EP1001052A2 - Verfahren zur Metallisierung einer Kunststoffoberfläche - Google Patents
Verfahren zur Metallisierung einer Kunststoffoberfläche Download PDFInfo
- Publication number
- EP1001052A2 EP1001052A2 EP99115967A EP99115967A EP1001052A2 EP 1001052 A2 EP1001052 A2 EP 1001052A2 EP 99115967 A EP99115967 A EP 99115967A EP 99115967 A EP99115967 A EP 99115967A EP 1001052 A2 EP1001052 A2 EP 1001052A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- plastic surface
- pickling
- treatment
- salt solution
- 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
Links
- 229920003023 plastic Polymers 0.000 title claims abstract description 102
- 239000004033 plastic Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims description 81
- 238000005554 pickling Methods 0.000 claims abstract description 81
- 239000000243 solution Substances 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000012266 salt solution Substances 0.000 claims abstract description 48
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001465 metallisation Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000009189 diving Effects 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical class [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 239000012286 potassium permanganate Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
-
- 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
Definitions
- the invention relates to a method for metallization a plastic surface.
- Process is the plastic surface of a plastic object or become plastic surfaces of several Metallized plastic objects.
- Metallized plastics become decorative on the one hand Purposes, for example in the sanitary area or at Automotive manufacturing. On the other hand, one finds Metallization of plastics but also in the context of the coating of electronic components for the purpose of electronic Shielding instead. For decorative purposes especially surfaces of plastics such as acrylonitrile-butadiene-styrene (ABS) and possibly ABS polycarbonate blends metallized.
- ABS acrylonitrile-butadiene-styrene
- ABS ABS polycarbonate blends
- the Plastic surface first by vigorous pickling, for example with chromic acid or chromic acid, roughened.
- Roughening means in particular that by strong stains in the plastic surface of micro caverns be generated.
- the micro caverns usually have Diameters in the order of 0.1 to 10 ⁇ m. In particular, these micro-caverns have a depth (i.e. H. an extension from the plastic surface into the Plastic interior), which are of the order of 0.1 to 10 ⁇ m.
- the pickling takes place here at relatively high Temperatures and usually over a relatively long time Periods.
- the concentration of one used in the pickling solution Oxidizer is usually relatively high.
- the roughening of the plastic surface serves that an subsequently applied activation layer and / or Metal layer as it were in the roughened plastic surface can anchor or get caught. Liability a layer of metal on the roughened plastic surface is as it were in this known method reached a push button principle.
- the surface becomes roughened first with colloidal palladium or ionogenic palladium activated. This activation follows in the case of the colloidal Process a detachment of a tin protection colloid or a reduction in the case of the ionogenic process elemental palladium. It then becomes chemical Copper or chemical nickel as a conductive layer on the Plastic surface deposited. Then the galvanic coating or metallization instead. This Direct metallization of the plastic surfaces works in practice only for certain plastics.
- Plastic surface is then covered with a copper salt solution treated and then with a second solution treated that contains sulfide ions or polysulfide ions.
- a copper salt solution treated and then with a second solution treated that contains sulfide ions or polysulfide ions.
- an electronically conductive layer of non-stoichiometric copper sulfide on the plastic surface generated.
- the invention is based on the technical problem to specify a procedure of the type mentioned at the beginning, with which a large number of plastics can be produced in a less complex manner reliable and reproducible metallized can be and the plastics with a metal layer provided that meets all requirements.
- the method steps according to the invention can be further Process steps, in particular rinsing steps, interposed his.
- Mild pickling conditions means in the context of the invention in particular that the "pickling" or the corresponding treatment the plastic surface with a pickling solution at low Temperatures and / or during a short treatment time and / or carried out at a low concentration of the pickling solution becomes. Mild pickling conditions can in principle can already be realized if one of the above three conditions are met.
- Low temperature means within the scope of the invention a temperature of maximum 40 ° C. If mild pickling conditions due to a low temperature are set, this is expediently a maximum 30 ° C, preferably between 15 ° C and 25 ° C.
- the pretreatment mentioned low temperatures takes place with the pickling solution, especially over a period of time from 3 to 15 minutes, preferably from 5 to 15 minutes, is preferred from 5 to 10 minutes. It is within the scope of Invention that the treatment time is shorter, ever higher the temperature is. Mild pickling conditions can, however can also be realized at temperatures above 40 ° C, if the treatment time is chosen accordingly short becomes.
- the Pickling treatment at temperatures from 40 ° C to 95 ° C, preferably 50 ° C to 70 ° C over a treatment period from 15 seconds to 5 minutes, preferably from 0.5 to 3 minutes. instead of. It is also within the scope of the invention that the The higher the treatment temperature, the shorter the treatment time is.
