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    • 专利摘要:
    PLASTIC STRIPING USING ACID SOLUTIONS CONTAINING TRIVALENT MANGANESE. Method of preparing a solution capable of etching a metallisable plastic. The method comprises the steps of: (a) providing an electrolyte comprising a solution of manganese(II) in a 9 to 15 molar solution of sulfuric acid or phosphoric acid to an electrolytic cell; (b) applying a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode; and (c) oxidizing the electrolyte to form manganese(III) ions, wherein the manganese(III) ions form a metastable sulfate complex. Thereafter, a metallisable plastic can be immersed in the metastable sulfate complex for a period of time to strip the metallisable substrate prior to subsequent plating steps.
    公开号:BR112014017638B1
    申请号:R112014017638-8
    申请日:2013-01-03
    公开日:2021-04-20
    发明作者:Trevor Pearson；Craig Robinson
    申请人:Macdermid Acumen, Inc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates in general to methods for the preparation of plastics for subsequent galvanizing therein. BACKGROUND OF THE INVENTION
    [002] It is well known in the prior art to galvanize non-conductive substrates (eg plastics) with metal, for a variety of purposes. Plastic moldings are relatively inexpensive to produce, and metallized plastic is used for many applications. For example, metallized plastics are used for decoration and for manufacturing electronic devices. An example of decorative use includes auto parts such as trim. Examples of electronic uses include printed circuits, where metallised with a selective pattern comprise printed circuit board conductors, and metallised plastics used for EMI shielding. ABS resins are the most common metallized plastics for decorative purposes, while phenolic and epoxy resins are the most common metallized plastics for manufacturing printed circuit boards.
    [003] The preparation of plastics for subsequent plating is a multi-step process, and typical process steps include: 1) pickling the substrate with a chromic acid pickling solution; 2) neutralizing the etched surface with a chromium neutralizing solution; 3) activation of the etched surface using a palladium and tin colloidal activator; 4) tin removal with an acceleration step; and 5) depositing a layer of autocatalytic copper or autocatalytic nickel, followed by electrolytic copper and/or nickel plating.
    [004] The initial pickling of plastic substrates is an essential part of the overall process, and essentially all commercial processes have used a chromic acid pickling solution as a source of hexavalent chromium for the plastic pickling step. This process has several attributes. Various plastics, including ABS and ABS/polycarbonate blends, can be metalized with good metalized appearance and adhesion. The immersion time and/or temperature in the chromic acid stripping solution can be increased to metallize the more difficult plastics containing higher levels of polycarbonate or polypropylene. Extremely difficult plastics that are resistant to pickling, such as pure polycarbonate, can also be metallized by incorporating a solvent prior to the chromium pickling step.
    [005] Only a few types of plastic components are suitable for galvanizing and, as discussed above, the most common types of plastic for electroplating are Acrylonitrile/Butadiene/Styrene (ABS), or a mixture of this material with polycarbonate (ABS/PC ). ABS consists of two phases. There is a relatively hard phase consisting of an acrylonitrile/styrene copolymer, and a softer polybutadiene phase. Currently, this material is metallized almost exclusively using a mixture of chromic and sulfuric acids. This acidic oxidizing mixture is highly effective as a paint stripper for ABS and ABS/PC. The polybutadiene phase of the plastic contains double bonds in the polymer backbone, and these are oxidized by chromic acid, thus causing the complete disaggregation and dissolution of the polybutadiene phase exposed on the plastic surface, thus giving an effective pickling to the surface. of plastic.
    [006] The purpose of the pickling step is twofold. First, the plastic is stripped to increase the surface area. Second, the plastic is made hydrophilic, making the surface receptive to the subsequent stages of activation and plating. Typical chromic acid pickling solutions are described, for example, in US patent no. 4,610,895 by Tubergen et al. 6,645,557 by Joshi, and US patent no. 3,445,350 by Klinger et al., which are incorporated herein by reference in their entirety.
