PREVENTION OF UNWANTED PLATING ON FRAME COATINGS FOR ELECTRODEPOSITING

Abstract

A support for supporting a component to be plated in a chromic acid-free plating process, the support having a contact surface comprising iodine-treated and / or bromine-treated plastic.

Description

PREVENTION OF UNWANTED PLATING ON FRAME COATINGS FOR ELECTRODEPOSITING FIELD OF INVENTION The invention relates to a support for supporting a component to be plated in a chromic acid-free plating process, a plating apparatus for use in a chromic acid-free plating process, a method for treating a support for supporting a component to be plated in a chromic acid-free plating process, a process for plating a component, and the use of an iodine and / or bromine pretreatment on a support for supporting a component to be plated. BACKGROUND OF THE INVENTION Plastic plating (POP) is a technique with wide-ranging applications in industries such as automotive and bathroom and shower fixtures. The most common substrate for plating is an acrylonitrile, styrene, and butadiene copolymer known as ABS. This is a two-phase plastic consisting of a rigid acrylonitrile / styrene copolymer phase and a softer polybutadiene phase. Sometimes, the ABS polymer is combined with a percentage of polycarbonate to produce ABS / PC. To plate these components, they are mounted on metal frames. Ref. 333214 transmits the plating current to the components after the initial metallization stage. The metal plating racks are coated with a PVC plastisol coating to prevent the entire rack from being plated. The plating process for ABS involves etching the plastic to roughen the surface, ensuring good adhesion during subsequent plating steps and making the surface hydrophilic enough to fully wet when immersed in aqueous solutions. After etching, the non-conductive ABS must first be metallized with a thin layer of nickel or copper to make it electrically conductive for the subsequent plating operation. This is achieved by immersing plating racks that hold the ABS components in an aqueous solution of a catalyst (typically a palladium colloid), which deposits a thin layer of the catalyst onto the plastic surface. This then acts as a catalyst for a non-electrolytic nickel or copper plating process that produces a thin metallic layer on the ABS components.Such aqueous solutions of catalysts are known as activating solutions, and plastic surfaces treated in such baths are known as activated surfaces. The initial etching stage for ABS plating has traditionally been a solution of chromic and sulfuric acid that oxidizes (primarily) the polybutadiene phase of the ABS to produce the necessary roughness of the plastic. The chromic acid solution is highly penetrating, and some of it is absorbed by the PVC plastisol material of the rack coatings. After subsequent immersion in colloidal palladium, some of the colloid binds to the PVC plastisol but is inactivated by the absorbed chromic acid. Therefore, when the racks holding the ABS components are immersed in the non-electrolytic nickel or copper solution, the catalyst adsorbed on the ABS components catalyzes the deposition of copper or nickel onto the components, but due to the presence of chromic acid in the PVC plastisol of the rack coatings, no nickel or copper is deposited on the rack coatings. Chromic acid is a category 1 carcinogen and is subject to increasing legislative pressure. Its use is currently being phased out in Europe. It can currently only be used for a few authorized applications, and even this limited use is likely to be further restricted to the point of elimination. Recently, a new method for etching ABS plastic has been developed using a combination of acids with manganese(III) ions (see, for example, Pearson's US9534306B2 and US10260000B2, the appendices of which are incorporated herein by reference). However, manganese-based etchings do not inhibit the palladium colloid bound to PVC plastisol coatings effectively enough to prevent nickel or copper deposition during the non-electrolytic deposition stage of the POP process. Several patents have been issued detailing compounds that can be used to treat PVC frame coatings to avoid this problem (e.g., EP3059277B1 by Noffke, US9506150B2 by Weitershaus, US9181622B2 by Middeke, and applications US2015233011A1 by Herdman and US2019112712A1 by Dalbin, the appendices of which are incorporated herein by reference).Most of the compounds currently used are organosulfur compounds. While these are effective at preventing nickel or copper deposition during the non-electrolytic plating stage, they can cause a surprising problem during the galvanizing stages. This problem is that, although there is no detestable nickel or copper on the PVC plastisol coatings after immersion in the non-electrolytic process, the frames are subsequently coated with copper during the acid copper plating stage that follows the initial metallization of the ABS components. Without wishing to be bound by theory, this is most likely due to the reaction of copper ions with the organosulfur compounds adsorbed on the PVC coatings, leading to the formation of copper sulfide.This is a p-type semiconductor with high specific conductivity, and, without being bound by theory, this is considered the main reason for the tendency of plating racks to be coated with copper. Therefore, there is a need for an improved method to inhibit plating on PVC rack coatings during ABS and ABS / PC plating when using processing technology that does not involve the use of chromic acid. WO2015 / 150156A1 relates to a composition and a process for