EP1745163A1 - Method for producing electroplated plastic sanitary articles - Google Patents
Method for producing electroplated plastic sanitary articlesInfo
- Publication number
- EP1745163A1 EP1745163A1 EP06743085A EP06743085A EP1745163A1 EP 1745163 A1 EP1745163 A1 EP 1745163A1 EP 06743085 A EP06743085 A EP 06743085A EP 06743085 A EP06743085 A EP 06743085A EP 1745163 A1 EP1745163 A1 EP 1745163A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- sanitary
- sanitary object
- water
- sealing ring
- 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
- 229920000642 polymer Polymers 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000001465 metallisation Methods 0.000 claims abstract description 40
- 239000004033 plastic Substances 0.000 claims abstract description 28
- 229920003023 plastic Polymers 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 62
- 238000007789 sealing Methods 0.000 claims description 28
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000012815 thermoplastic material Substances 0.000 claims description 4
- 239000012811 non-conductive material Substances 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 239000011651 chromium Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 8
- 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 7
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 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 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- -1 chromium Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 241000093804 Berzelia galpinii Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 101000836084 Homo sapiens Serpin B7 Proteins 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 102100025521 Serpin B7 Human genes 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- JZULKTSSLJNBQJ-UHFFFAOYSA-N chromium;sulfuric acid Chemical compound [Cr].OS(O)(=O)=O JZULKTSSLJNBQJ-UHFFFAOYSA-N 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
-
- 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
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/06—Suspending or supporting devices for articles to be coated
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
-
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
-
- 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
- C23C18/28—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49428—Gas and water specific plumbing component making
- Y10T29/49432—Nozzle making
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49428—Gas and water specific plumbing component making
- Y10T29/49432—Nozzle making
- Y10T29/49433—Sprayer
Definitions
- the invention relates in the first place to a method for producing sanitary articles made of plastic with galvanically metallized surfaces, a component which can be used in this method and sanitary articles provided with this component.
- Galvanized plastics d. H. Plastic materials with metallic coatings have become indispensable in the manufacture of sanitary items.
- the preferred plastic material here is, for example, ABS (acrylonitrile-butadiene-styrene copolymer), which is especially galvanized with chromium as the outermost surface layer.
- ABS acrylonitrile-butadiene-styrene copolymer
- the production of galvanized plastic sanitary items is rational and inexpensive to carry out in particular because of unnecessary grinding and polishing effort, as it is necessary for metal bodies. Added to this are the favorable design options resulting from the use of plastic injection technology and a significant reduction in weight compared with sanitary articles with metal bodies.
- the said galvanized plastic sanitary articles are produced in process steps which are basically known to the person skilled in the art.
- a pretreatment process is usually necessary in order to render the plastic surface electrically conductive in order to ensure adequate adhesion of the metal layers applied galvanically with current (ie with external current source) to the plastic.
- current ie with external current source
- all surface areas of the treated article are rendered electrically conductive. This is mainly because the treatment used for electroless pre-treatment solutions to all external and internal surfaces of the article. In the case of sanitary articles, this means that even the water-bearing areas with their corresponding surfaces at least partially become electrically conductive during this pretreatment.
- WO 03/096859 A2 proposes a covering layer or protective layer to at least a part of the surfaces of the sanitary object in order to connect the water-carrying areas of the sanitary object with the external galvanic metallization Disconnect power source from current flow.
- the corresponding layers consist of a lacquer which is applied in a suitable manner, in particular by printing in the so-called tampon printing process.
- this approach can lead to difficulties in practical use.
- the preferred tampon printing process is a comparatively sophisticated technique that can only be mastered by qualified personnel.
- cover / protective layer must be applied to sanitary objects to relatively complicated geometries, which in turn requires qualified personnel and a lot of time.
- paints used for the corresponding layers are complicated to use and sometimes physiologically questionable, so that appropriate precautions must be taken in production.
- the object of the invention is to make it possible for plastic plumbing articles to have a targeted galvanic metallization (with current flow) only in certain surface areas.