    [007] A problem with the traditional chromic acid pickling step is that chromic acid is a recognized and increasingly regulated carcinogen, insisting that whenever possible, the use of chromic acid be replaced by safer alternatives. The use of a chromic acid stripper also has well-known and serious disadvantages, including the toxicity of chromium compounds that makes them difficult to dispose of, the chromic acid residues remaining on the polymer surface that inhibit autocatalytic deposition, and the difficulty of washing chromic acid residues from the polymer surface after treatment. In addition, hot hexavalent chromic sulfuric acid solutions are naturally hazardous to workers. Upper airway burns and bleeding are common in workers routinely involved with these chromium stripper solutions. Thus, it is highly desirable that safer alternatives to chromic acid pickling solutions be developed.
    [008] Permanganate solutions are described in US patent no. 3,625,758 by Stahl et al., which is incorporated herein by reference in its entirety. Stahl suggests the suitability of either a sulfuric and chromic acid bath, or a permanganate solution for surface preparation.
    [009] US patent no. 4,948,630 by Courduvelis et al., which is hereby incorporated by reference in its entirety, describes a hot alkaline permanganate solution, which also contains a material, such as sodium hypochlorite, that has an oxidation potential higher than the potential of oxidation of the permanganate solution, and is capable of oxidizing the manganate ions to the permanganate ions. US patent no. 5,648,125 by Cane, which is hereby incorporated by reference in its entirety, describes the use of an alkaline permanganate solution comprising potassium permanganate and sodium hydroxide, wherein the permanganate solution is maintained at an elevated temperature, i.e., between about of 165°F and 200°F. US patent no. 4,042,729 by Polichette et al, which is hereby incorporated by reference in its entirety, describes a pickling solution comprising water, permanganate ion, and manganate ion, wherein the molar ratio of manganate ion to permanganate ion is controlled , and the pH of the solution is maintained at 11 to 13.
    [010] US patent no. 5,229,169 to Chao, which is hereby incorporated by reference in its entirety, describes a process for depositing a metal layer onto the surface of a polycarbonate-ABS resin (or other similar resin), comprising the steps of contacting the surface with a solution of aqueous metal hydroxide, contact the surface with an aqueous alkaline solution of water-soluble permanganate, remove any residual manganese compounds by contacting a reducing agent, and deposit a layer of autocatalytic metal on the surface. The alkaline permanganate generally comprises potassium or sodium permanganate, and the reducing agent may comprise, for example, a solution of hydroxylamine salts.
    [011] However, attempts to use permanganate for pickling plastics (except epoxy based printed circuit boards) have not been very successful. First, the surface treatment of plastic is inconsistent, sometimes producing good adhesion and sometimes producing poor adhesion under identical treatment conditions. Second, permanganate solutions can be unstable, have a short life, and are rapidly decomposed to manganese dioxide. Furthermore, compared to chrome strippers, permanganate is less effective and not suitable for the wide range of metallized plastic mixtures in general metal finishing operations.
    [012] None of these attempts to condition the plastic using permanganate ions have been able to produce pickling characteristics that correspond to those obtained using chromic acid, and the stability of pickling solutions is also poor, resulting in the formation of deposits. manganese dioxide.
    [013] Other attempts to replace pickling with chrome are also described in the prior art. For example, US patents nos. 4,941,940, 5,015,329, and 5,049,230, all of Patel et al, which are hereby incorporated by reference in their entirety, describe a single or multi-step process for pre-swelling and stripping functionalized polymers, such as polycarbonates, using a solution conditioner comprising at least one swelling agent and at least one degradation agent. The prepared substrates are then metallized with autocatalytic nickel or electrolytic copper.
    [014] US patent no. 5,160,600 to Patel et al., which is incorporated herein by reference in its entirety, replaces the chromic acid stripping solution with a stripping solution comprising sulfuric acid, and optionally phosphoric acid and/or nitric acid. The treated substrate is then immersed in an aqueous palladium suspension.
    [015] Regardless of whether the oxidizing solution is a hexavalent chromium solution, or a permanganate solution, contact with the solution leaves an oxidizing residue on the surface of the plastic part that acts to corrupt the catalytic surface, interfering with deposition metal and often resulting in the formation of voids. A simple water wash is generally inadequate to remove residue, and the prior art has then resorted to an additional step of contacting a solution of a reducing agent, although more chemistry is involved in removing the oxidant residue than reduction simple. Removal of the permanganate residue with a reducing agent is disclosed in the above-referenced U.S. Patents No. 4,610,895 by Tubergen, and No. 6,645,557 by Joshi.