- the treatment temperature is expedient and / or the treatment time of the pickling treatment depending on the type of pickling solution used chosen.
- Mild pickling also means within the scope of the invention that in contrast to the known methods explained at the outset a roughening of the plastic surface or a generation of micro-caverns in the plastic surface takes place.
- the state-of-the-art in pickling Usually have micro-caverns or cavities Diameters or depths on the order of 0.1 to 10 ⁇ m.
- the Pickling conditions are set so that the Plastic surface only small openings or pores are generated that have a diameter and in particular a Depth ⁇ 0.09 ⁇ m, preferably ⁇ 0.05 ⁇ m. Depth means the extension of the opening / gates from the plastic surface inside the plastic.
- pickling conditions means that the Pickling conditions are set with the proviso that only the small pores mentioned in the plastic surface generated and micro-caverns or inner There are no voids in the plastic surface. Expediently in the area of the plastic surface Diffusion openings or diffusion channels generated that have a depth of ⁇ 0.09 microns, preferably ⁇ 0.05 microns.
- the mild pickling treatment according to the invention can be carried out with a Pickling solution and / or basically also by plasma treatment or plasma etching can be realized.
- a pickling solution used for pickling preferably contains at least one oxidizing agent. Mild pickling also means in the context of the invention that an oxidizing agent is used in a relatively low concentration. Permanganate and / or peroxodisulfate and / or periodate and / or peroxide can be used as the oxidizing agent. In one embodiment, pickling is carried out using an acidic pickling solution which contains at least one oxidizing agent. An acidic aqueous pickling solution which contains permanganate and phosphoric acid (H 3 PO 4 ) and / or sulfuric acid is preferably used. Potassium permanganate is expediently used as the permanganate.
- an acidic pickling solution which contains only phosphoric acid or mainly contains phosphoric acid and only a little sulfuric acid is very preferably used.
- the pickling treatment is carried out with an alkaline aqueous solution containing permanganate.
- potassium permanganate is preferably used.
- the alkaline aqueous solution expediently contains sodium hydroxide solution.
- the type of pickling solution used is selected depending on the type of plastic treated.
- the oxidizing agent is preferably contained in the pickling solution in a concentration of 0.05 to 0.6 mol / l.
- the pickling solution expediently contains 0.05 to 0.6 mol / l permanganate or persulfate.
- the pickling solution contains 0.1 to 0.5 mol / l periodate or hydrogen peroxide.
- the pickling solution very preferably contains permanganate.
- the content of permanganate is preferably 1 g / l up to the solubility limit of the permanganate, preferably the potassium permanganate.
- a permanganate solution expediently contains 2 to 15 g / l permanganate, preferably 2 to 15 g / l potassium permanganate. It is within the scope of the invention that the permanganate solution contains a wetting agent.
- a mild pickling can also be demonstrated with a diluted one aqueous persulfate solution or periodate solution or one dilute aqueous peroxide solution.
- a pickling solution carried out with stirring.
- the plastic surface is expediently pickled rinsed, for example 1 to 3 minutes in water.
- a temperature of at most 30 ° C, preferably at a Temperature between 15 and 25 ° C carried out It is therefore within the scope of the invention, also the treatment with the Metal salt solution in the range of room temperature.
- the treatment with the metal salt solution is expedient without stirring instead.
- the treatment time is preferably 30 seconds to 15 minutes, preferably 3 to 12 minutes.
- a metal salt solution is preferably used, in which a pH between 7.5 and 12.5, preferably between 8 and 12 is set.
- the invention is with a metal salt solution worked that contains ammonia and / or at least one amine.
- the above pH adjustment can be done with Aid made of ammonia and in this case is under the invention an ammoniacal metal salt solution used.
- an ammoniacal metal salt solution used.
- the metal salt solution can, for example Contain monoethanolamine and / or triethanolamine.
- Treatment with the metal salt solution means in the frame the invention in particular dipping the plastic surface into the metal salt solution.
- a cobalt salt solution is used as the metal salt solution.
- the cobalt salt solution preferably contains 0.1 to 15 g / l of Co (II) salt, preferably 5 to 12 g / l of Co (II) salt.
- the cobalt (II) solution expediently contains cobalt (II) sulfate and / or cobalt (II) chloride.
- the cobalt (II) solution preferably contains 0.1 to 15 g / l CoSO 4 .7H 2 O, very preferably 1 to 10 g / l CoSO 4 .7H 2 O.
- a metal salt solution worked in particular cobalt salt solution that contains at least one oxidizing agent.
- the oxidizing agent can be, for example, hydrogen peroxide.
