  • the plastic parts to be metallized are mounted on the frame at the beginning of the metallization process.
  • the frame and the plastic parts to be metalized that are mounted on it are then brought into contact with the pickling solution. This is followed by the metallization of the pickled plastic parts mounted on the frame without first being mounted on a new frame.
  • chromium-free pickling solutions such as pickling solutions based on permanga nates, it was found that in the metallization step that follows the pickling step, not only the metalized plastic parts, but also the PVC-based plastic that covers the frame.
  • WO 2020/095152 describes a method in which the metallization is to be prevented by inhibition with a C8-C18 thiol.
  • the object is achieved by a frame for holding a plastic part to be metallized, the frame being covered by a plastic, the plastic covering the frame comprising polyvinyl chloride and at least one plasticizer, the at least one plasticizer being an alkyl sulfonic acid ester or a mixture of alkylsulfonic acid esters.
  • the plastic that covers the frame is different than the plastic of the plastic part to be metalized.
  • the frame for holding a plastic part to be metallized is an electroplating frame on which at least one part to be metallized Plastic part can be attached.
  • the plastic part to be metallized should be provided with a metal layer for decorative or technical reasons.
  • the frame for accommodating a plastic part to be metallized can be made of metal and is covered by a plastic material which includes polyvinyl chloride and at least one plasticizer.
  • Plastic compositions comprising PVC and at least one plasticizer are also referred to as PVC plastisols.
  • a plastisol is a dispersion of a plastic and optionally other additives in at least one plasticizer.
  • the plastic that covers the frame is typically a different plastic than the plastic that makes up the plastic part to be metalized.
  • the plastic covering the frame may include one plasticizer or two or more plasticizers.
  • the at least one plasticizer is an alkyl sulfonic acid ester or a mixture of alkyl sulfonic acid esters.
  • a rack conducts electricity and includes brackets for receiving plastic objects and contact wires for transmitting electricity to the plastic objects. Except in the area of the contact wires, the frame is coated with a plastic.
  • the plastic covering the frame includes polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the polyvinyl chloride is emulsion-polymerized PVC with k-values of 60-90 (e.g. VESTOLIT E 7031, E 7037, both manufacturers Vestolit GmbH), micro-suspension-polymerized PVC with k-values of 60 -90 (e.g. VESTOLIT B 7021 Ultra, manufacturer Vestolit GmbH or Vinnolit P70, manufacturer Vinnolit GmbH & Co. KG), suspension-polymerized PVC with k values of 60-90 (e.g. VESTOLIT S 6058, manufacturer Vestolit GmbH) or mixtures of them.
  • 60-90 e.g. VESTOLIT E 7031, E 7037, both manufacturers Vestolit GmbH
  • micro-suspension-polymerized PVC with k-values of 60 -90 e.g. VESTOLIT B 7021 Ultra, manufacturer Vestolit GmbH or Vinnolit P70, manufacturer Vinnolit GmbH & Co. KG
  • the k value (also referred to as inherent viscosity) is determined by measuring the viscosity of polymer solutions. It serves as a measure of the molar mass of polymers. Methods for determining the k value of various types of PVC are known to those skilled in the art.
  • the polyvinyl chloride is post-chlorinated polyvinyl chloride.
  • the polyvinyl chloride is a mixture of at least one of the aforementioned types of PVC with PVC-vinyl acetate copolymers or with PVC-polyacrylic ester copolymers (e.g. Vinnolit S 3157/11, Vinnolit K 704, manufacturer Vinnolit GmbH & Co. KG, VINNOL H15/45 M, manufacturer Wacker Chemie AG).
  • the polyvinyl chloride may be a blend of two or more of the types of polyvinyl chloride described in the preferred embodiments above.
  • the plastic covering the frame comprises 45 to 75% by weight polyvinyl chloride, more preferably 50 to 65% by weight polyvinyl chloride.
  • Plasticizers are used as solvents in the manufacture of plastisols.