    [016] As is easily observed, several pickling solutions have been suggested as substitutes for chromic acid in processes for the preparation of non-conductive substrates for metallization. However, none of these processes have proven satisfactory for various economic, performance, and/or environmental reasons, and thus none of these processes have achieved commercial success, or been accepted by the industry as a suitable replacement for chromic acid pickling.
    [017] The tendency of permanganate-based solutions to form deposits and undergo self-decomposition was observed. Under strongly acidic conditions, permanganate ions can react with hydrogen ions to produce manganese(III) ions and water, according to the following reaction:

    [018] The manganese (II) ions formed by this reaction can then undergo further reaction with the permanganate ions, forming a deposit of manganese dioxide according to the following reaction:

    [019] Thus, formulations based on strongly acidic solutions of permanganate are intrinsically unstable, regardless of whether the permanganate ion is added by alkali metal salts of permanganate, or is electrochemically generated IN SITU. Compared to currently used chromic acid paint strippers, the low chemical stability of acid permanganate makes it effectively useless for large-scale commercial application. Alkaline permanganate paint strippers are more stable, and are widely used in the printed circuit board industry for epoxy-based printed circuit board stripping, but alkaline permanganate is not an effective paint stripper for plastics such as ABS or ABS/PC. Thus, manganese (VII) is unlikely to gain widespread commercial acceptance as a paint stripper for these materials.
    [020] Other attempts to etch ABS without the use of chromic acid have included the use of electrochemically generated silver(II) or cobalt(III). For many years, it has been recognized that certain metals can be anodically oxidized to oxidation states that are highly oxidizing. For example, manganese (II) can be oxidized to permanganate (manganese VI), cobalt can be oxidized from cobalt (II) to cobalt (III), and silver can be oxidized from silver (I) to silver (II) .
    [021] There is currently no commercially successful paint stripper suitable for plastics, based on permanganate (in both acidic and alkaline forms), on manganese in any oxidized state, or through the use of other acids or oxidants.
    [022] Thus, there remains a need in the prior art for an improved paint stripper for the preparation of plastic substrates for subsequent electrodeposition, which does not contain chromic acid and which is commercially acceptable. SUMMARY OF THE INVENTION
    [023] It is an object of the invention to provide a paint stripper for plastic substrates that does not contain chromic acid.
    [024] It is another objective of the present invention, a paint stripper for plastic substrates that is commercially acceptable.
    [025] It is yet another objective of the present invention to provide a paint stripper for plastic substrates, which is based on manganese ions.
    [026] The present invention refers in general to a composition suitable for the pickling of ABS, ABS/PC and other plastic materials, and a method of using it.
    [027] In one embodiment, the present invention relates generally to a method of preparing a solution capable of chemically attacking a plastic substrate, the method comprising the steps of:
    [028] provide an electrolyte comprising a solution of manganese (II) in a 9 to 15 molar solution of sulfuric acid or phosphoric acid to an electrolytic cell;
    [029] apply a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode;
    [030] oxidize the electrolyte to form manganese (III) ions, in which the manganese (III) ions form a metastable sulfate complex; and
    [031] treat the plastic substrate in the electrolyte.
    [032] In another embodiment, the present invention relates in general to an electrolyte capable of etching a plastic substrate, the electrolyte comprising a solution of manganese (III) in a 9 to 15 molar solution of sulfuric acid or phosphoric acid .
    [033] In a preferred embodiment, the electrolyte composition can be used to pick the ABS or ABS/PC at a temperature of between 30 to 80°C. DETAILED DESCRIPTION OF PREFERRED MODALITIES
    [034] The inventors of the present invention found that trivalent manganese can be easily produced by low current density electrolysis of divalent manganese ions into strong sulfuric acid. More particularly, the inventors of the present invention have found that a solution of trivalent manganese ions in the strongly acidic solution is capable of etching the ABS.
    [035] Trivalent manganese is unstable and is highly oxidizing (standard redox potential 1.51 VERSUS the normal hydrogen electrode). In solution, it is rapidly disproportionate to manganese dioxide and divalent manganese, through the following reaction:

    [036] However, in a strong sulfuric acid solution, the trivalent manganese ion becomes metastable and forms a cherry red/purple colored sulfate complex. The inventors have found that this sulfate complex is a suitable medium for stripping ABS, and has many advantages over the chromium-free strippers described above.