- the deposition of metals in the water-bearing areas of the sanitary object should be reliably prevented.
- the process should be as seamless as possible in existing production processes and not affect the quality of the metallization on the decorative surfaces of the sanitary object.
- This object is achieved by the method with the features of claim 1.
- Preferred embodiments of this method are shown in the dependent claims 2 to 15.
- the component preferably used in this method is defined in claims 16 to 18.
- Claim 19 describes the sanitary article provided with the component, preferred embodiments of this sanitary article being content of the dependent claims 20 to 28.
- An inventive product carrier for electroplating is disclosed in claims 29 and 30. The wording of all claims is hereby incorporated by reference into the content of this specification.
- the sanitary object before the galvanic metallization with an external power source at least one electrically non-conductive component, which at least partially the water-bearing areas of the sanitary object in the galvanic metallization with the external power source , preferably completely, decoupled from the current flow.
- the mentioned component can be formed in the inventive method in a first group of embodiments of the sanitary object itself.
- the component forms in these embodiments, quasi a part of the sanitary object itself.
- the component can be integrated into the construction of the sanitary object, that it after fulfilling its function to decouple the water-bearing areas from the flow of electricity can remain on the sanitary object. It may also be preferable if this component can be removed or separated from the sanitary object after fulfilling its function, for example by the presence of a suitable predetermined breaking point, with the aid of which the component can be separated from the sanitary object itself by hand or with a suitable tool.
- said component is designed as a preferably separate component which can be connected to the sanitary object or can interact with it in a comparable manner.
- the component is in particular designed so that it is reversibly connectable to the sanitary object, d. H. after fulfilling its function in a simple manner can be removed from the sanitary object again.
- the preferably separate component with the sanitary object is preferably plugged together, in particular in this plugged. This makes it possible to realize the aforementioned reversible connectivity with the sanitary object in a simple manner.
- the preferably separate component is preferably designed in the manner of a sleeve. In this way, it can interact with the corresponding water-bearing parts of a sanitary object, which usually have circular cross-sectional areas.
- the necessary seal between the sleeve-like component and the sanitary object is z. B. achieved by the outer surface of the component or by a section or projection provided there together with the inner surface of the article or there provided (circumferential) notch or groove.
- At least one sealing element is preferably located at the sleeve-like components mentioned on the outer circumference of the component, wherein these sealing elements are, in particular, conventional sealing rings.
- this component is preferably at least partially introduced into the sanitary object. This can be realized, for example, by placing the component in a recess or recess provided on the sanitary object, in particular in the manner of a (preferably circumferential) groove.
- the preferably separate component is preferably of annular design, which may also be, in particular, conventional sealing rings.
- recesses or openings are provided in the invention in the described component, which can serve different purposes.
- such recesses or openings serve to receive holding elements for the component, ie. H. those holding elements that are necessary or useful for the function of the component in the galvanic metallization.
- sanitary articles can be galvanically metallized.
- Preferred sanitary items are sanitary outlet devices such as fittings, showers, hand showers and the like.
- these are sanitary articles, in whose production the water-bearing parts or areas are injected with the same.
- the sanitary article which is galvanically metallized according to the invention is a shower or a shower head, preferably a hand shower.
- the described component is provided at the so-called water inlet and / or at the so-called water outlet. The exact arrangement of the component on the sanitary object will also be explained later in connection with the drawings.
- the component is preferably formed as a sleeve-like component and then provided on or in the water inlet.
- the component can also be designed as a sealing ring and then be provided on or preferably in the water inlet.
- the component is preferably designed as a sealing ring and then provided at the water outlet, or the component is preferably designed as a sleeve-like component and then provided at the water outlet.
- the component described in connection with the invention is preferably made of plastic.
- plastic in particular, PVDF (polyvinylidene fluoride) or PTFE (polytetrafluoroethylene) may be used here as plastic.
- the sanitary object itself in particular the shower or shower head, made of plastic, wherein preferably a so-called thermoplastic material is used.