metallizing non-conductive plastic surfaces. WO2013 / 135862A2 relates to a process for metallizing non-conductive plastic surfaces. The processes in both documents use iodate (IO3⁻) solutions to pretreat a plating frame. Since no reducing agent is present in the solutions, the iodate ions remain as iodate ions and do not form iodine, i.e., I2⁻. The effect of such pretreatment is described as providing special protection to the plastic housing of the frames against metal deposition. One problem with such processes is that it is not possible to confirm whether the frame has been pretreated or not, as there is no visual change in the frame after pretreatment.Consequently, the pretreatment stage must be carried out each time the deposit process is performed, or alternatively, the risk must be accepted that the pretreatment has not been carried out or has disappeared / become ineffective. BRIEF DESCRIPTION OF THE INVENTION The present invention seeks to address at least some of the problems associated with the prior art or at least to provide a commercially acceptable alternative solution to them. In particular, the present invention seeks to provide an improved support for use in a chromic acid-free plating process. In a first aspect, the present invention provides a support for supporting a component to be plated in a chromic acid-free plating process; the support has a contact surface comprising iodine-treated and / or bromine-treated plastic. The inventors have surprisingly discovered that when a component is mounted on the substrate during a chromic acid-free plating process, there may be substantially no copper or nickel deposit on the substrate during a non-electrolytic deposition stage, and there may also be substantially no deposit on the substrate during a subsequent galvanizing stage. Not being bound by theory, it is considered that, unlike organosulfur-treated substrates, the contact surface of the substrate of the present invention is not significantly activated such that it is plated in an acid copper galvanizing process. While iodate-treated plastics have been described in the prior art as resistant to metal deposition, it is surprising that this effect is also exhibited by iodine- and / or bromine-treated plastics. This is because iodate and iodine are chemically very different: iodate is an ionic species (IO3⁻), containing iodine atoms in the +5 oxidation state combined with oxygen atoms, whereas iodine is a covalent species (I2⁻) containing only iodine atoms in the elemental state (oxidation state of zero). Each aspect or modality as defined herein may be combined with any other aspect or modality unless explicitly stated otherwise. In particular, any feature listed as preferred or advantageous may be combined with any other feature listed as preferred or advantageous. When introducing elements of the present description or the preferred embodiment(s) thereof, the brackets a, an, the, and the are intended to signify that there is one or more of the elements. The terms comprising, including, and having are intended to be inclusive and mean that there may be additional elements besides those listed. The term consisting of is intended to mean that no elements other than those listed may be present. The term essentially consisting of is intended to mean that no elements other than those listed may be present unless the other elements do not materially affect the basic and novel features of the invention. The substrate is for use in a chromic acid-free plating process, preferably a plastic plating (POP) process. The plating process is substantially free of chromic acid, particularly substantially free of chromic acid during the etching stage of the plating process. The contact surface of the substrate is the (external) surface that comes into contact with the etching and plating solutions during a typical treatment process. Typically, substantially the entire contact surface of the substrate comprises iodine-treated and / or bromine-treated plastic, more typically the entire contact surface of the substrate. The contact surface of the support comprises (or essentially consists of) iodine-treated and / or bromine-treated plastic. "Treated" means that the plastic contains iodine and / or bromine, typically through contact with an iodine and / or bromine solution (i.e., I₂ and / or Br₂). Without being subject to theory, it is considered that, as a result of this contact, the iodine and / or bromine (i.e., I₂ and / or Br₂) infuses into the surface of the plastic. In other words, the iodine-treated and / or bromine-treated plastic may be iodine-infused and / or bromine-infused plastic (i.e., molecular iodine / I₂-infused plastic and / or molecular bromine / Br₂-infused plastic), respectively. The infusion of iodine and / or bromine into the plastic can be observed by a color change, typically brown for iodine-infused plastic and orange for bromine-infused plastic.Since the use of iodine and / or bromine changes the color of the plastic, in contrast to the use of iodate solutions in conventional processes, the present invention allows a user to identify whether the plastic has been treated or not. Over time and / or with prolonged use, the effect of the iodine and / or bromine treatment may diminish, and the color of the plastic may change accordingly, allowing an operator to identify when further treatment of the substrate may be required. The contact surface comprises plastic treated with iodine and / or bromine. The contact surface preferably comprises plastic treated with iodine. While still effective, bromine is