    [037] In one embodiment, the present invention relates generally to a method of preparing a solution capable of etching a plastic substrate, the method comprising the steps of:
    [038] provide an electrolyte comprising manganese (II) ions in a 9 to 15 molar solution of sulfuric acid or phosphoric acid to an electrolytic cell;
    [039] apply a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode;
    [040] oxidize the electrolyte to form manganese (III) ions, in which the manganese (III) ions form a metastable sulfate complex; and
    [041] treat the plastic substrate with electrolyte to strip the surface of the plastic substrate.
    [042] In a preferred embodiment, the plastic substrate comprises ABS or ABS/PC.
    [043] While it is contemplated that both phosphoric acid and sulfuric acid would work in compositions of the present invention, in a preferred embodiment, the acid is sulfuric acid. The stability of manganese(III) ions in sulfuric and phosphoric acids was studied. At ambient temperatures, the half-life of manganese(III) ions in 7M sulfuric acid is on the order of 2 years. By comparison, the half-life of similar concentrations of manganese(III) ions in 7M phosphoric acid was about 12 days. It is suggested that the much higher stability of manganese(III) ions in sulfuric acid is due to the formation of manganese-sulfate complexes, and the higher concentration of hydrogen ion concentration available in the sulfuric acid solution. An additional problem with the use of phosphoric acid is the limited solubility of manganese(III) phosphate. Thus, although other inorganic acids, such as phosphoric acid, can be used in the compositions of the present invention, the use of sulfuric acid is generally preferred.
    [044] The remarkable stability of the manganese(III) ions in strong sulfuric acid offers the following advantages in use: 6) Since the Mn(III) ions are formed at low current density, the energy requirements for the process are usually very low. 7) Since the anode operates at a low current density, a small cathode in relation to the area of the anode can be used to avoid cathodic reduction of Mn(III) ions. This makes the need for a split cell obvious, and makes engineering a stripper regeneration cell simpler. 3)Since the process does not produce permanganate ions, there is no possibility of producing manganese heptoxide in the solution (this is a considerable safety risk as it is highly explosive). 8) Due to the high stability of Mn(III) ions in strong sulfuric acid, the paint stripper can be sold ready to use. In production, pickling requires only a small regeneration cell on the side of the tank in order to maintain the Mn(III) content of pickling, and to prevent accumulation of Mn(II) ions. 9) Since the other pickling processes are based on permanganates, the result of the reaction of the permanganate with Mn(II) ions causes rapid "settling" with manganese dioxide, and a short pickling lifetime. This should not be a problem with Mn(III) based pickling (although there may be some disproportion over time). 10) The electrolytic production of Mn(III) according to the present invention does not produce any toxic gases. Some hydrogen can be produced at the cathode, but due to the low current requirements this would be less than that produced by various plating processes.
    [045] As described herein, in a preferred embodiment the acid is sulfuric acid. The sulfuric acid concentration can be between about 9 and about 15 molar. The concentration of sulfuric acid is important for the process. Below a concentration of about 9 molar the pickling rate becomes too slow for use, and above about 14 molar the solubility of the manganese ions in the solution becomes too low to obtain a useful concentration. of manganese in the solution. Also, very high concentrations of sulfuric acid tend to absorb moisture from the air, and are dangerous to deal with. Thus, in a preferred embodiment, the concentration of sulfuric acid is between about 12 and 13 molar. This concentration of sulfuric acid is diluted enough to allow safe addition of water for pickling, and strong enough to optimize the plastic pickling rate. At this sulfuric acid concentration, up to about 0.08M manganese sulfate can be dissolved at a preferred pickling operating temperature. For optimal pickling, the concentration of manganese ions in solution should be as high as possible.
    [046] Manganese (III) ions are preferably selected from the group consisting of manganese sulfate, manganese carbonate, and manganese hydroxide, although other similar sources of manganese (II) ions known in the art, could also be used in the practice of the invention. The concentration of manganese(II) ions can range between about 0.005 molar and saturation. In one embodiment, the electrolyte also comprises colloidal manganese dioxide. This can be formed, to some extent, as a natural result of the disproportion of manganese(III) in solution, or it can be added deliberately. Methods of preparing colloidal manganese dioxide are well known in the state of the art.