- the sanitary article is made of ABS in these cases.
- the invention also includes the already described component itself, which is used for the production of sanitary articles made of plastic with galvanic metallic sated surfaces is provided by galvanic metallization with external power source.
- This component is inventively characterized in that it is made of an electrically non-conductive material and formed in the manner of a sleeve.
- This component according to the invention preferably has on the outer circumference at least one sealing element, preferably at least one sealing ring. Further, the component may in particular recesses or openings, which are provided for receiving retaining elements for the component in the exercise of its function. With regard to the disclosure of the component according to the invention, reference is expressly made to the corresponding passages in the description of the method according to the invention and referenced.
- the invention also includes sanitary articles made of plastic, in particular showers or shower heads, which are connected to at least one separate component, which at least partially decouples the water-carrying areas of the sanitary object from the current flow during a galvanic metallization with an external current source.
- the component directly, for example in one piece, be molded to the sanitary object. After performing the function, the component can then either remain on the sanitary object or be separated from this again.
- the component can be reversibly connectable to the sanitary object.
- the component with the sanitary object can be plugged together or inserted into this.
- sleeve-like components or the described annular components wherein recesses or openings may be provided in the component.
- the component is, as mentioned, preferably made of plastic, in particular PVDF or PTFE.
- the sanitary article according to the invention is preferably a hand shower.
- the sanitary article is preferably made of a thermoplastic material, in particular of ABS.
- the invention also includes a goods carrier in the form of a galvanic frame, which is provided according to the invention with at least one of the described sleeve-shaped components according to the invention.
- these components can be applied to the goods carrier, ie the electroplating rack, before the sanitary articles to be electroplated are applied.
- the components can be fastened via the recesses and openings preferably provided there to corresponding holding elements of the goods carrier.
- the sanitary objects can be attached directly to the components on the goods carrier, for example, inserted into the corresponding openings of a hand shower and also contacted. This facilitates the work processes in the production.
- the components can then optionally remain on the goods carrier and also be used for the galvanization of other sanitary items.
- the invention has a number of advantages over the initially described prior art.
- the decoupling of the water-bearing areas or parts of the sanitary object in the invention is carried out with a component which is either formed on the object or in a simple manner connectable to this.
- in the invention must not be handled with chemical substances such as paints or the like, so that no corresponding regulations for occupational safety must be complied with.
- the components described can optionally be removed again in a simple manner from the sanitary object, which is either not possible at all or only with great effort in the application of covering or protective layers. With appropriate design, the components can even be reused after their removal from the sanitary object.
- a holder of the sanitary object in the galvanic metallization can be provided over the component (see the optionally existing recesses or openings).
- the invention can be integrated in a special way in processes in which the plastic objects are made conductive by the so-called direct metallization process (see later).
- the method according to the invention is preferably configured such that the surfaces of the sanitary object are pretreated with external current source prior to the galvanic metallization. This is preferably true for all surfaces.
- pretreatment steps can be applied, as they are known from the prior art.
- the pretreatment preferably comprises at least one degreasing or pickling step, in which case a pretreatment with an oxidizing agent should be mentioned in particular.
- oxidizing agents can be used here, for example potassium permanganate solution, it being possible for different agents to be selected depending on the plastic material used for the sanitary object.
- Preferred oxidizing agents are acids, in which case a treatment with chromic acid-containing solutions (with or without sulfuric acid) is to be emphasized.
- the pretreatment with chromic acid-containing solutions is particularly suitable for plastic articles made of ABS.
- the pretreatment in the inventive method preferably comprises at least one activation step, which usually follows the degreasing or pickling step.
- the activation can take place in several steps, with activation in two steps being preferred.
- Activation is carried out according to the invention, in particular a so-called electroless chemical metallization.
- metals are deposited without external power source of suitable solutions.
- various procedures are known which are separated from each other or in combination with each other can be applied.
- solutions for chemical metallization can be used which contain tin or palladium.