  • PVC powder can be dispersed with the plasticizers.
  • a PVC plastisol is thereby obtained.
  • the proportion and type of plasticizer and the types of PVC used determine the physical and chemical properties of the PVC plastisols obtained.
  • the physical and chemical properties of the PVC plastisols obtained can be influenced by any other additives present (eg stabilizers, colored pigments, fillers, deaerating agents, drying agents and/or viscosity regulators).
  • the PVC plastisol can exhibit Newtonian, pseudo-plastic or dilatant flow behavior.
  • the PVC plastisol is usually applied to the parts to be coated by immersion, casting or rotational molding.
  • plasticizer diffuses into the PVC polymer.
  • Suitable conditions for thermal treatment are known to those skilled in the art.
  • So-called primary plasticizers such as phthalic acid esters (phthalates), trimellitic acid esters (trimellitates), phosphoric acid esters (phosphates), polymer plasticizers (polyesters) and alkyl pyrrolidones can be mixed with polyvinyl chloride over a wide concentration range.
  • Secondary plasticizers such as adipic acid esters (adipates), azealic acid esters (azelates) and sebacic acid esters (sebazates) have a lower polarity than primary plasticizers and are mostly used in combination with primary plasticizers.
  • Extenders such as chlorinated paraffins alone are incompatible with polyvinyl chloride and can only be used in combination with primary plasticizers.
  • Organic solvents that do not have plasticizing properties have a diluting effect, but cannot replace the function of the plasticizer and cannot be used alone to produce PVC plastisols.
  • the at least one plasticizer contained in the plastic covering the frame according to the invention is preferably an alkylsulfonic acid ester of phenol or a mixture of alkylsulfonic acid esters of phenol.
  • the alkyl sulfonic acid esters of phenol can be alkyl sulfonic acid esters or alkyl disulfonic acid diphenyl esters.
  • the mixtures of alkyl sulfonic acid esters can be mixtures of alkyl sulfonic acid esters and/or alkyl disulfonic acid diphenyl esters.
  • the at least one plasticizer is preferably (C10-C21) Alkanesulfonic acid phenyl ester.
  • C10-C21 examples of commercially available (C10-C21) phenyl alkanesulfonate are Mesamoll and Mesamoll II (manufacturer Lanxess).
  • the at least one plasticizer is a mixture of secondary phenyl alkanesulfonates, secondary diphenyl alkanedisulfonates and non-sulfonated alkanes. Before given to it is a mixture of
  • non-sulfonated alkanes with alkyl chains of the secondary phenyl alkanesulfonate, the secondary diphenyl alkanedisulfonate and the non-sulfonated alkanes preferably having a chain length of 13 to 17 carbon atoms.
  • the at least one plasticizer is preferably contained in the plastic covering the frame in an amount of between 25 and 55% by weight, more preferably in an amount of between 35 and 50% by weight.
  • the plastic that covers the frame can include other plasticizers in addition to the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters.
  • the other plasticizers can be, for example, phthalates such as diisononyl phthalate, didecyl phthalate, diundecyl phthalate, diisotridecyl phthalate, butylcyclohexyl phthalate or octyldecyl phthalate, adipates such as diethylhexyl adipate, diethyloctyl adipate, diisononyl adipate, dibutyl adipate or octyldecyl adipate, benzoates such as isodecyl benzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate or triethylene glycol dibenzoate, to citrates such as acetyl phthalate,
  • the plastic covering the frame has a total plasticizer content of between 25 and 55% by weight, more preferably between 35 and 50% by weight.
  • the proportion of the alkylsulfonic acid ester or the mixture of alkylsulfonic acid esters is preferably at least 50% by weight, more preferably at least 55% by weight, more preferably at least 60% by weight, more preferably at least 65% by weight %, more preferably at least 70% by weight, more preferably at least 80% by weight, more preferably at least 85% by weight and even more preferably at least 90% by weight, based in each case on the Total plasticizer content in the plastic.