    [047] The manganese (III) ions can be conveniently generated by electrochemical means, through the oxidation of the manganese (II) ions. The methodology for the efficient production of trivalent manganese ions was determined, and it was found that with the use of a platinum titanium or platinum anode, manganese(II) can be efficiently oxidized to manganese(III) at a specific density. current between 0.1 and 0.4 A/dm2. At these current densities, the inventors of the present invention have found that the conversion efficiency of manganese(II) under these circumstances approaches 100%. Furthermore, at a current density between 0.1 and 0.4 A/dm2 using a platinum titanium anode, the anode potential is less than the oxygen discharge potential, and manganese(III) ions are produced with high efficiency. The inventors have discovered that ABS pickling can be achieved using this method.
    [048] The electrodes may comprise a material selected from the group consisting of platinum, platinum titanium, iridium oxide coated titanium, niobium, and other suitable materials. The cathode may also be made of platinum, platinum titanium, niobium, iridium oxide coated titanium, or any other suitable material, and is preferably platinum or platinum titanium. The anode can be made of platinum titanium, platinum, tantalum/iridium oxide, niobium, or any other suitable material, and is preferably platinum or platinum titanium. For efficient generation of manganese(III) ions, it is generally necessary to use an anode area that is large compared to the cathode area. Preferably, the anode to cathode area ratio is at least about 10:1. By this means, the cathode can be immersed directly into the electrolyte, and it is not necessary to have a split cell arrangement (although the process would work with a split cell arrangement, this would introduce unnecessary complexity and expense).
    [049] Furthermore, it is generally preferable that the electrolyte does not contain any permanganate ions.
    [050] In another embodiment, the present invention comprises the immersion of the metallizable plastic in the metastable sulfate complex, for a period of time to strip the surface of the metallizable plastic. In one embodiment, the metallisable plastic is immersed in the solution at a temperature of between 30 and 80°C. The pickling rate increases with temperature, and is very slow below 50°C. The upper temperature limit is determined by the nature of the plastic being pickled. ABS starts to deform above 70°C, therefore, in a preferred modality, the electrolyte temperature is kept between about 50 and about 70°C, especially when stripping ABS materials. The time period for immersing the plastic in the electrolyte is preferably between about 20 to about 30 minutes.
    [051] Articles pickled in this way can then be galvanized using conventional pretreatment for metallised plastics, or the pickled surface of the plastic can be used to improve the adhesion of paints, varnishes or other surface coatings.
    [052] As described in the examples below, the inventors of the present invention have determined by means of cyclic voltammetry that in the concentration of manganese (II) ions used in the pickling of the present invention, the oxidation is controlled by diffusion, so that the agitation efficient pickling solution is required during the electrolytic oxidation process.
    [053] In another embodiment, the present invention relates generally to an electrolyte capable of etching a metallisable plastic, the electrolyte comprising a solution of manganese (II) in a 9 to 15 molar solution of sulfuric acid or phosphoric acid. The electrolyte oxidizes to form manganese(III) ions, where manganese(III) ions form a metastable sulfate complex, where sulfuric acid is used.
    [054] The invention will now be illustrated with the following non-limiting examples. Comparative Example I:
    [055] A solution of 0.08 molar manganese sulfate in 12.5 molar sulfuric acid (500 ml) was heated to 70°C, and a piece of metallizable grade ABS was immersed in the solution. Even after an hour immersed in this solution, there was no discernible pickling of the test plate, and after washing the surface was not "wet" and would not support a continuous film of water. Example 1:
    [056] The solution of Comparative Example 1 was electrolyzed by immersing a platinum titanium anode of an area of 1 dm2 and a platinum titanium cathode of a surface area of 0.01 dm2 in the solution, and a current was applied. 200 mA for 5 hours.
    [057] During this period of electrolysis, the solution was observed to change from nearly colorless to a deep red/purple color. It was confirmed that no permanganate ions were present.
