EP1268880A2 - Procede de galvanoplastie directe d'un substrat plastique - Google Patents

Procede de galvanoplastie directe d'un substrat plastique

Info

Publication number
EP1268880A2
EP1268880A2 EP20010921064 EP01921064A EP1268880A2 EP 1268880 A2 EP1268880 A2 EP 1268880A2 EP 20010921064 EP20010921064 EP 20010921064 EP 01921064 A EP01921064 A EP 01921064A EP 1268880 A2 EP1268880 A2 EP 1268880A2
Authority
EP
European Patent Office
Prior art keywords
active surface
substrate
carbonyl
metal
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20010921064
Other languages
German (de)
English (en)
Other versions
EP1268880B1 (fr
Inventor
Andrea Marsales
William E. Armstrong
Gary F. Chevalier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Decoma Exterior Trim Inc
Original Assignee
Decoma Exterior Trim Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Decoma Exterior Trim Inc filed Critical Decoma Exterior Trim Inc
Publication of EP1268880A2 publication Critical patent/EP1268880A2/fr
Application granted granted Critical
Publication of EP1268880B1 publication Critical patent/EP1268880B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/2033—Heat
    • 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
    • C23C18/208—Multistep pretreatment with use of metal 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
    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • 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
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper

Definitions

  • the present invention relates to a process for direct metal-plating of a plastic substrate.
  • Metal-plating of substrate materials is known. For example, chrome-plating of automobile trim components is periodically popular. Many years ago such chrome-plating was achieved by plating a metal substrate
  • a bumper (e.g., a bumper).
  • chrome-plating of metal substrates for use in automobile trim parts has been reduced for a variety of reasons, including: the need to reduce the weight of the vehicle, corrosion problems with the metal substrate, the advance of other systems for energy absorption if the substrate was being used as a bumper and the like.
  • the protective layer comprises clear urethane resin, black pigment paste, a solvent blend and a catalyst solution. Thereafter, a layer of corrosion prone metal is vacuum deposited to form a discontinuous film covering the combined primer/basecoat layer.
  • United States patent 5,985,418 [Lein et al. (Lein)] teaches a process for manufacturing a metallized substrate using a so-called island coating method. Particularly adapted for application of a metal layer to a substrate used in the apparel industry.
  • the process comprises depositing a first coating layer containing a radiation curable non- volatile film former.
  • the coated substrate is then vacuum metallized to form the metal islands of the invention and thereafter, a layer of clear resinous protective dielectric top coat containing a radiation curable non-volatile film former is deposited to completely cover the layer of "metal islands" .
  • the substrate can be polymeric or metallic.
  • TPO Thermoplastic Olefin
  • vehicles are commonly fitted with a front and rear fascia which cover or conceal a front and rear bumper beam assembly.
  • Molded TPO rocker panels and fenders are also commonly utilized on vehicles.
  • the trim panels are molded and then painted to match the color of the remaining portion of the vehicle.
  • TPO thermoplastic olefin
  • the present invention provides a process for direct metal-plating of a plastic substrate comprising the steps of:
  • thermoplastic olefin (TPO) substrate i.e., the active surface of the substrate
  • the active surface of the substrate comprise carbon atoms of which at least about 7 % are in the form of carbonyl in order to produce a durable, good quality metal plate coating on the substrate. If the active surface of the substrate comprises carbon atoms of which is less than about 7% in the form of carbonyl, the metal-plate coating will be inferior and subject to detachment from the thermoplastic olefin substrate.
  • active surface is intended in denote a surface layer of the TPO substrate having a thickness of from about 3 to about 5 nm.
  • modified TPO is intended to mean polypropylene-based materials such as polyolefin modified with a first elastomeric material such ethylene propylene diene monomer (EPDM) and further modified with a second elastomer including a diene and triene type polymer.
  • first elastomeric material such as ethylene propylene diene monomer (EPDM)
  • second elastomer including a diene and triene type polymer.
  • Figure 1 is a perspective view of an automotive trim piece of the present invention.
  • Figure 2 is a cross sectional view of the automotive trim price of Figure 1.
  • the process of the present invention is useful to directly metallize a TPO substrate.
  • the TPO substrate is a modified TPO comprising a polyolefin material modified with a first elastomer, such as EPDM and then modified with a second elastomer, including diene and triene type polymers, such as acrylonitrile and butadiene.
  • the elastomers are added in effective amounts providing a basis for an active surface as discussed below.
  • the TPO is molded in a conventional manner into a substrate 10.
  • the substrate is in the form of an automotive component such as a grill.
  • other components such as fascia, trim panels, rocker panels, fenders, trim strips are also contemplated in the present invention.
  • a surface of the TPO substrate 14 is activated by one of the methods described below to provide an active surface 16.
  • the active surface 16 is a presentation or exterior-facing surface of the molded part on which a metal layer 18 is deposited.
  • the active surface 16 of the TPO substrate 14 comprises carbon atoms of which at least about 7 % are in the form of carbonyl. Preferably from about 7 % to about 25 % of carbon atoms at the active surface are in the form of carbonyl. More preferably, from about 7% to about 20% of carbon atoms at the active surface are in the form of carbonyl. Most preferably, about 7% to about 15% of carbon atoms at the active surface are in the form of carbonyl.