  • the proportion of the additional plasticizer or additional plasticizers is preferably at most 50% by weight, more preferably at most 45% by weight, more preferably at most 40% by weight, more preferably at most 35% by weight, more preferably at most 30% by weight, more preferably at 20% by weight, more preferably at most 15% by weight and even more preferably at most 10% by weight, based in each case on the total plasticizer content in the plastic.
  • the plastic that covers the frame comprises, in addition to the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters, 15% by weight or less, preferably 5% by weight or less, of other plasticizers, based on the total plasticizer content in the plastic.
  • the plastic preferably comprises 5% by weight or less plasticizer from the group of phthalic acid esters (phthalates) and/or from the group of terephthalic acid esters (terephthalates), based on the total plasticizer content in the plastic.
  • the plastic that covers the frame does not include a plasticizer from the group of phthalic acid esters (phthalates) and/or from the group of terephthalic acid esters (terephthalates) in addition to the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters.
  • a plasticizer from the group of phthalic acid esters (phthalates) and/or from the group of terephthalic acid esters (terephthalates) in addition to the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters means that less than 10 ppmw of these plasticizers are present, determined using gas chromatography coupled to mass spectrometry (GC/MS). Methods for determining the phthalate and terephthalate content in plastics by means of GC/MS are known to those skilled in the art.
  • the plastic covering the frame does not include any further plasticizers apart from the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters.
  • the fact that no further plasticizer is included in addition to the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters means that less than 10 ppmw of a further plasticizer are present, determined by means of gas chromatography coupled to mass spectrometry (GC/MS). Methods for determining the plasticizer content in plastics by means of GC/MS are known to those skilled in the art.
  • the plastic that covers the frame comprises only one alkyl sulfonic acid ester or a mixture of alkyl sulfonic acid esters as a plasticizer. It is preferably an alkylsulfonic acid ester of phenol or a mixture of alkylsulfonic acid esters of phenol. It is more preferably a (C10-C21) alkanesulfonic acid phenyl ester.
  • the alkyl sulfonic acid esters of phenol can be alkyl sulfonic acid esters or alkyl disulfonic acid diphenyl esters.
  • the mixtures of alkyl sulfonic acid esters can be mixtures of alkyl sulfonic acid esters and/or alkyl disulfonic acid diphenyl esters.
  • the plastic preferably does not comprise any C8-C18 thiol compound, ie less than 0.01% by weight, based on the plastic.
  • the plastic preferably does not comprise any thiol compound, ie less than 0.01% by weight, based on the plastic.
  • the plastic preferably comprises no further metallization inhibitor, i.e. less than 0.01% by weight, based on the plastic.
  • the plasticizer can also be a mixture of
  • the plastic that covers the frame can also include other additives, such as stabilizers.
  • the stabilizers can be temperature or heat stabilizers.
  • the temperature stabilizers can be preparations of barium, calcium, zinc, tin and cadmium compounds as well as inorganic lead salts.
  • the temperature stabilizers are preferably barium, calcium or zinc compounds or mixtures thereof or stabilizers based on calcium and zinc.
  • metal hydroxides, polyols, ß-diketones, organic phosphites or epoxides can be used as co-stabilizers.
  • the stabilizers are preferably present in an amount of 0.5 to 5% by weight.
  • the plastic covering the frame may additionally include fillers. These fillers affect the physico-chemical properties of the Plastic coatings and lead to a further improvement in the resistance of the plastic coating to the pickling solutions used.
  • the plastic that covers the frame can also include fluorinated polymers (such as polytetrafluoroethylene (PTFE) or ethylene chlorotrifluoroethylene (ECTFE)), polyamide, polypropylene, polyethylene or polycarbonate as additional additives.
  • fluorinated polymers such as polytetrafluoroethylene (PTFE) or ethylene chlorotrifluoroethylene (ECTFE)
  • PTFE polytetrafluoroethylene
  • ECTFE ethylene chlorotrifluoroethylene
  • polyamide polypropylene
  • the further additives are preferably contained in an amount of 1 to 25% by weight, more preferably in an amount of 5 to 10% by weight.