- the oxidizing agent can also be provided by blowing air into the metal salt solution.
- the metal salt solution is a cobalt (II) salt solution
- the oxidizing agent is preferably used with the proviso that at least part of the cobalt (II) is oxidized to cobalt (III). - After the treatment with the metal salt solution, the plastic surface is expediently rinsed.
- the treatment time or diving time is preferably 10 Sec. To 3. Min., Very preferably 0.5 to 2 Min. Preferably at a bath temperature of maximum 30 ° C, preferably 15 to 25 ° C, worked.
- the alkaline aqueous The solution expediently has a pH of 9 to 14 on. Diving in aqueous alkaline solution is very enjoyable preferably in dilute sodium hydroxide solution. It's in the frame of the invention for the preparation of the aqueous alkaline Solution of sodium hydroxide and / or potassium hydroxide and / or Use sodium carbonate. It very preferably contains aqueous alkaline solution 5 to 50 g / l sodium hydroxide or Potassium hydroxide.
- the concentration is preferred
- the plastic surface can be used instead of aqueous alkaline solution also with an aqueous acidic Solution to be treated. - It is within the Invention, a rinse after the immersion treatment with water or distilled water.
- the plastic surface is treated in accordance with process step 1.3) with an alkaline solution of an alkali metal sulfide.
- An ammonium sulfide can also be used.
- the sulfide can be, for example, a monosulfide, a disulfide, a trisulfide, a tetrasulfide or a polysulfide.
- Na 2 S sodium
- the concentration of the alkali metal monosulfide, preferably the sodium sulfide, is preferably 0.5 to 10 g / l, very preferably 2 to 8 g / l.
- the alkaline solution of the alkali metal sulfide expediently contains 5 to 25 g / l of sodium hydroxide, for example 10 g / l of sodium hydroxide.
- Treatment with the sulfide solution is preferably carried out over a period of 15 seconds to 5 minutes, very preferably 30 seconds to 2 minutes.
- Treatment with the sulfide solution according to process step 1.3) is preferably carried out at a temperature of at most 30 ° C. preferably carried out at a temperature between 15 and 25 ° C. - After the treatment with the sulfide solution, it is expedient to rinse, for example 1 to 3 minutes, with cold water.
- the metal salt solution preferably cobalt salt solution and / or the sulfide solution Complexing agent to stabilize the corresponding solution is clogged.
- the metal salt solution can therefore the metal at least partially in the form of a metal complex.
- the A wetting agent is added to the metal salt solution and / or sulfide solution is thus a better wetting of the plastic surface takes place.
- a sulfide solution can be used be at least one substance from the group "Alcohol, diol, polyol, polyalkane glycol, polyalkylene glycol, gel / sol forming substance such as silica gel or aluminum oxide gel " contains. It is within the scope of the invention Use mixtures of these substances in the sulfide solution. - It can in the context of the inventive method also with a metal salt solution, preferably cobalt salt solution be worked on, which at least one substance from the Group "alcohol, diol, polyol, polyalkane glycol, polyalkylene glycol, gel / sol forming substance such as silica gel or alumina gel ". It is within the scope of Invention, mixtures of the substances mentioned in the Use metal salt solution.
- the plastic surface is dried. It is within the scope of the invention that Drying by heat treatment of the plastic surface (at elevated temperature) is realized.
- the plastic surface is preferably metallized only after drying. Basically can when performing the method according to the invention Treatment with the metal salt solution and / or the treatment can be repeated with the sulfide solution. It's in the frame the invention that in multiple treatment with the sulfide solution the plastic surface after each treatment is dried.
- the plastic surface can be directly metallized.
- the plastic surface is nickel-plated in a nickel bath according to process step 1.4).
- direct electrolytic metallization can be carried out.
- Electrochemical nickel plating preferably takes place in a Watts electrolyte.
- the treatment time is expediently 10 to 15 minutes and the electrolyte temperature is preferably 30 to 40 ° C. It is within the scope of the invention that the electrochemical nickel plating is carried out with an initial current density of 0.3 A / dm 2 , with the current density is increased up to 3 A / dm 2 later.
- a nickel layer can be applied to the plastic surface by electrolytic metallization.
- the invention is based on the knowledge that by the mild pickling according to the invention the plastic surface is manipulated so that, ultimately, surprisingly a very firm adhesion of the applied metal layer is reached on the plastic surface.
- This firmly adhering metal layers have a high resistance to temperature changes accordingly and all pass accordingly usual temperature change shocks.