not as persistent on the plastic surface as iodine. The plastic preferably comprises (or essentially comprises or consists of) PVC, more preferably PVC plastisol. PVC, or polyvinyl chloride, is produced by the polymerization of the vinyl chloride monomer. PVC plastisol comprises a suspension of PVC particles in a liquid plasticizer. Treatment of such materials with iodine and / or bromine can be particularly effective in inhibiting plating during non-electrolytic plating and / or galvanizing. The support preferably comprises metal at least partially coated with plastic. The presence of the metal allows the transmission of a plating current to a component supported by the support during an electroplating process. The metal preferably comprises copper and / or iron alloys. The metal can function as an electrode (cathode or anode) during an electroplating process. Specifically, the support for holding the components is typically made of metal to transmit electrical current to the components during electroplating. The components are typically held in place on the support by contacts or spring clips, hereinafter referred to as support clips. To transmit current, these support clips necessarily have a small uncoated area so that electrical contact is maintained during the processing of the components.The remainder of the support is coated with an insulating plastic covering, typically PVC, to prevent the entire support from being galvanized. This coated surface is referred to hereafter as the support contact surface. Typically, the portion of the support where contact is made with the electrical supply to provide the galvanizing current, usually at the top of the support, is not coated since it is not immersed in the treatment solutions. The support preferably comprises a plating frame. A plating frame is particularly suitable for supporting one or more components during a plating process. Suitable shapes and configurations of the frames are known in the art. The frame may comprise, for example, one or more support hooks or fasteners for supporting a component during a plating process. The frame may also include a cathode and / or anode for use in an electroplating process. In a further aspect, the present invention comprises a plating apparatus for use in a chromic acid-free plating process, the plating apparatus comprising a plating container having one or more supports for supporting a component to be plated, the one or more supports having a contact surface comprising iodine-treated and / or bromine-treated plastic. To avoid any doubt, the advantages and preferable features of other aspects of the invention apply equally to this aspect. The support may be the support described in this description. The plating pot typically has a suitable shape and dimensions to hold a component to be plated during a plating process. Such plating pots are known in the art. The inner surface, i.e., the contact surface, of the pot is typically substantially inert to the etching and plating solutions used in the plating process. In a further aspect, the present invention provides a method for treating a support for supporting a component to be plated in a chromic acid-free plating process, the support having a contact surface comprising plastic, the method comprising: to provide a support to support a component to be plated in a chromic acid-free plating process, the support has a contact surface comprising plastic; provide an aqueous solution comprising one or both of iodine and bromine; and bring at least a portion of the plastic of the support's contact surface into contact with the aqueous solution. To avoid any doubt, the advantages and preferable features of other aspects of the invention apply equally to this aspect. Similar to the first aspect, when the substrate is used during a chromic acid-free plating process, there may be substantially no copper or nickel deposit on the substrate during a subsequent non-electrolytic deposition stage, and there may also be substantially no deposit on the substrate during a subsequent galvanizing stage. The treatment may result in the support described herein. The support may include, for example, a veneered frame. The plastic contact surface of the holder may come into contact with a component that will be plated during plating, and may come into contact with the etching and / or plating solutions used in the plating process. The aqueous solution comprises one or both of iodine and bromine, i.e., molecular iodine (I2) and molecular bromine (Brz). Bringing at least a portion of the plastic of the support's contact surface into contact with the aqueous solution typically comprises at least partially immersing the support in the aqueous solution, more typically fully immersing the support in the aqueous solution. The contact can be carried out, for example, between ambient temperature and 100 °C. Since ambient temperatures work adequately, it is preferred to carry out the method at ambient temperatures to reduce costs and improve safety. The aqueous solution primarily consists of iodine. While still effective, bromine is not as persistent on the plastic surface as iodine. The aqueous solution preferably comprises, but is not limited to, 0.005 to 0.1 M iodine, more preferably 0.01 to 0.05 M iodine. The use of such iodine concentrations is particularly effective in inhibiting plating on the substrate during a plating process. The aqueous solution primarily comprises iodide ions. Iodine (I₂) is not particularly soluble in water. The presence of iodide ions can increase the solubility of iodine in the aqueous