- the solutions preferably contain tin ions, while the palladium may be contained in the solutions in ionic form or else in metallic form (preferably colloidal).
- the chemical metallization can be carried out with the aid of solutions containing cobalt ions. These cobalt ions are then converted to cobalt sulfide in a second step.
- Direct metallization means that after pretreatment and activation, an electrolytic layer (under current flow) can be built directly. This reduces the number of production steps and simplifies the process as a whole. Especially when using such direct metallizations method of the invention brings with its component according to the invention additional advantages, since then a total metallization of the water-bearing parts of a sanitary object can be reliably prevented and the process is further simplified on the whole.
- layers, and in particular outermost cover layers of at least one noble metal or of binary, ternary or quaternary alloys of such metals are applied.
- noble metals are gold and the metals of the group of the so-called platinum metals.
- a layer sequence is applied in which this layer sequence terminates with an outermost covering layer of chromium.
- the advantages of a chromium plating as the outermost cover layer also need not be emphasized and are known in the art. In these embodiments, those are still preferred in which layers of nickel and / or copper are located below the covering layer of chromium.
- the method according to the invention can be configured in such a way that after the galvanic metallization with external current source, a post-treatment takes place.
- This aftertreatment preferably relates to all surfaces of the sanitary article.
- the aftertreatment consists, in particular, of a so-called stripping, in which a conductive layer (metal layers), which is optionally applied by electroless chemical deposition, is removed again.
- This stripping is preferably carried out by treating the corresponding surfaces with an oxidizing agent, in particular an oxidizing acid.
- the oxidizing agent may be, in particular, nitric acid or solutions which are in particular persulphate. fat or hydrogen peroxide. Stripping preferably removes all metal layers that have not been current deposited.
- the water-bearing parts of the sanitary object are completely metal-free, so that the disadvantages listed above can not occur.
- FIG. 1 is a schematic sectional view of a component according to the invention, as used in the inventive method,
- Fig. 2 is a schematic sectional view of another component according to the invention, as used in the inventive method, and
- Fig. 3 is a schematic sectional view of a sanitary object according to the invention with inventive component.
- Fig. 1 shows the component 1 according to the invention in sectional view.
- This component is made of PVDF in a conventional manner known to those skilled in the art.
- the component 1 is designed in the manner of a sleeve with a circular cross-sectional area and has a first section 2, to which a second section 3 immediately adjoins.
- Section 3 has a peripheral on the outer circumference of the component 1 projection 4, which forms a groove-like recess 6 together with another projection 5.
- a sealing element 7 is inserted in the form of a sealing ring, which projects beyond the projections 4 and 5 and thus provides a corresponding sealing surface for the component 1 to the outside.
- the interaction of the sealing element 7 with the corresponding surfaces of a sanitary object will be explained in more detail below, in connection with FIG. 3.
- section 2 of the component 1 there are two, mutually opposite openings 8 a and 8 b, which can accommodate at least one holding element for the component 1. This will also be explained in more detail in connection with FIG.
- the walls of the component 1 are reduced. As a result, the introduction and removal of the component from the corresponding openings of the sanitary article is facilitated by the increased elasticity of the corresponding regions.
- the component 1 is an embodiment of the component according to the invention, in which the component 1 is designed as a separate component. It can interact with a sanitary object in the manner shown in FIG. 3 and assume its function in galvanic metallization.
- Fig. 2 shows a further inventive component 1 'in sectional view. Since its structure is similar to the structure of the component 1, reference can be made to the description of the component 1. For green For reasons of clarity, the same reference numerals have also been used to a large extent.
- the component 1 ' is also configured in the manner of a sleeve with a circular cross-sectional area.
- the component V has a projection 4 which extends on the outer circumference and can cooperate sealingly with a corresponding recess on a sanitary object.
- the sealing function is ensured despite dispensing with an additional sealing element 7 with respect to the embodiment of the component according to the invention shown in FIG. This simplifies the construction and production of the component 1 'relative to the component 1.
- the component V also has two opposing openings 8a and 8b, which can receive at least one holding element for the component 1.