  • the presence of the carbonyl groups at the active surface may be confirmed by conventional techniques - e.g., FTIR (Fourier Transform Infrared spectroscopy).
  • the concentration of carbonyl groups at the active surface may be confirmed by conventional techniques - e.g. , XPS (X-ray photoelectron spectroscopy).
  • a modified TPO is utilized and the desired amount of carbonyl content can be conferred to the surface of a modified TPO substrate by controlling preferred pretreatment steps in the process. .
  • the etching technique comprises contacting the modified TPO substrate with an etching solution comprising chromic acid or a mixture of chromic acid and sulfuric acid. During this etching step the active surface is formed. It is believed that chromic acid is reduced on the surface of the modified TPO substrate to provide oxygen containing moieties (e.g., hydroxyl, ether and the like), including the desired carbonyl groups. The amount of desired carbonyl groups may be controlled by the time period during which the substrate is immersed in the etching solution.
  • the chemical(s) used in the above-mentioned etching step may be obtained commercially from Atotech Canada Ltd. under the tradename FuturonTM.
  • the active surface of the modified TPO substrate is subjected to chromic acid reduction to reduce any residual chromic acid left in the pores of the substrate from Cr 6+ to Cr 3+ (the reason for this is that Cr 6+ is detrimental if present during later steps in the process).
  • the active surface of the modified TPO substrate is contacted with an acid.
  • a non-limiting useful such acid is hydrochloric acid.
  • the chemicals used in the above-mentioned chromic acid reduction and pre- dipping steps are commercially available under the tradename FuturonTM from Atotech Canada Ltd.
  • the active surface of the modified TPO substrate is then ready for further activation wherein a surface thereof is fully activated for electrolytic metallization.
  • the solution comprises palladium chloride and stannous chloride.
  • stannic palladium in a concentration of from about 5 to about 20,000 ppm (0.005 to 20 g/L), preferably 20 to about 300 ppm (0.02 to 0.3 g/L), more preferably from about 20 to about 250 ppm (0.02 to 0.25 g/L) for a period of at least about one minute, preferably from about one minute to about ten minutes, more preferably from about two minutes to about four minutes.
  • This activation step serves to anchor the palladium/tin complex to the surface of the TPO substrate.
  • This activation step serves to anchor the palladium/tin complex to the surface of the TPO substrate.
  • a desirable level of palladium/tin complex is dispersed over the surface of the substrate.
  • the next step in the process is to exchange the tin in the palladium/tin complex with copper.
  • This is done in a conventional manner.
  • the chemical(s) used in the above-mentioned electrolytic metallization steps may be obtained commercially from Atotech Canada Ltd. under the tradename FuturonTM.
  • a layer of nickel or copper can be deposited on the active surface in a conventional manner, including electroless deposition whereby nickel or copper salt is reduced onto the active surface of the TPO substrate.
  • Advantages of the nickel or copper layer include increased conductivity, reduced bath time and lower palladium concentrations ( ⁇ lOOppm or 0.1 g/L) in the palladium bath discussed above.
  • Step (ii) of the present process comprises electrochemically depositing a metal layer 18 on the active surface 14 of the TPO substrate 14. This can be done in a conventional manner.
  • a modified TPO obtained from Solvay Engineered Polymers was activated, treated and electrolytically metallized in the following manner.
  • the FuturonTM pre-plating process comprises the following general steps: (i) cleaner (optional); (ii) etching (typically with chromic sulfuric acid); (iii) reduction (typically with Cr (VI), (iv) pre-dip solution; (v) Pd/Sn activation and (vi) Cu-link.
  • the modified TPO substrate was treated according to the particulars set out in Tables 1 and 2.
  • Etch time was varied as set out in Table 3 below.
  • Pre-plate tank conditions (dwell times, concentrations, temperatures) are reported below. All panels were plated using a conventional acid copper-electroplating bath, followed by conventional electroplating nickel and chrome baths. Panels were plated for 60 minutes at 30 amps/ft 2 to achieve 40+/- 5 microns of copper thickness for peel testing as defined in ASTM B533.
  • test panels were stripped of palladium and copper using a solution of Aqua Regia (1: 1). Solutions were analysed for metal content using Atomic Adsorption spectrophotometry. Samples were tested for peel strength using the 90° tensile test, on an InstronTM instrument in accordance with ASTM B533. Each sample panel was cut into three strips and each strip tested. The overall average of the strips for each
  • Example is reported as the peel strength of the panel.
  • the peel test results illustrate that significantly improved adhesion of the metal plating layer is achieved in Examples 2 and 3 (carbonyl content of at least 7%) compared with that achieved in Example 1 (carbonyl content less than 7%).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé de galvanoplastie directe d'un substrat plastique (14). Ledit procédé consiste (i) à activer une surface d'un substrat polyoléfinique modifié afin d'obtenir une surface active (16), ladite surface active (16) comprenant au moins 7 % d'atomes de carbone sous forme de carbonyle, et (ii) à déposer par un procédé électrochimique une couche métallique (18) sur la surface active (16).
EP01921064A 2000-04-05 2001-04-05 Procede de galvanoplastie directe d'un substrat plastique Expired - Lifetime EP1268880B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US19469300P 2000-04-05 2000-04-05
US194693P 2000-04-05
PCT/CA2001/000463 WO2001077419A2 (fr) 2000-04-05 2001-04-05 Procede de galvanoplastie directe d'un substrat plastique