    [058] The solution was then heated to 70°C, and a piece of metallizable grade ABS was immersed in the solution. After 10 minutes of immersion, the test piece was completely wet, and would support a continuous film of water after washing. After 20 minutes of immersion, the sample was washed in water, dried and examined using a scanning electron microscope (SEM). Examination revealed that the test piece was substantially blasted, and many blast pores were visible. Example 2:
    [059] A metallizable grade ABS test piece was conditioned in a solution prepared as in Example 1 for 30 minutes at 70°C. The sample was then washed and metallized using the following pretreatment sequence: 1) Treatment in a proprietary preparation for plating onto plastic (M-Neutralization, available from MacDermid, Inc.) 2) Washing 3) Pre-dip in 30% hydrochloric acid 4) Activation in a proprietary palladium colloidal activator (D34 C, available from MacDermid, Inc.) 5) Wash 6) Acceleration in a proprietary preparation (Macuplex Ultracel 9369, available from MacDermid, Inc.) .) 7) Wash 8) Metallize in autocatalytic nickel process (Macuplex J64, available from MacDermid, Inc.) 9) Wash 10) Metallize in copper acid process, to a thickness of 30 microns (CuMac Optima, available from MacDermid)
    [060] In all cases, the process parameters were as recommended in the technical sheet of each product.
    [061] After the copper pickling process was completed, the sample was dried and analyzed. The copper deposit was bright and clear, with no evidence of bubbles, and showed good adhesion of the deposit to the substrate. Example 3
    [062] A solution containing 12.5 M sulfuric acid and 0.08 M manganese (II) sulfate was electrolyzed using a platinum titanium anode at a current density of 0.2 A/dm2. A platinum titanium cathode having an area of less than 1% of the anode area was used in order to avoid cathodic reduction of the manganese(III) ions produced at the anode. Electrolysis was carried out long enough for enough coulombs to be passed to oxidize all of the manganese(II) ions to manganese(III) ions. The resulting solution had a deep cherry red/purple color. There were no permanganate ions generated during this step. This was also confirmed by visible spectroscopy - the Mn(III) ions produced an absorption spectrum completely different from that of a permanganate solution. Example 4
    [063] The stripping solution prepared as described above in Example 3 was heated to 65 to 70°C on a magnetic stirrer/hot plate, and ABS test coupons were immersed in the solution for time periods of 20 and 30 minutes. Some of these test coupons were examined by SEM, and some were processed in a normal plating in a plastic pretreatment sequence (reduction in M-neutralization, pre-immersion, activation, acceleration, autocatalytic nickel, copper plate to 25 at 30 microns). These test coupons were then annealed and subjected to peel strength testing using an Instron machine.
    [064] The scaling resistance test performed on metallized coupons for 30 minutes, demonstrated resistance to scaling ranging between about 1.5 and 4 N/cm.
    [065] Cyclic voltammograms were obtained from a solution containing 12.5 M sulfuric acid and 0.08 M manganese sulfate, using a rotating platinum disc (RDE) electrode, having a surface area of 0.196 cm2 at various rotation speeds. A model 263A potentiostat and a silver/silver chloride reference electrode were used in conjunction with the RDE.
    [066] In all cases, the next scan showed a peak of about 1.6V vs. Ag/AgCl, followed by a plateau of up to about 1.75V and followed by, and an increase in current. The reverse scan produced a similar plateau (with a slightly lower current and a peak around 1.52V. The dependence of these results on the electrode rotation rate indicates that mass transport control is a major factor in the mechanism. The plateau indicates the potential range over which Mn(III) ions are formed through electrochemical oxidation.
    [067] The potentiostatic scan was performed at 1.7V. It was observed that the current initially dropped, and then increased over a period of time. The current density at this potential ranged between 0.15 and 0.4 A/dm2.
    [068] After this experiment, a galvanostatic measurement was taken at a constant current density of 0.3 A/dm2. Initially, the applied current density was obtained by a potential of about 1.5 V but throughout the experiment, after about 2400 seconds, an increase in potential of about 1.75 V was observed.
    [069] The results of these experiments demonstrate that manganese (III) ions can be generated through electrosynthesis at low current densities, using a platinum catalyst or platinum titanium anode.
    [070] After a pickling period of more than 10 minutes, it was observed that the surface of the ABS test coupons were completely wetted, and would support a continuous film of water after washing. After a period of 20 or 30 minutes, the boards were remarkably pickled.