solution. For example, the presence of iodide ions can allow the formation of an aqueous solution containing up to 12% iodine. The iodide can be introduced into the aqueous solution in the form of, for example, potassium iodide. The molar ratio of iodide to iodine ions in aqueous solutions is preferably at least 1:1, more preferably at least 1.5:1, and even more preferably at least 2:1. Such ratios can allow the aqueous solution to contain a favorably high amount of iodine. Alternatively, other suitable means could be employed to increase the solubility of iodine, for example, introducing a cosolvent in an amount effective to produce the desired concentration of soluble iodine. Suitable solvents are numerous and may include, but are not limited to, ML / t / ZUZZ / U4 I0 alcohols, glycols and alkylene carbonates. The step of providing the aqueous solution preferably comprises contacting iodide ions with iodate ions in the aqueous solution. From a commercial point of view, it is not preferable to dissolve iodine in, for example, potassium iodide solution, to provide iodine and iodide ions in the aqueous solution. Advantageously, contacting iodide ions with iodate ions leads to the in situ generation of iodine according to the following chemical reaction: 103' + 51- + 6H+-» 3H2O + 3I2 As an alternative to iodate ions, other oxidizing agents capable of oxidizing iodide ions to iodine could be used; for example, persulfate ions, nitrate ions, or hydrogen peroxide could be used. The invention is not limited by the type of oxidizing agent used to oxidize the iodide ions to iodine. Iodide ions are typically present in excess of the oxidizing agent. When the aqueous solution comprises bromine, the bromine can also be generated in situ using a corresponding bromate / bromide reaction. The support is preferably placed in contact with the aqueous solution for at least 10 seconds, more preferably at least 30 seconds, even more preferably 1 to 10 minutes, even more preferably 1 to 5 minutes. Such contact times can result in the substrate being particularly resistant to plating. Longer contact times may result in only a negligible improvement in plating resistance. The plastic of the substrate's contact surface preferably comprises (or essentially consists of) PVC, more preferably PVC plastisol. Treatment of such materials with iodine and / or bromine can be particularly effective in inhibiting plating on these materials during non-electrolytic plating and / or galvanizing. The plating process preferably comprises plating with ABS polymer and / or ABS / PC polymer. Such plating processes are particularly susceptible to causing plating on other plastic substrates used in the process, such as plastic supports. ABS, or acrylonitrile butadiene styrene, has the chemical formula (CsHs) x · (C4H6)y· (C3H3N)z and is a common thermoplastic polymer known in the art. ABS / PC comprises a mixture of acrylonitrile butadiene styrene and polycarbonate. In an additional aspect, the present invention provides a method for manufacturing the support described herein, the method comprising the treatment method described herein. To avoid any doubt, the advantages and preferable features of other aspects of the invention apply equally to this aspect. In a further aspect, the present invention provides a process for plating a component, the process comprising: to provide a component to be plated, the component has an outer surface comprising a plastic; providing a plating apparatus comprising a plating container having one or more supports for supporting a component to be plated, the one or more supports having a contact surface comprising iodine-treated and / or bromine-treated plastic; mount the component on a plating appliance bracket to provide a mounted component; to bring at least a portion of the plastic of the outer surface of the assembled component into contact with an electrolyte to at least partially etch the plastic to form an etched surface of the component, the electrolyte being substantially free of chromic acid; to contact at least a portion of the etched surface of the component with an activating solution to form an activated surface of the component; and to contact at least a portion of the activated surface of the component with a non-electrolytic nickel solution or a non-electrolytic copper solution to form a plated surface of the component. To avoid any doubt, the advantages and preferable features of other aspects of the invention apply equally to this aspect. The plating apparatus may comprise the plating apparatus as described herein. The support may comprise the support as described herein. Before contacting at least a portion of the plastic surface of the assembled component with an electrolyte, a pre-etching step can be performed. This might involve, for example, contacting at least a portion of the plastic surface with a mixture of aqueous solvents containing propylene carbonate and butyrolactone. Such a pre-etching step is not always necessary, but it can modify the plastic surface so that it is more easily etched. Suitable chromic acid-free electrolytes are known in the art. Bringing at least a portion of the plastic outer surface of the mounted component into contact with the electrolyte preferably comprises at least partially immersing the mounted component in the electrolyte, and more preferably, completely immersing the mounted component in the electrolyte. The contact may be made at room temperature. However, the contact is preferably made at elevated temperatures, for example, at temperatures above room temperature, more