- the invention also lies based on the knowledge that with the invention Process achieved conditions in a relatively short time can be used for the subsequent application of the Metal layer or nickel layer are optimally suitable. Although it is basically within the scope of the invention, to repeat the method steps according to the invention and in particular to repeat process steps 1.2) and 1.3), surprisingly, optimal results are also achievable without repeating these process steps.
- ABS polyoxymethylene
- PEEK polyether ether ketone
- PP polypropylene
- an acidic pickling solution is used for the mild pickling which contains 100 to 300 ml / l water, 700 to 900 ml / l concentrated phosphoric acid and 3 to 7 g / l potassium permanganate.
- the acidic pickling solution consists of 74% by weight phosphoric acid, 26% by weight water and 5 g potassium permanganate.
- an alkaline pickling solution is used for mild pickling, which advantageously contains 20 to 40 g / l sodium hydroxide and 5 to 15 g / l potassium permanganate.
- the alkaline aqueous pickling solution consists of 30 g / l sodium hydroxide and 10 g / l potassium permanganate.
- pickling is preferably carried out at room temperature and over a treatment time of 10 minutes. Following the pickling treatment, the plastic surface is expediently rinsed with water.
- an ammoniacal metal salt solution which contains 0.1 to 12 g / l cobalt (II) sulfate and 10 to 50 ml / l 25% ammonia solution.
- the cobalt salt solution is preferably activated at room temperature for a treatment time of 5 to 10 minutes.
- the plastic surface is expediently rinsed with water after the activation with the cobalt salt solution.
- 10 to 50 g / l sodium hydroxide are dissolved in water.
- an aqueous alkaline solution with 20 g / l sodium hydroxide is used.
- the immersion in the aqueous alkaline solution expediently takes place at room temperature and over a treatment period of 0.5 to 2 minutes.
- An alkaline sulfide solution which contains 0.5 to 10 g / l sodium sulfide (Na 2 S) and advantageously 5 to 25 g / l sodium hydroxide is preferably used as the sulfide solution.
- an alkaline alkali sulfide solution which contains 5 g / l sodium sulfide (Na 2 S) and 10 g / l sodium hydroxide.
- the sulfide treatment is preferably carried out at room temperature and for a treatment period of 0.5 to 5 minutes.
- the plastic surface is expediently rinsed with water after the sulfide treatment. It is within the scope of the invention that the plastic surface is dried before metallization, in particular nickel plating.
- Exemplary embodiments 1 and 2 correspond to the prior art (comparative examples), while exemplary embodiments 3 to 6 illustrate the method according to the invention.
- examples 1, 3 and 5 discs made of ABS plastic with a surface area of 50 cm 2 were used, while in examples 2, 4 and 6, molded products made of impact-resistant polystyrene with a surface area of 70 cm 2 were used.
- the specification "M” corresponds to the concentration specification "mol / l”.
- Disks made of ABS plastic with a surface area of 50 cm 2 were pickled for 3 minutes at 70 ° C. in a pickling solution made of 4 M H 2 SO 4 and 3.5 M CrO 3 . Then it was rinsed with water.
- the plastic objects were then treated for 30 seconds in an ammoniacal solution with 0.5 M CuSO 4 .5H 2 O, which had a pH of 9.5 and a temperature of 20 ° C.
- the plastic objects were immersed in distilled water for 20 seconds and then treated for 30 seconds with a sulfide solution containing 0.1 M Na 2 S 2 and having a temperature of 20 ° C. After this treatment, the plastic articles were washed again with cold water. This was followed by the electrochemical nickel plating.
- Molded objects made of impact-resistant polystyrene with a surface area of 70 cm 2 were pickled for 30 seconds in a pickling solution which contained 15 MH 2 SO 4 and 0.1 M CrO 3 and had a temperature of 20 ° C. It was then washed with water and then immersed in an emulsion of 0.2 g / l xylene and 0.2 g / l sintanol at 20 ° C. for 30 seconds. After the pickling treatment, the articles were washed with distilled water. The objects were then treated for 30 seconds in a metal salt solution which contained 0.5 M CuSO 4 .5H 2 O and in which the pH had been adjusted to 9.8 with monoethanolamine. The temperature of the solution was 20 ° C.
- the articles were then immersed in distilled water for 20 seconds and then treated for 30 seconds with a sulfide solution which contained 0.1 M Na 2 S and which had a temperature of Had 20 ° C. Thereafter, the treatment in the metal salt solution and the subsequent treatment with the sulfide solution were repeated in the order described above. After this treatment, the objects were rinsed with distilled water and nickel-plated electrochemically in a Watts electrolyte according to embodiment 1.
- the surface of the ABS plastic parts was pickled at room temperature in a solution containing 15 MH 2 SO 4 and 0.05 M KMnO 4 .
