WO2024251772A1 - Procédé de décapage de matières plastiques non conductrices - Google Patents

Procédé de décapage de matières plastiques non conductrices Download PDF

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Publication number
WO2024251772A1
WO2024251772A1 PCT/EP2024/065401 EP2024065401W WO2024251772A1 WO 2024251772 A1 WO2024251772 A1 WO 2024251772A1 EP 2024065401 W EP2024065401 W EP 2024065401W WO 2024251772 A1 WO2024251772 A1 WO 2024251772A1
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WIPO (PCT)
Prior art keywords
pickling
solution
process according
plastic
permanganate
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Ceased
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PCT/EP2024/065401
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English (en)
Inventor
Tom Nicolai BREMICKER
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Dr Hesse & Cie KG GmbH
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Dr Hesse & Cie KG GmbH
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Publication of WO2024251772A1 publication Critical patent/WO2024251772A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/26—Roughening, e.g. by etching using organic liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the present invention relates to a process for metallizing non-conductive plastic materials, wherein said pickling is effected without using chromium(VI) compounds. After the pickling, the plastics can be metallized by using known processes.
  • Articles made of electrically non-conducting plastic can be metallized with an electroless metallizing method, or alternatively with a direct metallizing method. In both methods, the plastic article is cleaned and pickled at first, then mostly treated with a precious metal, and finally metallized.
  • the state of the art is pickling in chromosulfuric acid. The pickling serves to create the base for subsequent metallization. This takes place by the formation of minute cavities, which provide that the surface of the plastic can be wetted, and by which a sufficient adhesion of the deposited metal can be realized.
  • the components are fixed on frames with frame hooks.
  • frame hooks Usually, several components are fixed on one frame.
  • Such frames are coated with a plastic insulation, mostly of poly(vinyl chloride) (PVC).
  • PVC poly(vinyl chloride)
  • plastics such as acrylonitrile-butadiene-styrene copolymer (ABS copolymer) are etched or pickled using the known chromosulfuric acid method in such a way that the microcavities as mentioned above form in sufficient number to ensure a metallic deposition with sufficient adhesion.
  • the chromosulfuric acid which contains chromium(VI), performs an oxidative attack on the polybutadiene moieties of the polymer. These polybutadiene moieties are removed oxidatively from the polymer surface, so that cavities form at the corresponding positions. In other plastics, the oxidative attack correspondingly takes place at different polymer moieties.
  • the plastics to be metallized are activated by means of an electroless activator, which usually contains precious metals, but mostly either palladium or silver particles, and are thereafter either metallized by electroless plating, which is in the case of direct metallization, or subject to electroless acceleration at first, followed by electroless plating. Thereafter, the components can be directly subjected to electroplating.
  • an electroless activator usually contains precious metals, but mostly either palladium or silver particles
  • the known pickling solutions based on chromosulfuric acid are also used to coat so-called multicomponent plastics.
  • multicomponent plastics several plastics are bonded together in an injection-molding process, or successively injected into the mold. This results in areas that are mostly made of pure PC (polycarbonate), for example, and ABS or an ABS-PC mixture on the other side.
  • Such components are utilized for preparing, for example, buttons in automobile industry with an optical fiber in the form of some lettering or the like.
  • the optical fiber is the pure PC (polycarbonate) component, while the other component is a pure ABS or ABS-PC blend that is to be electroplated exclusively.
  • At least one additional tank with a separate activation process and at least one additional tank with a separate accelerating process must be respectively present. These are then usually used exclusively for such multicomponent assemblies, because in part different activators and other accelerators or modified parameters are employed here.
  • non- conductive plastics are selected from acrylonitrile-butadiene-styrene copolymer (ABS copolymer), polyamide (PA), polycarbonate (PC), mixtures of an ABS copolymer with at least one further polymer, and multicomponent plastics.
  • ABS copolymer acrylonitrile-butadiene-styrene copolymer
  • PA polyamide
  • PC polycarbonate
  • multicomponent plastics should be capable of selective plating after pickling as described above. Surprisingly, it has been found that a process in which a monomer is detached from the plastic surface meets these criteria.