preferably above 30°C, even more preferably above 50°C, and even more preferably above 60°C. Such elevated temperatures can help provide a suitable level of etching.To avoid electrolyte loss, contact is preferably made at a temperature below 100 °C, more preferably below 90 °C, and even more preferably below 80 °C. Contact is preferably maintained for at least 30 seconds, more preferably at least one minute, even more preferably at least five minutes, even more preferably from one to thirty minutes, and even more preferably from five to twenty minutes. Such contact times can provide an adequate level of etching. Suitable activating solutions are known in the art. Bringing at least a portion of the etched surface of the component into contact with the activating solution preferably comprises at least partially immersing the etched component in the activating solution, and more preferably, completely immersing the etched component in the activating solution. The contact is typically made at room temperature, although elevated temperatures may be used. The contact is preferably made for at least 30 seconds, more preferably for at least one minute, and even more preferably for 1 to 20 minutes, and even more preferably for 1 to 10 minutes. Before contacting at least a portion of the etched surface of the component with the activator solution, the etched surface may be contacted with an acid, for example, hydrochloric acid. This is because typical activators comprise colloids that sometimes exhibit limited stability in water. If the wet plastic surface is immersed directly in the colloid solution, the colloid on the plastic surface may become unstable. Suitable non-electrolytic nickel and non-electrolytic copper solutions are known in the art. Typical non-electrolytic solutions comprise nickel or copper ions together with a reducing agent such as, for example, a hypophosphite reducing agent. Contacting at least a portion of the activated surface of the component with a non-electrolytic nickel or non-electrolytic copper solution preferably comprises at least partially immersing the activated component in the non-electrolytic nickel or non-electrolytic copper solution, and more preferably fully immersing the activated component in the non-electrolytic nickel or non-electrolytic copper solution. The component is typically rinsed, most typically in water, after coming into contact with the electrolyte and / or activating solution and / or non-electrolytic nickel solution and / or non-electrolytic copper solution and before the next stage. The component can typically comprise any plastic component that needs to be galvanized. Examples include automotive brackets (e.g., car grilles, headlight bezels, door handles, and decorative trim), shower accessory brackets, bathroom accessory brackets, household and furniture fittings, and electronic components (e.g., cameras, computers, phones). The iodine-treated and / or bromine-treated plastic preferably comprises (or essentially consists of, excluding iodine and / or bromine) PVC, most preferably PVC plastisol. The plastic of the outer surface of the component preferably comprises (or essentially consists of) ABS and / or ABS / PC. The etching electrolyte can be any suitable etching electrolyte that is substantially free of chromium(VI) and may include, for example, permanganate ions or another strong oxidizing agent. A preferred electrolyte comprises manganese(III) ions, preferably in a 9 to 15 molar sulfuric or phosphoric acid solution. Such an electrolyte is particularly effective for etching plastic without the use of chromic acid. The activator solution preferably comprises a precious metal colloid. More preferably, the precious metal colloid comprises a first core metal and a second colloid metal that colloidally surrounds the core. The core metal comprises at least one metal selected from the group consisting of silver, platinum, palladium, and nickel, with palladium being particularly preferred. The second colloid metal comprises at least one metal selected from the group consisting of tin and lead, with tin being particularly preferred. The core metal is capable of catalytically activating the deposition of non-electrolytic copper or non-electrolytic nickel. Such an activator solution is particularly effective in promoting the deposition of nickel or copper in the subsequent non-electrolytic plating stage. An example of a suitable commercially available activator is Evolve Activator from MacDermid Enthone. After contacting at least a portion of the etched surface of the component with an activator solution, at least a portion of the etched surface can be contacted with an accelerator solution. This can remove the colloidal metal from the core catalytic metal; otherwise, the catalytic metal may remain protected and be ineffective. In other words, the post-activator treatment removes the second colloidal metal from the activated surface, thereby exposing the first core metal and enabling catalytic function. Suitable accelerator solutions are known in the art. Accelerator solutions can vary widely in composition and can be acidic or alkaline. Preferably, the accelerator solution is acidic and, for example, may comprise chloride ions in combination with organic and inorganic acids.An example of a suitable commercially available accelerator is the Evolve Accelerator from MacDermid Enthone. Bringing at least a portion of the etched surface of the component into contact with the accelerating solution preferably comprises at least partially immersing the etched and activated component in