Publications (2)

Publication Number Publication Date
EP1268880A2 true EP1268880A2 (fr) 2003-01-02
EP1268880B1 EP1268880B1 (fr) 2005-03-16

Family

ID=22718560

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01921064A Expired - Lifetime EP1268880B1 (fr) 2000-04-05 2001-04-05 Procede de galvanoplastie directe d'un substrat plastique

Country Status (8)

Country Link
US (1) US20040222103A1 (fr)
EP (1) EP1268880B1 (fr)
AU (1) AU2001248179A1 (fr)
BR (1) BR0109887A (fr)
CA (1) CA2404946A1 (fr)
DE (1) DE60109432T2 (fr)
MX (1) MXPA02009785A (fr)
WO (1) WO2001077419A2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060104074A1 (en) * 2004-09-10 2006-05-18 Boniface Robert E Vehicle body
US7666471B2 (en) * 2006-03-22 2010-02-23 Mark Wojtaszek Polyimide substrate and method of manufacturing printed wiring board using the same
FR2930180B1 (fr) * 2008-04-22 2010-12-17 Inst Superieur De Plasturgie D Alencon Entpr S Procede de metallisation d'un substrat non conducteur en matiere plastique
EP3019711B1 (fr) 2013-07-09 2023-11-01 RTX Corporation Nosecône en polymère plaqué pour turbine à gas
EP3019710A4 (fr) 2013-07-09 2017-05-10 United Technologies Corporation Ventilateur en polymère plaqué
WO2015006487A1 (fr) 2013-07-09 2015-01-15 United Technologies Corporation Protection contre l'érosion et l'usure pour composites et polymères plaqués
EP3019723A4 (fr) 2013-07-09 2017-05-10 United Technologies Corporation Compresseur polymère plaqué
CA2917955A1 (fr) * 2013-07-09 2015-01-15 United Technologies Corporation Placage d'un composite pour renforcer le collage d'elements metalliques
WO2015053832A2 (fr) 2013-07-09 2015-04-16 United Technologies Corporation Revêtement à module élevé pour le raidissement local de bords de fuite d'un plan de sustentation
WO2015006421A1 (fr) 2013-07-09 2015-01-15 United Technologies Corporation Article polymère sous encapsulation métallique
CN105112971A (zh) * 2015-09-22 2015-12-02 太仓市金鹿电镀有限公司 一种汽车散热格栅沙镍电镀工艺