  • the object of the present invention is achieved by a process for pickling non-conductive plastic surfaces, wherein said plastic contains polystyrene moieties, characterized by the steps of a) providing an article having a surface made of a non-conductive plastic material, b) contacting said surface with a pickling solution, wherein said pickling solution contains a solvent and a pickling agent, and c) rinsing the surface to remove the pickling agent, wherein said pickling agent is capable of detaching polystyrene moieties from a polymer.
  • a pickling agent is employed for pickling a non-conductive plastic surface.
  • the surface of an article is pickled thereby.
  • the article as a whole may be made of a plastic material.
  • an article having a surface of plastic is also included according to the invention.
  • the plastic is, according to the present invention, free of particulate foreign matter, such as solid particles or crystallization particles.
  • the plastic surface to be pickled consists only of the non-conductive plastic.
  • the non-conductive plastic is selected from acrylonitrile-butadiene-styrene copolymer (ABS copolymer), polyamide (PA), polycarbonate (PC), mixtures of an ABS copolymer with at least one further polymer, and multicomponent plastics, such as glassfiber reinforced plastics, such as PEEK (polyether ether ketone), ABS/PC, i.e., a component made of acrylonitrile-butadiene-styrene copolymer and polycarbonate (PC), especially selected from acrylonitrile-butadiene-styrene copolymer (ABS copolymer), polyamide (PA), polycarbonate (PC), and mixtures of an ABS copolymer with at least one further polymer.
  • ABS copolymer acrylonitrile-butadiene-styrene copolymer
  • PA polyamide
  • PC polycarbonate
  • ABS copolymers have polymer chains made from the monomers acrylonitrile, butadiene and styrene:
  • Previous methods are based on the principle that polybutadiene, in particular, is oxidatively attacked and removed. This is enabled, for example, by chromosulfuric acid. However, it has been surprisingly found that it is possible to detach polystyrene moieties selectively from the surface of a plastic material to form cavities, which allow for subsequent plating.
  • the solvents are also capable of dissolving polystyrene- 1 ike compounds, so that polyether ketones, such as PEEK, can also be treated with the process according to the invention, with an adapted aftertreatment.
  • the content of ABS should not be less than 20% by weight (100% by weight being the whole weight of the plastic). When the amounts are lower, sufficient cavities cannot be obtained on the surface, so that the plating may not be uniform on the surface. Depending on the desired result, this may be relevant.
  • Acetone and its derivative have proven to be particularly suitable pickling agents.
  • Acetone is suitable because it dissolves polystyrene moieties effectively and selectively.
  • a derivative of acetone is used as a pickling agent, wherein said pickling agent has a higher flash point than that of acetone itself.
  • the flash point is the lowest temperature at which a vapor-air mixture above a substance can ignite.
  • the pickling process according to the invention is effected, in particular, at temperatures from room temperature (i.e., 20 °C) to 80 °C, preferably from 30 °C to 65 °C, especially from 40 °C to 60 °C. In this temperature range, the pickling is effective.
  • the energy consumed for heating the pickling solution is acceptable from an economic point of view.
  • the step of pickling also occurs, but the duration is so long then, that the process can no longer be integrated effectively into existing plating processes.
  • temperatures of above 70 °C, especially above 65 °C, or above 60 °C the energy consumption is high, and the pickling is not more effective, so that the process is preferably performed in the mentioned temperature range.
  • the pickling agent has a flash point that is above the process temperature. Since the flash point of acetone is around -20 °C, specific safety precautions are necessary when acetone is used as pickling agent.
  • the pickling agent is preferably a derivative of acetone whose flash point is higher than that of acetone, preferably higher than 60 °C, especially higher than 65 °C, more preferably higher than 70 °C.
  • Suitable derivatives include, for example, acetophenone, benzalacetone, or 4- hydroxy-4-methyl-2-pentanone.
  • acetone with one or more of the mentioned derivatives may also be employed.
  • the process according to the invention includes that 2, 3 or more derivatives are employed in one mixture as a pickling agent. More preferably, only one acetone derivative is employed as the pickling agent. More preferably, the pickling agent is selected from acetone, acetophenone, benzalacetone, and/or 4-hydroxy-4-methyl-2-pentanone. These have a sufficiently high flash point and can also otherwise be integrated into existing plating methods under usual working safety conditions.
  • the concentration of the pickling agent in the pickling solution is preferably at least 0.01% by weight, based on the total weight of the pickling solution. It can be employed up to the solubility limit. Preferably, the concentration is from 1% by weight to 10% by weight, especially from 3% by weight to 5% by weight, respectively based on the total weight of the pickling solution.