the accelerating solution, and more preferably fully immersing the etched and activated component in the accelerating solution. The contact is typically carried out at an elevated temperature (e.g., 50 °C), although ambient or higher temperatures may be used. The contact is preferably carried out for at least 30 seconds, more preferably for at least one minute, and even more preferably for 1 to 20 minutes, and even more preferably for 1 to 10 minutes. In a preferred embodiment, the process further comprises galvanizing the plated surface of the component, wherein the substrate comprises metal coated at least partially with the iodine- and / or bromine-treated plastic. As described above, the presence of the metal may allow the transmission of a plating current to the component during the galvanizing process. The galvanizing preferably comprises copper galvanizing. In an additional aspect, the present invention provides a plated component according to the process described herein. To avoid any doubt, the advantages and preferable features of other aspects of the invention apply equally to this aspect. In an additional aspect, the present invention provides the use of an iodine and / or bromine pretreatment on a support to support a component to be plated, the use of which inhibits plating on the support during a chromic acid-free plating process, the support having a contact surface comprising plastic. To avoid any doubt, the advantages and preferable features of other aspects of the invention apply equally to this aspect. BRIEF DESCRIPTION OF THE FIGURES The invention will now be described with reference to the following non-limiting figures, in which: Figure 1 shows a schematic of an example of a support according to the present invention. Figure 2 shows a cross-section of part of the support in Figure 1 along line A - B. Figure 3 shows a schematic of an example of a plating apparatus according to the present invention. Figure 4 shows a flowchart of an example of a method according to the present invention. Figure 5 shows a flow diagram of an example of a process according to the present invention. DETAILED DESCRIPTION OF THE INVENTION With reference to Figures 1-3, an example of a plating frame (support) 1 for use in a chromic acid-free plating process according to the present invention is illustrated. The frame comprises a number of support hooks or fasteners 2 on which a component to be plated can be mounted during a plating process. The support has a contact surface comprising iodine- and / or bromine-treated plastic 3. The interior of the support may comprise metal 4. At least a portion of the metal 4 of the support fasteners 2 is not coated with the iodine- and / or bromine-treated plastic 3 so that it is capable of transmitting an electric current to the component during plating.Figure 3 shows a plating apparatus 5 for use in a chromic acid-free plating process. The plating apparatus 5 comprises a plating vessel 6 having one or more supports 1 having a contact surface comprising iodine-treated and / or bromine-treated plastic 3. With reference to Figure 4, a method 7 is shown for treating a support for supporting a component to be plated in a chromic acid-free plating process, the support having a contact surface comprising plastic, the method comprises: i. provide a support to support a component to be plated in a chromic acid-free plating process, the support having a contact surface comprising plastic; ii. provide an aqueous solution comprising one or both of iodine and bromine; and ii. bring at least a portion of the plastic of the support's contact surface into contact with the aqueous solution. With reference to Figure 5, a process 8 for plating a component is shown; the process comprises: a. provide a component to be plated, the component having an outer surface comprising a plastic; b. providing a plating apparatus comprising a plating container having one or more supports for supporting a component to be plated, the one or more supports having a contact surface comprising iodine-treated and / or bromine-treated plastic; c. mount the component in a plating apparatus holder to provide a mounted component; d. bringing at least a portion of the plastic of the outer surface of the assembled component into contact with an electrolyte to at least partially etch the plastic to form an etched surface of the component, the electrolyte being substantially free of chromic acid; e. bringing at least a portion of the etched surface of the component into contact with an activating solution to form an activated surface of the component; and f. to put at least a portion of the activated surface of the component into contact with a non-electrolytic nickel solution or a non-electrolytic copper solution to form a plated surface of the component. The process optionally also includes: g. galvanizing the plated surface of the component, and wherein the support comprises metal coated at least partially with the iodine-treated and / or bromine-treated plastic. The invention will now be described in relation to the following non-limiting examples. All examples used the same piece of PVC plastisol coating. Example 1 (Comparative example) A veneered frame with a PVC plastisol coating was treated using the following sequence (rinsing steps omitted for brevity): 1. Immersion in an aqueous solvent mixture containing 100 ml / 1 of propylene carbonate and 50 ml / 1 of butyrolactone at 35 °C for 3 minutes 2. Etched on a chrome-free etching tool based on the teachings of U.S. Patent No. 10260000B2 (MacDermid Enthone's Evolve Etch) at 68°C for 10 minutes 3. Immersion in a 30% hydrochloric acid solution at 35% w / w room temperature for 30 seconds 4. Immersion in a proprietary palladium colloid solution (MacDermid Enthone's Evolve Activator) at room temperature for 3 minutes. 