    权利要求:
    Claims (22)
    [0001]
    1. Electrolyte capable of etching a metallisable plastic, CHARACTERIZED by the fact that it comprises manganese(III) ions in a 9 to 15 molar solution of sulfuric acid or phosphoric acid.
    [0002]
    2. Electrolyte, according to claim 1, CHARACTERIZED by the fact that the acid is sulfuric acid.
    [0003]
    3. Electrolyte, according to claim 2, CHARACTERIZED by the fact that sulfuric acid has a concentration of 12 to 13 molar.
    [0004]
    4. Electrolyte according to claim 1, CHARACTERIZED by the fact that the electrolyte additionally comprises colloidal manganese dioxide.
    [0005]
    5. Electrolyte, according to claim 1, CHARACTERIZED by the fact that the electrolyte does not contain any permanganate.
    [0006]
    6. Electrolyte, according to claim 1, CHARACTERIZED by the fact that the concentration of manganese (III) ions in the electrolyte is between 0.005 molar and saturation
    [0007]
    7. Method of preparing a solution capable of etching a metallisable plastic, CHARACTERIZED by the fact that it comprises the steps of: providing an electrolyte as defined in claim 1 comprising manganese (II) ions in a 9 to 15 molar acid solution sulfuric or phosphoric acid to an electrolytic cell; applying a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode; and oxidizing the electrolyte to form manganese(III) ions, where the manganese(III) ions form a metastable phosphate or sulfate complex.
    [0008]
    8. Method according to claim 7, CHARACTERIZED by the fact that the acid is sulfuric acid.
    [0009]
    9. Method according to claim 8, CHARACTERIZED by the fact that sulfuric acid has a concentration of 12 to 13 molar.
    [0010]
    10. Method according to claim 7, CHARACTERIZED by the fact that manganese (II) ions are selected from the group consisting of manganese sulfate, manganese carbonate and manganese hydroxide.
    [0011]
    11. Method according to claim 7, CHARACTERIZED by the fact that the solution additionally comprises colloidal manganese dioxide.
    [0012]
    12. Method according to claim 7, CHARACTERIZED by the fact that the concentration of manganese (II) ions in the electrolyte is between 0.005 molar and saturation.
    [0013]
    13. Method according to claim 7, CHARACTERIZED by the fact that the cathode comprises a material selected from the group consisting of platinum, platinum titanium, tantalum/iridium oxide, and niobium.
    [0014]
    14. Method according to claim 13, CHARACTERIZED by the fact that the cathode is platinum titanium or platinum.
    [0015]
    15. Method according to claim 7, CHARACTERIZED by the fact that the anode area is larger than the cathode area.
    [0016]
    16. Method according to claim 15, CHARACTERIZED by the fact that the anode to cathode area ratio is at least 10:1.
    [0017]
    17. Method according to claim 7, CHARACTERIZED by the fact that the anode current density is between 0.1 to 0.4 A/dm2.
    [0018]
    18. Method according to claim 7, CHARACTERIZED by the fact that the electrolyte temperature is maintained between 30°C and 80°C.
    [0019]
    19. Method according to claim 7, CHARACTERIZED by the fact that the electrolyte does not contain any permanganate.
    [0020]
    20. Method according to claim 7, CHARACTERIZED by the fact that it further comprises the step of immersing the metallizable plastic in the metastable sulfate complex, for a period of time to pick off the metallizable substrate.
    [0021]
    21. Method according to claim 20, CHARACTERIZED by the fact that the metallizable plastic is immersed in the metastable sulfate complex for 20 to 30 minutes.
    [0022]
    22. Method according to claim 21, CHARACTERIZED by the fact that the metallisable plastic comprises acrylonitrile-butadiene-styrene or acrylonitrile-butadiene-styrene/polycarbonate.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-08| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-02-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/356,004|2012-01-23|
    US13/356,004|US10260000B2|2012-01-23|2012-01-23|Etching of plastic using acidic solutions containing trivalent manganese|
    PCT/US2013/020115|WO2013112268A2|2012-01-23|2013-01-03|Etching of plastic using acidic solutions containing trivalent manganese|
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