  • the pickling solution is a solution in which the pickling agent according to the invention is dissolved in a solvent.
  • the solvent may be any solvents in which the pickling agent is highly soluble.
  • the solvent of the pickling solution is selected from water and/or glycol and/or glycol compounds.
  • a glycol compound is selected from the group consisting of ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, butylglycol, ethylene glycol monobutyl ether, ethylene glycol diacetate, and mixtures thereof.
  • Particularly preferred are diethylene glycol monoethyl ether acetate, ethylene glycol acetate, ethylene glycol diacetate, butylglycol, and mixtures thereof.
  • the pickling process according to the invention serves, in particular, for preparing surfaces for subsequent plating/metallization.
  • Plating (or metallization - both terms have the same meaning in this invention) is usually carried out in an aqueous solution. If the solvent in the pickling process according to the invention is water, there is as little as possible contamination from foreign substances in the subsequent steps.
  • the pickling solution may also contain wetting agents in addition to the pickling agent and the solvent; wetting agents enable a particularly effective action of the pickling agent on the surface.
  • wetting agents include, for example, surfactants, such as sodium olefinesulfonate, alkylbenzenesulfonates, or alcoholic compounds or glycol compounds as defined above.
  • the pickling solution further includes precious metal compounds in a concentration of from 0.01 mg/l to 80 mg/l, preferably from 0.05 mg/l to 70 mg/l.
  • Said precious metal is, in particular, a metal that is employed as an activator in the metallization. In particular, it is palladium.
  • Suitable compounds for preparing activators, or activators themselves, are well known to those skilled in the art.
  • a suitable compound for preparing activators is, for example, palladium chloride. Surprisingly, it has been found that this causes the later metallization to proceed particularly effectively.
  • the pickling according to the invention changes the plastic surface in such a way that precious metals and, in particular, palladium will adhere to the surface. This enables the subsequent metallization.
  • the plastic surface to be metallized or to be pickled is contacted with the process for pickling according to the invention for a period of from 0.1 to 60 minutes, preferably from 1 to 20 minutes, and more preferably from 6 to 12 minutes.
  • the polymer moiety detached by the pickling solution is to be removed from the surface, this can be done by an oxidative process in a preferred embodiment.
  • step b) includes the following substeps: bl) the surface is contacted with a pickling solution, wherein said pickling solution contains a solvent and a pickling agent, and subsequently b2) the surface is contacted with a permanganate solution.
  • the permanganate solution does not have the effect of a pickling solution.
  • the treatment with permanganate is effected after the pickling and merely serves for the oxidative cleavage of the polymer components detached by the pickling. Therefore, the permanganate solution preferably has a concentration of from 5 g/l to 200 g/l, especially from 10 g/l to 150 g/l, more preferably from 15 g/l to 100 g/l.
  • the permanganate solution is an aqueous or alcoholic (ethanolic) solution.
  • the oxidative purification of the surface with the permanganate- containing solution can be effected in accordance with the prior art.
  • this step can be performed as described in EP 1 001 052 Bl.
  • the surface may also be rinsed between steps bl) and b2) of the process preferred according to the invention.
  • water is used as a rinsing means for rinsing the surface.
  • step c) The rinsing in step c) is also performed with water, in particular.
  • this step is effected, in particular, at temperatures from room temperature (i.e., 20 °C) to 70 °C, preferably from 30 °C to 65 °C, especially from 40 °C to 60 °C.
  • room temperature i.e., 20 °C
  • 70 °C preferably from 30 °C to 65 °C, especially from 40 °C to 60 °C.
  • the pickling is effective.
  • the energy consumed for heating the permanganate solution is acceptable from an economic point of view.
  • the step of oxidative cleavage also takes place at lower temperatures, but the duration is so long then, that the process can no longer be integrated effectively into existing plating processes.
  • the energy consumption is high, and the pickling is thus less cost-efficient, so that the process is preferably performed in the mentioned temperature range.
  • the present invention relates to an article having a surface of non-conductive plastic that contains polystyrene moieties, characterized in that the concentration of polystyrene at the surface is reduced.
  • the surface is obtained by the process described above.
  • the plastic reference is made to the discussions relating to the process.