  • the invention also relates to a method for metallizing a plastic part, comprising the steps:
  • a plastic part to be metallized is attached to a frame according to the invention.
  • Plastic parts that are mounted on the frame can all have the same shape or size or have different shapes or sizes.
  • the frame together with the at least one plastic part to be metallized mounted thereon is brought into contact with a pickling solution.
  • the frame can be immersed in the pickling solution. It is also possible to spray the frame, together with the at least one plastic part to be metalized mounted thereon, with the pickling solution.
  • the plastic part to be metallized can be pickled with the help of the pickling solution. This creates pores on the surface of the plastic part.
  • the at least one pickled plastic part to be metallized that is mounted on the frame is metallized.
  • the frame, together with the at least one etched plastic part to be metallized mounted on it, is brought into contact with compositions that are suitable for depositing a metal layer on an etched plastic surface.
  • the pickled plastic parts are left on the same rack that was previously contacted with the pickling solution and do not have to be mounted on a new rack.
  • the pickling solution can be a chromium(VI)-containing pickling solution or a chromium-free pickling solution. It is preferably a chromium-free pickling solution. It is preferably a chromium-free pickling solution based on manganese compounds, in particular based on Mn(III) or permanganates. Such mordants based on manganese compounds are known to those skilled in the art.
  • Other chromium-free pickling solutions for example pickling solutions based on sulfur trioxide, perchlorate or ozone, can also be used.
  • the frame is preferably not metallized during the metallization of the at least one plastic part to be metallized.
  • Another object of the invention is the use of a plastic for covering a frame for holding a plastic part to be metalized, the plastic comprising polyvinyl chloride and at least one plasticizer, the at least one plasticizer being an alkyl sulfonic acid ester or a mixture of alkyl sulfonic acid esters.
  • the plastic used according to the invention for covering a frame for receiving a plastic part to be metalized is the plastic already described above, which covers the frame according to the invention. All the statements made above with regard to the composition and the properties of the plastic that covers the frame according to the invention also apply to the plastic that is used according to the invention to coat a frame for receiving a plastic part to be metalized.
  • the plastic comprising polyvinyl chloride and the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters is used to coat a frame for receiving at least one plastic part to be metallized, when the frame and the plastic parts to be metallized attached thereto are brought into contact with compositions which have a Cause metal deposition on the plastic part to be metallized, not metallization of the frame. This metallization also does not occur if the frame covered by the plastic together with the plastic parts to be metallized mounted thereon were previously treated with a pickling solution.
  • the alkylsulfonic acid ester or the mixture of alkylsulfonic acid esters ensure that the plastic that covers the frame for holding the plastic part to be metalized is not pickled during the pickling process. As a result, during the metalization of the plastic part to be metalized, no metalization of the plastic covering the frame takes place.
  • a further object of the invention is the use of an alkyl sulfonic acid ester or mixtures of alkyl sulfonic acid esters in a plastic which comprises polyvinyl chloride to prevent the metalization of the plastic during the metalization of a plastic part to be metalized.
  • the alkyl sulfonic acid esters or the mixtures of alkyl sulfonic acid esters can act as plasticizers in the plastic.
  • the plastic that is obtained by using the alkylsulfonic acid ester or the mixtures of alkylsulfonic acid esters according to the invention is the plastic already described above, which covers the frame according to the invention. All the statements made above with regard to the composition and properties of the plastic covering the frame according to the invention also apply to the plastic obtained by using the alkylsulfonic acid ester or the mixtures of alkylsulfonic acid esters according to the invention.