- the objects were rinsed with water and then treated for 10 minutes in an ammoniacal solution which contained 0.1 M CoSO 4 and had a pH of 10 and a temperature of 20 ° C.
- the articles were then treated with water acidified to a pH of 1 with H 2 SO 4 . This was followed by treatment with a sulfide solution containing 0.01 M Na 2 S 2 for a period of 30 seconds.
- the objects were rinsed with distilled water, dried and then electrochemically nickel-plated in a Watts electrolyte according to embodiment 1.
- the surface of the impact-resistant polystyrene articles was pickled for 10 minutes at room temperature with a solution containing 17 MH 2 SO 4 and 1 MH 2 O 2 .
- the objects were rinsed with water and then treated for 10 minutes in a solution which contained 0.01 M CoF 3 and monoethanolamine up to a pH of 8 at a temperature of 20 ° C.
- the articles were then immersed in an aqueous alkaline solution containing enough sodium hydroxide for 20 seconds to have a pH of 14. It was then treated for 30 seconds with a sulfide solution containing 0.05 MK 2 S 4 .
- the treated articles were then rinsed with distilled water, dried and then nickel-plated for 15 minutes in a Watts electrolyte according to Example 1.
- the surfaces of the ABS plastic objects were pickled at room temperature with a solution containing 13 MH 3 PO 4 and 0.5 MK 2 S 2 O 8 . After pickling, the objects were rinsed with water. Thereupon they were treated for 10 minutes in a solution containing 0.25 M CoSO 4 and triethanolamine up to a pH of 9 at 20 ° C. Then the articles were immersed in an aqueous alkaline solution adjusted to pH 9 with sodium carbonate. Thereafter, treatment was carried out for 30 seconds in a sulfide solution containing 0.02 K 2 S 3 . After the treatment, the plastic objects were rinsed with distilled water, dried and then electrochemically nickel-plated in a Watts electrolyte according to working example 1 over a period of 15 minutes.
- the surface of the impact-resistant polystyrene articles was pickled at room temperature with a solution containing 17 M H 2 SO 4 and 0.5 M KJO 4 . After pickling, the articles were rinsed with water and then treated for 10 minutes in a solution which contained 0.01 M CoF 3 and in which a pH of 12 had been set with ammonia and which had a temperature of 20 ° C. . Then the objects were immersed for 20 seconds in an acidic solution in which a pH of 5 was set using acetic acid. The articles were then treated in a sulfide solution containing 0.01 M Na 2 S for 30 seconds. After this treatment, the objects were rinsed with distilled water, dried and then nickel-plated for 15 minutes in a Watts electrolyte according to working example 1.
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Abstract
Description
Claims (16)
- Verfahren zur Metallisierung einer Kunststoffoberfläche, wobei die folgenden Verfahrensschritte nacheinander durchgeführt werden:1.1) die Kunststoffoberfläche wird einer Beizbehandlung unter milden Beizbedingungen unterzogen,1.2) im Anschluß daran wird die Kunststoffoberfläche mit einer Metallsalzlösung behandelt, die zumindest ein Salz aus der Gruppe "Kobaltsalz, Silbersalz, Zinnsalz, Bleisalz" enthält,1.3) die Kunststoffoberfläche wird mit einer Sulfidlösung behandelt,1.4) letztendlich wird die Kunststoffoberfläche in einem Metallisierungsbad metallisiert.
- Verfahren nach Anspruch 1, wobei die Beizbehandlung bei einer Temperatur von maximal 40° C, vorzugsweise maximal 30° C, während eines Behandlungszeitraumes von 3 bis 15 Min., vorzugsweise 5 bis 10 Min., durchgeführt wird.
- Verfahren nach Anspruch 1, wobei die Beizbehandlung bei Temperaturen von über 40° C bis 95° C, vorzugsweise von über 30° C bis 90° C während eines Behandlungszeitraumes von 15 Sek. bis 5 Min., vorzugsweise von 0,5 bis 3 Min., durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 3, wobei mit einer sauren Beizlösung, die zumindest ein Oxidationsmittel enthält, gebeizt wird.
- Verfahren nach einem der Ansprüche 1 bis 4, wobei mit einer sauren wäßrigen Beizlösung, die Permanganat und Phosphorsäure und/oder Schwefelsäure enthält, gearbeitet wird.
- Verfahren nach einem der Ansprüche 1 bis 5, wobei die Beizbehandlung mit einer permanganathaltigen alkalischen wäßrigen Lösung durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 6, wobei die Behandlung mit der Metallsalzlösung bei einer Temperatur von maximal 30° C, vorzugsweise bei einer Temperatur zwischen 15 und 25° 0, durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 7, wobei mit einer Metallsalzlösung gearbeitet wird, in der ein pH-Wert zwischen 7,5 und 12,5, vorzugsweise zwischen 8 und 12, eingestellt wird.