- the wall thickness is also reduced in order to facilitate an increased elasticity for the introduction and removal of the component from the corresponding openings of the sanitary object.
- Fig. 3 shows a sanitary object according to the invention in the form of a hand shower 11, which is in a conventional manner known in the art by injection molding, preferably made of ABS. It can be clearly seen the merging water-bearing areas 12a (water chamber) and 12b (water supply channel) with their associated (inner) surfaces. These water-bearing areas are in the functional state of the sanitary object flows through the water / drinking water, in the direction of the water inlet area (water inlet 13) to the water outlet area (water outlet 14).
- water inlet area water inlet 13
- water outlet area water outlet 14
- a component 1 according to FIG. 1 is introduced into the water inlet 13, in the present case inserted.
- the section 3 of the component 1 shown in FIG. 1 is inserted into the water inlet 13, wherein the sealing element 7 cooperates with the projection 4 with the inner wall of the water inlet 13 in a form-fitting manner.
- the section 2 of the component 1 with its openings 8a and 8b is shown in FIG. 3 out of the water inlet 13 and on the one hand supports the decoupling from the current flow and provides on the other via the openings 8a and 8b a way to mount the component 1 and Hand shower 11 in the galvanic coating itself available.
- This holder is accomplished, for example, by passing one or two support rods through the two opposite openings 8a and 8b, wherein the support rods are preferably provided on a product carrier for the galvanic coating of the hand shower 11.
- the support rods are preferably provided on a product carrier for the galvanic coating of the hand shower 11.
- other support rods in the region of the water outlet 14 can act on the hand shower 11.
- the hand shower 11, preferably at the water inlet 13 and the water outlet 14, only to be contacted, and the galvanic deposition can begin.
- the component 1 'shown in FIG. 2 can be introduced into the hand shower 11.
- an inventive component 1 is present only at the water inlet 13.
- the duration of galvanic metallization under current flow can be determined based on experience. be controlled to ensure that only the outer (decorative) surfaces of the hand shower 11 are coated with metal and no (unwanted) coating of water-bearing areas via the water outlet 14 takes place. Since the metal layer grows up in this procedure, starting from the water inlet 13 forth, in these cases, the galvanic coating is simply canceled in time.
- an inventive component 1 at the water outlet 14 which also ensures there a corresponding decoupling of the water-carrying areas from the current flow.
- an inventive component 1 at the water outlet 14 which also ensures there a corresponding decoupling of the water-carrying areas from the current flow.
- a hand shower as shown in Fig. 3, made of ABS, z. B. Novodur P2MC (Bayer AG, Germany) or Ronvalin TP55 (BASF AG, Germany) is treated prior to the entire galvanic treatment with a nem component according to the invention, as shown in Fig. 1, provided.
- the component is inserted in the manner shown in Fig. 3 in the water inlet of the hand shower.
- the hand shower is fixed on a galvanic frame.
- the sprayed body which has been prepared in this way, runs through the galvano process in the drive-through principle, fixed on the galvanizing stand.
- This GaI-vano process can look like this, for example:
- the stains contain some fluorosurfactant such as FT248
- the outer regions have a pre-nickel layer, the water chamber and the inner wall of the water guide channel remain in the state of chemical nickel plating.
- Brightener system such as Cuprorapid 1518 (Fa.
- step 4 Replacement of step 4 with a higher Pd concentration colloidal Sn / Pd solution, e.g. B. 240 mg / l
- the colloidal Sn / Pd solution can be replaced by a solution containing palladium sulfate, chromic acid and sulfuric acid.
- the accelerator then contains an organic boron-hydrogen compound and sodium hypophosphite. The process steps 2 and 3 are omitted.
- the chromium-sulfuric acid as a stain additionally about 10 mg / l Pd - also applies to direct metallization.