  • the alkyl sulphonic acid ester or the mixtures of alkyl sulphonic acid esters can be used in an amount between 25 and 55% by weight, more preferably in an amount between 35 and 50% by weight in the plastic. If, for example, other plasticizers are used in addition to the alkylsulfonic acid ester or the mixtures of alkylsulfonic acid esters, the alkylsulfonic acid esters or the mixtures of alkylsulfonic acid esters are used in an amount which ensures that the total plasticizer content is between 25 and 55% by weight. %, more preferably between 35 and 50% by weight.
  • the plastic in which the alkyl sulfonic acid ester or mixtures of alkyl sulfonic acid esters are used, coats a frame for receiving a plastic part to be metallized.
  • the use of the alkyl sulfonic acid ester or the mixture of alkyl sulfonic acid esters in the plastic means that when the frame, together with the plastic parts to be metallized attached thereto, is brought into contact with compositions that cause metal deposition on the plastic part to be metallized, there is no metallization of the frame . This metalization also does not occur if the frame, together with the plastic parts to be metalized mounted on it, was previously treated with a pickling solution.
  • a preferred embodiment of the invention is an electroforming frame, the electroforming frame being covered by a plastic, the plastic comprising polyvinyl chloride and at least one plasticizer, the at least one plasticizer being an alkyl sulfonic acid ester or a mixture of alkyl sulfonic acid esters.
  • a preferred embodiment of the invention is a method for protecting an electroformed frame from metallization during chrome-free pickling, comprising covering the electroformed frame with a plastic, the plastic comprising polyvinyl chloride and at least one plasticizer, the at least one plasticizer being an alkyl sulfonic acid ester or a mixture of alkylsulfonic acid esters.
  • the plastic in which the alkyl sulfonic acid ester or the mixtures of alkyl sulfonic acid esters are used and which covers the frame for receiving the plastic part to be metallized preferably differs from the plastic from which the plastic part to be metallized is made. Unless otherwise stated, all volumes are measured at 23°C.
  • FIG. 1 shows a photograph of a stainless steel plate partially metallized on the upper and right edge and provided with a PVC coating after 5 passes through the plastic metallization process using a manganese-based stain.
  • the PVC plastisol used for the coating contains the plasticizer diisononyl phthalate in a concentration of 50 pphp (parts per 100 parts PVC).
  • the PVC plastisol used is a comparison composition.
  • a clear dark discoloration can be seen on the upper and right edge of the plate. This is the partial metal layer deposited on the coated stainless steel plate. No metallization can be observed in the middle of the plate. This gray area represents the non-metallized PVC coating.
  • Figure 2 shows a photograph of a PVC-coated stainless steel panel after 150 passes through the plastic metallization process using a manganese-based stain.
  • the PVC plastisol used to coat the plate contains 75 pphp Mesamoll (manufacturer Lanxess) as a plasticizer.
  • the edge has no dark discoloration—that is, no metallization.
  • an electroforming frame was coated once, or multiple times, with a plastic comprising polyvinyl chloride and at least one plasticizer (PVC plastisol) by means of a dipping process. This water was then cured. Alternatively, in some tests, stainless steel plates were also coated with the PVC plastisols mentioned and cured. Tests with PVC coatings of different compositions are described below. Their suitability as a coating for a frame for receiving a plastic part to be metalized was evaluated relatively. To evaluate the durability of the PVC coatings in a) chromium-free manganese-based stain and b) chromium-sulfuric acid stain, sample frames or panels were coated once or several times with the plastic compositions and cured under suitable conditions.
  • PVC plastisol plasticizer
  • the resistance of the sample coatings in plastic metallization processes using a manganese-based stain was determined in a test facility under production conditions.
  • HSO EcoBond ® manufactured by the manufacturer. The pickling and coating conditions recommended by the manufacturer were used. It was determined after how many pickling and coating cycles a change in the surface texture or metallization of the surface could be detected.
  • plasticizer 30% by weight based on the total weight of the PVC plastisol.
  • stabilizers, additives, color pigments and fillers were used to regulate the paste properties of the PVC plastisols, such as viscosity and thermal stability.