5. Immersion in a patented accelerator solution (MacDermid Enthone's Evolve Accelerator 800) at 50 °C for 2 minutes 6. Immersion in a non-electrolytic nickel solution (Evolve EN-60 from MacDermid Enthone) at room temperature for 7 minutes After this treatment, the entire plated frame was coated with a nickel coating. Example 2 (Comparative example) A veneered frame with a PVC plastisol coating was treated using the following sequence (rinsing steps omitted for brevity): 1. Immersion in a solution containing 10 g / 1 of thiourea at 70 °C for 10 minutes 2. Immersion in an aqueous solvent mixture containing 100 ml / 1 of propylene carbonate and 50 ml / 1 of butyrolactone at 35 °C for 3 minutes 3. Etched on a chrome-free etching tool based on the teachings of U.S. Patent No. 10260000B2 (MacDermid Enthone's Evolve Etch) at 68°C for 10 minutes 4. Immersion in a 30% hydrochloric acid solution at 35% w / w room temperature for 30 seconds 5. Immersion in a proprietary palladium colloid solution (MacDermid Enthone's Evolve Activator) at room temperature for 3 minutes. 6. Immersion in a proprietary accelerator solution (MacDermid Enthone's Evolve Accelerator 800) at 50 °C for 2 minutes. Immersion in a non-electrolytic nickel solution (MacDermid Enthone's Evolve EN-60) at room temperature for 7 minutes. 8. Plating in an acid copper electrolyte at room temperature for 40 minutes at a current density of 2 Adm-2 It was observed that after stage 6, no nickel coating was observed on the frame, but after stage 7, there was a significant amount of copper plating on the PVC plastisol coating. Example 3 A veneered frame with a PVC plastisol coating was treated using the following sequence (rinsing steps omitted for brevity): 1. Immersion in a solution containing 0.05 M iodine at room temperature for 5 minutes 2. Immersion in an aqueous solvent mixture containing 100 ml / 1 of propylene carbonate and 50 ml / 1 of butyrolactone at 35 °C for 3 minutes 3. Etched on a chrome-free etching tool based on the teachings of U.S. Patent No. 10260000B2 (MacDermid Enthone's Evolve Etch) at 68°C for 10 minutes 4. Immersion in a 30% hydrochloric acid solution at 35% w / w room temperature for 30 seconds 5. Immersion in a proprietary palladium colloid solution (MacDermid Enthone Evolve Activator) at room temperature for 3 minutes. 6. Immersion in a proprietary accelerator solution (MacDermid Enthone's Evolve Accelerator 800) at 50 °C for 2 minutes. Immersion in a non-electrolytic nickel solution (MacDermid Enthone's Evolve EN-60) at room temperature for 7 minutes. 8. Plating in an acid copper electrolyte at room temperature for 40 minutes at a current density of 2 Adm-2 After this sequence, no nickel coating or copper plating was observed after treatment. This sequence was repeated for four additional cycles that omitted step 1. No plating was observed on the PVC plastisol during these cycles. It was confirmed that in the etching bath or any of the treatment steps, the iodine did not undergo any change to form iodate ions. Example 4 A veneered frame with a PVC plastisol coating was treated using the following sequence (rinsing steps omitted for brevity): 1. Immersion in a solution containing 0.01 M iodine at room temperature for 5 minutes. 2. Immersion in a mixture of aqueous solvents containing 100 ml / L of propylene carbonate and 50 ml / L of butyrolactone at 35 °C for 3 minutes. 3. Etched on a chrome-free etching tool based on the teachings of U.S. Patent No. 10260000B2 (MacDermid Enthone's Evolve Etch) at 68°C for 10 minutes 4. Immersion in a 30% hydrochloric acid solution at 35% w / w room temperature for 30 seconds 5. Immersion in a palladium colloid solution ML / t / ZUZZ / U4 I0 patented (MacDermid Enthone's Evolve Activator) at room temperature for 3 minutes. 6. Immersion in a proprietary accelerator solution (MacDermid Enthone's Evolve Accelerator 800) at 50 °C for 2 minutes. Immersion in a non-electrolytic nickel solution (MacDermid Enthone's Evolve EN-60) at room temperature for 7 minutes. 8. Plating in an acid copper electrolyte at room temperature for 40 minutes at a current density of 2 Adm-2 After this sequence, no nickel coating or copper plating was observed after treatment. This sequence was repeated for two additional cycles that omitted step 1. No plating was observed on the PVC plastisol during these cycles. It was confirmed that in the etching bath or any of the treatment steps, the iodine did not undergo any change to form iodate ions. Example 5 (Comparative example) Two plastisol frames with different PVC plastisol coatings were immersed in a potassium iodate solution (30 g / L) at 70 °C for 20 minutes. No color change was observed in the PVC plastisol of either frame. This is consistent with the colorless nature of potassium iodate solutions. The foregoing detailed description has been provided by way of explanation and illustration and is not intended to limit the scope of the appended claims. Many variations of the preferred embodiments currently illustrated in this description will be obvious to a person skilled in the art and remain within the scope of the appended claims and their equivalents. It is hereby stated that, as of this date, the best method known to the applicant for carrying out the aforementioned invention is the one that is clear from the present description of the invention.