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1488559A (fr) * 1965-08-03 1967-10-27
US3556955A (en) * 1966-02-18 1971-01-19 Union Carbide Corp Process of metal plating plastics
US4002595A (en) * 1973-12-27 1977-01-11 E. I. Du Pont De Nemours And Company Electroplatable polypropylene compositions
US4298424A (en) * 1980-06-19 1981-11-03 Vbe Industries, Ltd. Method for etching polyamide shaped articles
JPS63247376A (ja) * 1987-04-03 1988-10-14 Citizen Watch Co Ltd プラスチツク成形品への無電解メツキの前処理方法
US5340451A (en) * 1990-10-04 1994-08-23 International Business Machines Corporation Process for producing a metal organic polymer combination
EP0905285B1 (fr) * 1997-02-03 2000-12-27 Okuno Chemical Industries Co., Ltd. Procede pour metalliser par voie electrolytique un materiau non conducteur
GB9722028D0 (en) * 1997-10-17 1997-12-17 Shipley Company Ll C Plating of polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0177419A2 *

Also Published As

Publication number Publication date
EP1268880B1 (fr) 2005-03-16
US20040222103A1 (en) 2004-11-11
WO2001077419A3 (fr) 2002-09-12
BR0109887A (pt) 2003-06-03
DE60109432T2 (de) 2006-04-06
MXPA02009785A (es) 2004-09-06
WO2001077419A2 (fr) 2001-10-18
AU2001248179A1 (en) 2001-10-23
DE60109432D1 (de) 2005-04-21
CA2404946A1 (fr) 2001-10-18

Similar Documents

Publication Publication Date Title
EP1268880B1 (fr) Procede de galvanoplastie directe d'un substrat plastique
JP3208410B2 (ja) 非導電性プラスチック成形品への電気めっき方法
JP4776033B2 (ja) スパッタリングによる樹脂導電化を利用した装飾めっき品の製造方法
CN100519838C (zh) 镀敷树脂材料的方法
EP1942207A1 (fr) Solution de prétraitement et procédé de formation d'une couche d'un métal de revêtement sur un substrat doté d'une surface en plastique
EP1793013B1 (fr) Métallisation de diélectriques
KR102366687B1 (ko) 무전해 도금의 전처리용 조성물, 무전해 도금의 전처리 방법, 무전해 도금 방법
US4005238A (en) Metallized articles and method of producing the same
US20040132300A1 (en) Procedure for activation of substrates for plastic galvanizing
US5300140A (en) Hydroprimer for metallising substrate surfaces
JPH05148686A (ja) 耐衝撃性プラスチツクの電気メツキ法
US6506293B1 (en) Process for the application of a metal film on a polymer surface of a subject
US20040115353A1 (en) Method of pretreatment of material to be electrolessly plated
DE102020118642A1 (de) Verfahren zur Herstellung und Farbgebung eines metallisierten Kunststoffbauteils, metallisiertes Kunststoffbauteil sowie dessen Verwendung
US5316867A (en) Method for adhering metal coatings to thermoplastic addition polymers
US20030108751A1 (en) Plated articles and methods for producing the plated articles
US4445979A (en) Method of forming composite surface on a dielectric substrate
WO2008004558A1 (fr) Procédé de production un objet ornemental plaqué en convertissant une résine en une résine conductrice par métallisation sous vide et gabarit suspendu pour la fixation du moulage de résine
US6541080B1 (en) Double-dip Pd/Sn crosslinker
EP1546435B1 (fr) Procede pour le pretraitement d'une surface d'un materiau non conducteur devant subir une electrodeposition
JPH06279609A (ja) 合成樹脂成形品
JP2001011643A (ja) 不導体のめっき方法
JPH1018055A (ja) プラスチック表面のメッキによる金属化方法
EP1454999A1 (fr) Matériau ou article présentant un revêtement métallique
EP2082631B1 (fr) Procédé de revêtement, et revêtement ainsi obtenu

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20021004

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20040127

RBV Designated contracting states (corrected)

Designated state(s): BE DE GB

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60109432

Country of ref document: DE

Date of ref document: 20050421

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20051219

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090402

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090428

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090401

Year of fee payment: 9

BERE Be: lapsed

Owner name: *DECOMA EXTERIOR TRIM INC.

Effective date: 20100430

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100430

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100405