  • a galvanic frame was coated with a thin film of the respective PVC plastisol using the dip drawing process.
  • the sample parts coated in this way showed in some cases severe discoloration and partial metallization in electroless nickel (EN Ecoplast 601, manufacturer Herbert Schmidt GmbH). This is shown by way of example for a stainless steel plate coated with a PVC plastisol containing 50 pphp diisononyl phthalate (FIG. 1).
  • the parts showed poor drainage of the electrolytes used in electroplating, indicating that the PVC coatings were attacked during the pickling process.
  • a PVC powder (VESTOLIT P1430 K70, manufacturer Vestolit GmbH) was mixed with the plasticizers DINP (manufacturer Evonik) and Mesamoll II (manufacturer Lanxess) dispersed. Sample frames were coated with the PVC plastisol obtained. DINP and Mesamoll II were contained in the PVC plastisol at a concentration of 37.5 pphp each. This corresponds to a total amount of plasticizer of 43% by weight based on the total weight of the PVC plastisol. The proportion of Mesamoll II and DINP is each 50% by weight based on the total plasticizer content in the plastic.
  • PVC plastisols containing the PVC VESTOLIT P1430 K70 (manufacturer Vestolit GmbH) and as a plasticizer either 56 pphp (33% by weight based on total weight), 75 pphp (40% by weight based on total weight) or 85 pphp (43% by weight based on total weight) Mesamoll (manufacturer Lanxess), coated.
  • the PVC coatings obtained in this way which contained only Mesamoll as a plasticizer in the formulation, proved to be particularly stable in the plastic electroplating process using the manganese pickling process.
  • the PVC coatings which only contained Mesamoll as a plasticizer, also proved to be particularly stable to chromic acid pickling.
  • Sample parts coated with these PVC plastisols showed excellent resistance both in the plastic electroplating process using the manganese pickling process and to chromic sulfuric acid. Even after 150 passes through the plastic electroplating process using the manganese pickling process, the PVC coatings showed no metallization whatsoever.
  • the PVC coatings obtained in this way which contained Mesamoll as the main plasticizer in the formulation, also proved to be particularly stable in the plastic electroplating process using the manganese pickling process.
  • a PVC coating with 65 pphp of Mesamoll in combination with 10 pphp of Fast Gelling Agent also showed no metallization after 150 passes through the plastic metallization process using a manganese based stain.
  • the PVC coatings also proved to be particularly stable to chromium-sulfuric acid pickling.

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Abstract

L'invention concerne un bâti destiné à recevoir une pièce en plastique destinée à être revêtue de métal, le bâti étant recouvert d'une matière plastique et la matière plastique recouvrant le bâti comprenant du polychlorure de vinyle et au moins un plastifiant, le ou les plastifiants étant un ester d'acide alkylsulfonique ou un mélange d'esters d'acide alkylsulfonique.
EP22730434.2A 2021-05-21 2022-05-23 Bâti destiné à être utilisé dans un procédé de décapage de pièces en plastique destinées à être revêtues de métal Pending EP4341464A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP21175430 2021-05-21
EP21179826 2021-06-16
PCT/EP2022/063910 WO2022243568A1 (fr) 2021-05-21 2022-05-23 Bâti destiné à être utilisé dans un procédé de décapage de pièces en plastique destinées à être revêtues de métal

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EP4341464A1 true EP4341464A1 (fr) 2024-03-27

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EP22730434.2A Pending EP4341464A1 (fr) 2021-05-21 2022-05-23 Bâti destiné à être utilisé dans un procédé de décapage de pièces en plastique destinées à être revêtues de métal

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Publication number Priority date Publication date Assignee Title
DE102007044689A1 (de) 2007-09-19 2009-04-02 Lanxess Deutschland Gmbh Schnell gelierende Weichmacherzubereitungen
IT201800010168A1 (it) 2018-11-08 2020-05-08 Montaldi S R L Inibitore di metallizzazione per attrezzature di trattamenti galvanici

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