Claims

CLAIMS Having described the invention as above, the following claims are claimed as property:

1. A support for supporting a component to be plated in a chromic acid-free plating process, the support having a contact surface, characterized in that it comprises plastic treated with iodine and / or treated with bromine.

2. The support according to claim 1, characterized in that the contact surface comprises iodine-treated plastic.

3. The support according to claim 1 or 2, characterized in that the plastic comprises PVC, preferably PVC plastisol.

4. The support in accordance with any of the preceding claims, characterized in that it comprises metal coated at least partially with plastic.

5. A plating apparatus for use in a chromic acid-free plating process, characterized in that it comprises a plating container having one or more supports for supporting a component to be plated, the one or more supports having a contact surface comprising iodine-treated and / or bromine-treated plastic.

6. A method for treating a support for supporting a component to be plated in a chromic acid-free plating process, the support having a contact surface comprising plastic, characterized in that it comprises: providing a support for supporting a component to be plated in a chromic acid-free plating process, the support having a contact surface comprising plastic; providing an aqueous solution comprising one or both of iodine and bromine; and contacting at least a portion of the plastic of the support's contact surface with the aqueous solution.

7. The method according to claim 6, characterized in that the aqueous solution comprises iodine.

8. The method according to claim 7, characterized in that the aqueous solution comprises 0.005 to 0.1 M iodine, preferably 0.01 to 0.05 M iodine.

9. The method according to claim 7 or 8, characterized in that the aqueous solution comprises iodide ions.

10. The method according to claim 8, characterized in that the molar ratio of iodide to iodine ions is at least 1:

1.

11. The method according to any of claims 7 to 10, characterized in that the step of providing the aqueous solution comprises contacting iodide ions with an oxidizing agent in aqueous solution, the oxidizing agent being selected from iodate ions, persulfate ions, nitrate ions, hydrogen peroxide and combinations of two or more of these, preferably wherein the oxidizing agent comprises iodate ions.

12. The method according to any of claims 6 to 11, characterized in that the support is placed in contact with the aqueous solution for at least 10 seconds, preferably at least 30 seconds, more preferably from 1 to 10 minutes, even more preferably from 1 to 5 minutes.

13. The method according to any of claims 6 to 12, characterized in that the plastic of the contact surface of the support comprises PVC, preferably PVC plastisol.

14. The method according to any of claims 6 to 13, characterized in that the plating process comprises plating in ABS polymer and / or ABS / PC polymer.

15. A method for manufacturing the support according to any of claims 1 to 4, characterized in that it comprises the method according to any of claims 6 to 14.

16. A process for plating a component, characterized in that it comprises: providing a component to be plated, the component having an outer surface comprising a plastic; providing a plating apparatus comprising a plating container having one or more supports for supporting a component to be plated, the one or more supports having a contact surface comprising iodine-treated and / or bromine-treated plastic; mounting the component onto a support of the plating apparatus to provide a mounted component; contacting at least a portion of the plastic of the outer surface of the mounted component with an electrolyte to at least partially etch the plastic to form an etched surface of the component, the electrolyte being substantially free of chromic acid; contacting at least a portion of the etched surface of the component with an activating solution to form an activated surface of the component;and to bring at least a portion of the activated surface of the component into contact with a non-electrolytic nickel solution or a non-electrolytic copper solution to form a plated surface of the component.; 17. The process according to claim 16, characterized in that: the iodine-treated and / or bromine-treated plastic comprises PVC, preferably PVC plastisol; and / or the outer surface plastic of the component comprises ABS and / or ABS / PC.

18. The process according to claim 16 or 17, characterized in that: the electrolyte comprises manganese(III) ions in a 9 to 15 molar sulfuric or phosphoric acid solution; and / or the activating solution comprises a precious metal colloid, preferably wherein the precious metal colloid comprises a first core metal and a colloid metal colloidally surrounding the core; the core metal comprises at least one metal selected from the group consisting of silver, platinum, palladium, and nickel; and the colloid metal comprises at least one metal selected from the group consisting of tin and lead.

19. The process according to any of claims 16 to 18, characterized in that the process further comprises galvanizing the plated surface of the component, and wherein the support comprises metal coated at least partially with the iodine-treated and / or bromine-treated plastic.

20. Use of an iodine and / or bromine pretreatment on a support to support a component to be plated, the use to inhibit plating on this during a chromic acid-free plating process, the support having a contact surface comprising plastic.