- Verfahren nach einem der Ansprüche 1 bis 8, wobei mit einer Metallsalzlösung gearbeitet wird, die Ammoniak und/oder zumindest ein Amin enthält.
- Verfahren nach einem der Ansprüche 1 bis 9, wobei mit einer Kobaltsalzlösung als Metallsalzslösung gearbeitet wird und die Kobaltsalzlösung 0,1 bis 15 g/l Kobalt(II)salz, bevorzugt 0,5 bis 12 g/l Kobalt(II)salz enthält.
- Verfahren nach einem der Ansprüche 1 bis 10, wobei mit einer Metallsalzlösung, insbesondere Kobaltsalzlösung gearbeitet wird, die zumindest ein Oxidationsmittel enthält.
- Verfahren nach einem der Ansprüche 1 bis 11, wobei zwischen den Verfahrensschritten 1.2) und 1.3) ein Tauchen der Kunststoffoberfläche in eine wäßrige alkalische Lösung durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 12, wobei im Verfahrensschritt 1.3) die Kunststoffoberfläche mit einer alkalischen Lösung eines Alkalimetallsulfids behandelt wird.
- Verfahren nach einem der Ansprüche 1 bis 13, wobei die Behandlung mit der Sulfidlösung gemäß Verfahrensschritt 1.3) bei einer Temperatur von maximal 30° C, vorzugsweise bei einer Temperatur zwischen 15 und 25° C durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 14, wobei zwischen dem Verfahrensschritt 1.3) und dem Verfahrensschritt 1.4) eine Trocknung der Kunststoffoberfläche durchgeführt wird.
- Verfahren nach einem der Ansprüche 1 bis 15, wobei die Kunststoffoberfläche gemäß Verfahrensschritt 1.4) in einem Nickelbad vernickelt wird.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA01004811A MXPA01004811A (es) | 1998-11-13 | 1999-11-05 | Proceso para metalizar una superficie de plastico. |
JP2000582621A JP2002530529A (ja) | 1998-11-13 | 1999-11-05 | プラスチック面の金属化処理プロセス |
AU12433/00A AU1243300A (en) | 1998-11-13 | 1999-11-05 | Process for metallizing a plastic surface |
PCT/US1999/026066 WO2000029646A1 (en) | 1998-11-13 | 1999-11-05 | Process for metallizing a plastic surface |
CNB998154938A CN1184361C (zh) | 1998-11-13 | 1999-11-05 | 塑料表面敷镀金属的方法 |
KR1020017006001A KR20010086023A (ko) | 1998-11-13 | 1999-11-05 | 플라스틱 표면을 금속 처리하는 방법 |
US09/831,008 US6712948B1 (en) | 1998-11-13 | 1999-11-05 | Process for metallizing a plastic surface |
BR9915280-0A BR9915280A (pt) | 1998-11-13 | 1999-11-05 | Processo para metalizar uma superfìcie plástica |
CA002350422A CA2350422A1 (en) | 1998-11-13 | 1999-11-05 | Process for metallizing a plastic surface |
TW088119793A TWI221163B (en) | 1998-11-13 | 1999-11-11 | Process for metallizing a plastic surface |
US10/703,057 US20040096584A1 (en) | 1998-11-13 | 2003-11-06 | Process for metallizing a plastic surface |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
LT9800161 | 1998-11-13 | ||
LT98-161A LT4713B (lt) | 1998-11-13 | 1998-11-13 | Elektrai laidžių dangų ant dielektriko paviršiaus gavimo būdas |
DE19904665 | 1999-02-04 | ||
DE1999104665 DE19904665A1 (de) | 1999-02-04 | 1999-02-04 | Verfahren zur Metallisierung einer Kunststoffoberfläche |
Publications (3)
Publication Number | Publication Date |
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EP1001052A2 true EP1001052A2 (de) | 2000-05-17 |
EP1001052A3 EP1001052A3 (de) | 2002-11-13 |
EP1001052B1 EP1001052B1 (de) | 2004-05-06 |
Family
ID=26051688
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Application Number | Title | Priority Date | Filing Date |
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EP99115967A Expired - Lifetime EP1001052B1 (de) | 1998-11-13 | 1999-08-13 | Verfahren zur Metallisierung einer Kunststoffoberfläche |
Country Status (5)
Country | Link |
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EP (1) | EP1001052B1 (de) |
KR (1) | KR20010086023A (de) |