  • the pickling process according to the invention serves, in particular, for preparing surfaces for subsequent plating.
  • the object of the present invention is achieved by a process for metallizing non- conductive plastic surfaces, characterized in that in a first step, the surface is pickled by a process as disclosed above, followed by plating the surface.
  • the metallization (plating) includes, in particular: i) activation of the surface with an activator solution, ii) especially electroless plating.
  • the process of plating as such can be effected by known methods.
  • a process for metallizing non- conductive plastic surfaces is provided that is characterized by the pickling process according to the invention. All the following steps, such as activation, accelerating or also, optionally, direct metallizing, can be used or applied in the same form as with the previously used chromosulfuric acid pickles.
  • nickel or copper layers are applied to the layer of nuclei on the plastic surface.
  • the pickling of the plastic surface with pickling solutions according to the invention pickles the plastics so strongly and uniformly, that pickling alone in this step leads to sufficient adhesion of the metal layer applied.
  • the pickling of the plastics according to the invention with the pickling solutions according to the invention surprisingly leads to a significantly higher amount of coating on the surface with a metal during the activation of the surface. This enables a reduction of the precious metal concentration employed during the activation, and thus enables a lower energy consumption.
  • the pickling process according to the invention can be used to coat far more plastics than was previously possible using chromosulfuric acid pickling, such as highly glass fiber-reinforced plastics like PEEK (polyether ether ketone).
  • chromosulfuric acid pickling such as highly glass fiber-reinforced plastics like PEEK (polyether ether ketone).
  • This aspect also enables the opening-up of new and forward-looking fields of application, because even plastics with a metal-like stability can now be coated in a decorative or also functional way. Further, with the process according to the invention, the coating of multicomponent plastics is also possible in an even simpler way than previously. While both a further activation step and a further accelerating step were required in the prior art, i.e., pickling with chromosulfuric acid, presently no further adapted process steps as compared to the conventional procedure for the coating of such components are necessary.
  • the process according to the invention enables a simple and flawless coating independently of the type and concentration in the accelerator, and in the activator, whereby these are avoided as sources of error, and a significantly higher process safety is created. Therefore, in a further embodiment, the present invention relates to an article having a surface of non-conductive plastic, wherein said plastic contains polystyrene moieties, characterized in that the surface was metallized by a process as described above.
  • the plastic component After the pickling, the plastic component had a uniformly roughened and easily wettable structure.
  • a plastic component made of ABC PC as used in Example 1 was treated as follows:
  • HESSOPLAST AKA is a palladium activator with an exemplary composition in the activator solution of 25 mg/l Pd, 3 g/l Sn 2+ , and 300 ml/l HCI 37%.
  • HESSONIC PL-H is an electroless depositing nickel method with an exemplary composition of 2.6 g/l Ni, 20 g/l sodium hypophosphite, about 30 g/l orthophosphite, and a stabilizer concentration of 3 mg/l.
  • the plastic component could be subjected to chemical nickel plating in a flawless and adhesion-strong way, followed by metallization.
  • Cleansing solution 1 (removal of manganese dioxide after pickling in permanganate-containing solutions): 50 ml/l sulfuric acid 96% technical grade concentrated, 50 ml/l hydrogen peroxide technical grade 33%
  • a plastic component made of ABC PC as used in Example 1 was treated as follows:
  • the plastic component could be subjected to chemical nickel plating in a flawless way, followed by metallization.
  • Cleansing solution 2 (removal of manganese dioxide after pickling in permanganate-containing solutions): 20 ml/l hydroxylammonium sulfate.
  • a plastic component made of ABC PC as used in Example 1 was treated as follows:
  • the plastic component could be subjected to chemical nickel plating in a flawless way, followed by metallization. This also enables another shortening of the procedure, since the rinsing steps between step 2 and step 3 are omitted.
  • the pickling process found is advantageously compatible with most of the existing lines for metallizing plastics. It results in a more uniform roughening and nucleation of the plastic surface and thus in a faster and more flawless metallization, for example, in autocatalytic nickel plating. The results obtained are very well reproducible, and up-scaling of the metallization process from laboratory scale can be dispensed with.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)