- the top layer could also be made of pure gold, hard gold, Platinum, palladium, ruthenium, etc., as long as the cover layer is resistant to the stripping medium.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Chemically Coating (AREA)
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005026633A DE102005026633A1 (de) | 2005-06-03 | 2005-06-03 | Verfahren zur Herstellung von galvanisierten Sanitärgegenständen aus Kunststoff |
| PCT/EP2006/005122 WO2006128664A1 (de) | 2005-06-03 | 2006-05-30 | Verfahren zur herstellung von galvanisierten sanitärgegenständen aus kunststoff |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1745163A1 true EP1745163A1 (de) | 2007-01-24 |
| EP1745163B1 EP1745163B1 (de) | 2011-03-16 |
Family
ID=36794423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP06743085A Not-in-force EP1745163B1 (de) | 2005-06-03 | 2006-05-30 | Verfahren zur herstellung von galvanisierten sanitärgegenständen aus kunststoff |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8011100B2 (de) |
| EP (1) | EP1745163B1 (de) |
| JP (1) | JP2008542538A (de) |
| AT (1) | ATE502136T1 (de) |
| DE (2) | DE102005026633A1 (de) |
| WO (1) | WO2006128664A1 (de) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010127866A2 (de) | 2009-05-08 | 2010-11-11 | Grohe Ag | Sanitärgegenstände |
| GB2470590B (en) * | 2009-05-29 | 2014-07-23 | Astron Advanced Materials Ltd | Electrodeposition of elemental zirconium |
| DE102022104380A1 (de) * | 2022-02-24 | 2023-08-24 | Grohe Ag | Verfahren zur Herstellung eines Armaturengehäuses für eine Sanitärarmatur und Sanitärarmatur mit einem Armaturengehäuse |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6714122A (de) * | 1967-10-18 | 1969-04-22 | ||
| US4275908A (en) * | 1979-08-16 | 1981-06-30 | Teledyne Industries, Inc. | Fluid coupling assembly |
| DE4123985C2 (de) | 1991-07-19 | 1994-01-27 | Hoellmueller Maschbau H | Vorrichtung zur elektrolytischen Behandlung von Leiterplatten, insbesondere zur elektrolytischen Beschichtung mit Kupfer |
| DE19510855C2 (de) * | 1995-03-17 | 1998-04-30 | Atotech Deutschland Gmbh | Verfahren zum selektiven oder partiellen elektrolytischen Metallisieren von Substraten aus nichtleitenden Materialien |
| DE19619254C1 (de) | 1996-05-13 | 1997-10-02 | Nussbaum Oberflaechentechnik G | Maskierungsvorrichtung und zugehöriges Verfahren |
| GB9925537D0 (en) * | 1999-10-29 | 1999-12-29 | British Aerospace | Masking techniques for metal plating |
| DE10223081A1 (de) * | 2002-05-17 | 2003-12-04 | Hansgrohe Ag | Verfahren zur Herstellung von galvanisierten Sanitärgegenständen aus Kunststoff |
-
2005
- 2005-06-03 DE DE102005026633A patent/DE102005026633A1/de not_active Withdrawn
-
2006
- 2006-05-30 DE DE502006009087T patent/DE502006009087D1/de active Active
- 2006-05-30 AT AT06743085T patent/ATE502136T1/de active
- 2006-05-30 JP JP2008514000A patent/JP2008542538A/ja active Pending
- 2006-05-30 EP EP06743085A patent/EP1745163B1/de not_active Not-in-force
- 2006-05-30 WO PCT/EP2006/005122 patent/WO2006128664A1/de not_active Ceased
- 2006-05-30 US US11/570,666 patent/US8011100B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2006128664A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070251826A1 (en) | 2007-11-01 |
| US8011100B2 (en) | 2011-09-06 |
| DE102005026633A1 (de) | 2006-12-28 |
| WO2006128664A1 (de) | 2006-12-07 |
| DE502006009087D1 (de) | 2011-04-28 |
| ATE502136T1 (de) | 2011-04-15 |
| EP1745163B1 (de) | 2011-03-16 |
| JP2008542538A (ja) | 2008-11-27 |
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