AT (1) | ATE266107T1 (de) |
DE (1) | DE59909392D1 (de) |
ES (1) | ES2224507T3 (de) |
Cited By (15)
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EP1281793A1 (de) * | 2001-08-04 | 2003-02-05 | Enthone Inc. | Verfahren zur Metallisierung von Kunststoffoberflächen |
EP1600528A2 (de) * | 2004-05-27 | 2005-11-30 | Enthone, Inc. | Verfahren zur Metallisierung von Kunststoffoberflächen |
EP2025708A1 (de) * | 2007-08-10 | 2009-02-18 | Enthone Inc. | Chromfreie Beize für Kunststoffoberflächen |
EP2639332A1 (de) | 2012-03-15 | 2013-09-18 | Atotech Deutschland GmbH | Verfahren zum Metallisieren nichtleitender Kunststoffoberflächen |
EP2639333A1 (de) | 2012-03-15 | 2013-09-18 | Atotech Deutschland GmbH | Verfahren zum Metallisieren nichtleitender Kunststoffoberflächen |
EP2639334A1 (de) | 2012-03-15 | 2013-09-18 | Atotech Deutschland GmbH | Verfahren zum Metallisieren nichtleitender Kunststoffoberflächen |
EP2767614A1 (de) | 2013-02-13 | 2014-08-20 | ATOTECH Deutschland GmbH | Verfahren zum Abscheiden einer ersten Metallschicht auf nicht leitfähigen Polymeren |
EP3034650A1 (de) | 2014-12-16 | 2016-06-22 | ATOTECH Deutschland GmbH | Plattierungsbadzusammensetzungen zur stromlosen Abscheidung von Metallen und Metalllegierungen |
WO2016146332A1 (de) * | 2015-03-18 | 2016-09-22 | Coventya Gmbh | Verfahren zur selektiven metallisierung von butadien-haltigen kunststoffbereichen in einem bauteil und kit zur durchführung des verfahrens |
EP3181726A1 (de) | 2015-12-18 | 2017-06-21 | ATOTECH Deutschland GmbH | Ätzlösung zur behandlung nichtleitenden kunststoffoberflächen und verfahren zum ätzen nichtleitender kunststoffoberflächen |
WO2017191260A1 (en) | 2016-05-04 | 2017-11-09 | Atotech Deutschland Gmbh | Process for depositing a metal or metal alloy on a surface of a substrate including its activation |
EP3327176B1 (de) | 2013-10-22 | 2019-06-26 | Okuno Chemical Industries Co., Ltd. | Zusammensetzung zur ätzbehandlung eines harzmaterials |
EP3578683A1 (de) | 2018-06-08 | 2019-12-11 | ATOTECH Deutschland GmbH | Stromloses kupfer- oder kupferlegierungsplattierungsbad und verfahren zur plattierung |
EP3660189A1 (de) | 2014-04-01 | 2020-06-03 | ATOTECH Deutschland GmbH | Zusammensetzung und verfahren zur metallisierung von nichtleitenden kunststoffoberflächen |
WO2022129492A1 (en) | 2020-12-18 | 2022-06-23 | Atotech Deutschland GmbH & Co. KG | Method for etching at least one surface of a plastic substrate |
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CN101255585B (zh) * | 2007-12-05 | 2010-06-09 | 天津大学 | 碳纤维增强环氧树脂复合材料的新型表面金属化方法 |
DE202023103135U1 (de) | 2023-06-07 | 2023-06-14 | Dr. Hesse GmbH & Cie. KG | Oberfläche aus nichtleitendem Kunststoff |
DE202023107029U1 (de) | 2023-11-28 | 2024-01-10 | Dr. Hesse GmbH & Cie. KG | Gegenstand mit einer gebeizten Oberfläche aus einem nichtleitenden Kunststoff |
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- 1999-08-13 AT AT99115967T patent/ATE266107T1/de not_active IP Right Cessation
- 1999-08-13 EP EP99115967A patent/EP1001052B1/de not_active Expired - Lifetime
- 1999-08-13 ES ES99115967T patent/ES2224507T3/es not_active Expired - Lifetime
- 1999-08-13 DE DE59909392T patent/DE59909392D1/de not_active Expired - Lifetime
- 1999-11-05 KR KR1020017006001A patent/KR20010086023A/ko not_active Application Discontinuation
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Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1281793A1 (de) * | 2001-08-04 | 2003-02-05 | Enthone Inc. | Verfahren zur Metallisierung von Kunststoffoberflächen |
CN100421912C (zh) * | 2001-08-04 | 2008-10-01 | 恩通公司 | 塑料表面金属化处理的方法 |