Abstract

De manière surprenante, le présent procédé est un procédé de décapage stable pour le placage ultérieur de matières plastiques, tel qu'un copolymère acrylonitrile-butadiène-styrène (copolymère ABS), sans utiliser de composés de chrome (VI) qui peuvent également être intégrés dans des installations de placage de matières plastiques existantes. En plus des avantages écologiques, une telle intégration présente également des avantages économiques, étant donné que ce procédé peut être mis en œuvre à des températures plus basses et donc à un coût énergétique plus faible. De plus, des avantages significatifs dans le revêtement d'ensembles multicomposants ont été trouvés de manière surprenante, étant donné que ceux-ci pourraient être revêtus sensiblement plus simplement que précédemment.
PCT/EP2024/065401 2023-06-07 2024-06-05 Procédé de décapage de matières plastiques non conductrices Ceased WO2024251772A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102023114956.3 2023-06-07
DE102023114956.3A DE102023114956A1 (de) 2023-06-07 2023-06-07 Verfahren zum Beizen nichtleitender Kunststoffe

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WO2024251772A1 true WO2024251772A1 (fr) 2024-12-12

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DE (1) DE102023114956A1 (fr)
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WO (1) WO2024251772A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202023107029U1 (de) 2023-11-28 2024-01-10 Dr. Hesse GmbH & Cie. KG Gegenstand mit einer gebeizten Oberfläche aus einem nichtleitenden Kunststoff

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445350A (en) * 1965-10-11 1969-05-20 Borg Warner Metal plating of plastic materials
US3671289A (en) * 1969-09-23 1972-06-20 Crown City Plating Co Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating
EP1001052B1 (fr) 1998-11-13 2004-05-06 LPW-Chemie GmbH Procédé pour metalliser une surface de plastique
JP2007100174A (ja) * 2005-10-05 2007-04-19 Okuno Chem Ind Co Ltd スチレン系樹脂成形体へのめっき用前処理方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019104407A1 (de) 2019-02-21 2020-08-27 EPIC Consulting GmbH Verfahren zur Herstellung eines beschichteten Kunststoffbauteils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445350A (en) * 1965-10-11 1969-05-20 Borg Warner Metal plating of plastic materials
US3671289A (en) * 1969-09-23 1972-06-20 Crown City Plating Co Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating
EP1001052B1 (fr) 1998-11-13 2004-05-06 LPW-Chemie GmbH Procédé pour metalliser une surface de plastique
JP2007100174A (ja) * 2005-10-05 2007-04-19 Okuno Chem Ind Co Ltd スチレン系樹脂成形体へのめっき用前処理方法

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DE102023114956A1 (de) 2024-12-12

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