EP1600528A2 (de) * | 2004-05-27 | 2005-11-30 | Enthone, Inc. | Verfahren zur Metallisierung von Kunststoffoberflächen |
EP1600528A3 (de) * | 2004-05-27 | 2008-09-24 | Enthone, Inc. | Verfahren zur Metallisierung von Kunststoffoberflächen |
EP2025708A1 (de) * | 2007-08-10 | 2009-02-18 | Enthone Inc. | Chromfreie Beize für Kunststoffoberflächen |
US9181622B2 (en) | 2012-03-15 | 2015-11-10 | Atotech Deutschland Gmbh | Process for metallizing nonconductive plastic surfaces |
EP2639333A1 (de) | 2012-03-15 | 2013-09-18 | Atotech Deutschland GmbH | Verfahren zum Metallisieren nichtleitender Kunststoffoberflächen |
EP2639334A1 (de) | 2012-03-15 | 2013-09-18 | Atotech Deutschland GmbH | Verfahren zum Metallisieren nichtleitender Kunststoffoberflächen |
WO2013135862A2 (en) * | 2012-03-15 | 2013-09-19 | Atotech Deutschland Gmbh | Process for metallizing nonconductive plastic surfaces |
WO2013135862A3 (en) * | 2012-03-15 | 2013-11-07 | Atotech Deutschland Gmbh | Process for metallizing nonconductive plastic surfaces |
EP2639332A1 (de) | 2012-03-15 | 2013-09-18 | Atotech Deutschland GmbH | Verfahren zum Metallisieren nichtleitender Kunststoffoberflächen |
EP2767614A1 (de) | 2013-02-13 | 2014-08-20 | ATOTECH Deutschland GmbH | Verfahren zum Abscheiden einer ersten Metallschicht auf nicht leitfähigen Polymeren |
WO2014124773A2 (en) | 2013-02-13 | 2014-08-21 | Atotech Deutschland Gmbh | Method for depositing a first metallic layer onto non-conductive polymers |
EP3327176B1 (de) | 2013-10-22 | 2019-06-26 | Okuno Chemical Industries Co., Ltd. | Zusammensetzung zur ätzbehandlung eines harzmaterials |
EP3660189A1 (de) | 2014-04-01 | 2020-06-03 | ATOTECH Deutschland GmbH | Zusammensetzung und verfahren zur metallisierung von nichtleitenden kunststoffoberflächen |
US9909216B2 (en) | 2014-12-16 | 2018-03-06 | Atotech Deutschland Gmbh | Plating bath compositions for electroless plating of metals and metal alloys |
EP3034650A1 (de) | 2014-12-16 | 2016-06-22 | ATOTECH Deutschland GmbH | Plattierungsbadzusammensetzungen zur stromlosen Abscheidung von Metallen und Metalllegierungen |
WO2016146332A1 (de) * | 2015-03-18 | 2016-09-22 | Coventya Gmbh | Verfahren zur selektiven metallisierung von butadien-haltigen kunststoffbereichen in einem bauteil und kit zur durchführung des verfahrens |
EP3181726A1 (de) | 2015-12-18 | 2017-06-21 | ATOTECH Deutschland GmbH | Ätzlösung zur behandlung nichtleitenden kunststoffoberflächen und verfahren zum ätzen nichtleitender kunststoffoberflächen |
WO2017191260A1 (en) | 2016-05-04 | 2017-11-09 | Atotech Deutschland Gmbh | Process for depositing a metal or metal alloy on a surface of a substrate including its activation |
US10975474B2 (en) | 2016-05-04 | 2021-04-13 | Atotech Deutschland Gmbh | Process for depositing a metal or metal alloy on a surface of a substrate including its activation |
EP3578683A1 (de) | 2018-06-08 | 2019-12-11 | ATOTECH Deutschland GmbH | Stromloses kupfer- oder kupferlegierungsplattierungsbad und verfahren zur plattierung |
WO2019234085A1 (en) | 2018-06-08 | 2019-12-12 | Atotech Deutschland Gmbh | Electroless copper or copper alloy plating bath and method for plating |
WO2022129492A1 (en) | 2020-12-18 | 2022-06-23 | Atotech Deutschland GmbH & Co. KG | Method for etching at least one surface of a plastic substrate |
Also Published As
Publication number | Publication date |
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DE59909392D1 (de) | 2004-06-09 |
ATE266107T1 (de) | 2004-05-15 |
KR20010086023A (ko) | 2001-09-07 |
ES2224507T3 (es) | 2005-03-01 |
EP1001052A3 (de) | 2002-11-13 |
EP1001052B1 (de) | 2004-05-06 |
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