US20060086620A1 - Textured decorative plating on plastic components - Google Patents
Textured decorative plating on plastic components Download PDFInfo
- Publication number
- US20060086620A1 US20060086620A1 US10/970,018 US97001804A US2006086620A1 US 20060086620 A1 US20060086620 A1 US 20060086620A1 US 97001804 A US97001804 A US 97001804A US 2006086620 A1 US2006086620 A1 US 2006086620A1
- Authority
- US
- United States
- Prior art keywords
- metal layer
- layer
- etchable
- etched
- 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.)
- Abandoned
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 32
- 229920003023 plastic Polymers 0.000 title claims abstract description 32
- 238000007747 plating Methods 0.000 title description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 163
- 239000002184 metal Substances 0.000 claims abstract description 163
- 238000000034 method Methods 0.000 claims abstract description 90
- 230000008569 process Effects 0.000 claims abstract description 75
- 238000009713 electroplating Methods 0.000 claims abstract description 46
- 238000004140 cleaning Methods 0.000 claims abstract description 25
- 238000005530 etching Methods 0.000 claims abstract description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003213 activating effect Effects 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 20
- 230000007797 corrosion Effects 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 230000000873 masking effect Effects 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000007772 electroless plating Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003021 water soluble solvent Substances 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 2
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 230000001680 brushing effect Effects 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims 2
- 239000012190 activator Substances 0.000 claims 1
- 238000005422 blasting Methods 0.000 claims 1
- 230000000153 supplemental effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 29
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000007654 immersion Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hydroxyl ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005494 tarnishing Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012799 electrically-conductive coating Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000009499 grossing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/22—Removing surface-material, e.g. by engraving, by etching
- B44C1/227—Removing surface-material, e.g. by engraving, by etching by etching
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/181—Hydrocarbons linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/188—Terpenes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
- C23G5/02861—Oxygen-containing compounds
- C23G5/02864—Alcohols
- C23G5/02867—Alcohols aliphatic
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
- C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
- C23G5/02883—Nitrogen-containing compounds
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
- C23G5/036—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds having also nitrogen
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- 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
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- C11D2111/16—
Definitions
- This invention relates to decorative finishes and more particularly to a process for creating a plated plastic article having a decorative relief pattern.
- Decorative chrome finishes on plastic components have long been popular in automotive, appliances, teletronics, and household applications. While chrome plated plastic articles having decorative relief patterns are known and desired, it is expected that the demand for more delicately textured or patterned chrome finishes will increase in the near future.
- a textured chrome finish on a plastic component can be achieved by applying a chrome plating over a pre-textured molded plastic component.
- this practice is not economically acceptable in the initial marketing phase of potential products, and is unacceptable for certain low volume or specialty products, because pre-textured molds are relatively expensive. Further, it is extremely difficult to consistently produce delicate and/or intricate textured patterns in a plastic molding process. In addition, because of the thicknesses of the multiple layers required for chrome plating a plastic substrate, much of the original detail in the molded relief pattern may be lost during the plating process.
- U.S. Pat. Nos. 3,843,763 and 3,869,535 disclose methods for modifying embossing rollers, plates or dies by subjecting machine engraved or electroformed roller to a combination of plating steps.
- the embossed roller is first subjected to a bright metal plating step with a metal characterized by a high or medium leveling effect to produce a combined brightening and smoothing effect on the roller.
- This step is followed by a second plating step used as a finishing coating for the roller.
- the second plating is suitably achieved using a metal having a relatively lower leveling effect such as chromium or nickel.
- the second plating step provides a hard coating surface which is resistant to corrosion and erosion while at the same time enhancing the textured pattern of the end desired product.
- the disclosed process starts with a substrate having the desired relief pattern.
- U.S. Pat. No. 4,278,739 discloses a method of metallizing materials by coating a substrate material with a hydrophilic composite material, electrolessly metal plating the hydrophilic composite material with a metal to render the surface conductive, and electroplating a metal onto the conductive surface.
- the method is said to be useful for producing metallized forms, embossing plates for reproduction of grains and textures, and decorative coatings for substrate materials.
- U.S. Pat. No. 4,600,480 discloses a method for plating selected surfaces of a plastic substrate without plating other selected surfaces.
- the disclosed method involves electrolessly plating the substrate to provide an electroless metal layer over all of the first selected surfaces and at least a portion of second selected surfaces, mounting the substrate on an electroplating rack so that the current density at the second selected surfaces is lower during electroplating than at the first selected surfaces, whereby the substrate is electroplated to provide intermediate metal layers which extend over at least all of the first selected surfaces, and then electroplating with a final metal different from the metals of the electroless and intermediate layers at a voltage whereby the final metal deposits over the first selected surfaces but not over the second selected surfaces.
- the electroplated substrate is then immersed in a stripping solution which dissolves the electroless and intermediate metals but not the final metal.
- U.S. Pat. No. 4,820,553 discloses a process for conditioning surfaces of a polyester or polyamide material for electroless plating.
- the method comprises exposing surfaces of the polyester and/or polyamide material to a composition which comprises a solvent system containing water, a water-soluble organic solvent and solvated hydroxyl ions to etch the surface of the substrate to improve adhesion of a metal coating with the substrate.
- U.S. Pat. No. 6,489,034 discloses a method of applying a metal onto a copper layer by steps of stabilizing a surface of a copper layer by applying an oxide layer to the copper layer, and vapor depositing a metal, such as chromium, directly onto the oxide surface of the copper layer.
- the invention provides an economically acceptable process for making plastic components having delicately textured or patterned finishes, and provides a flexible technology for producing decorative patterns having fine, crisp, clean lines and intricate details on a variety of plastic parts having a metal layer.
- the process includes steps of electroplating a layer of etchable metal on a surface of a plastic article; typically preventing the etchable metal surface from tarnishing; etching a desired relief pattern on the layer of etchable metal; typically cleaning and activating the surface of the relief patterned etched metal layer; and depositing a finish layer on the relief patterned etched metal layer.
- a process for preparing a plastic article having a desired relief pattern in a plated surface generally involves depositing a relatively thick layer of etchable metal on a surface of the article; forming the desired relief pattern on an exposed surface of the etchable metal layer; and depositing a finish layer over the relief pattern.
- Electroless coating generally involves steps of cleaning and etching the substrate, neutralizing the etched surface, catalyzing the neutralized surface (e.g. in a solution that contains palladium chloride, stannous chloride and hydrochloric acid), followed by immersion in an accelerator solution (which is either an acid or a base), and forming a metallic coating on the activated substrate.
- the surface of the substrate is typically conditioned by cleaning with a detergent solution and etched by dipping the substrate in an etchant (e.g., a mixed solution of chromic acid and sulfuric acid).
- a detergent solution e.g., a mixed solution of chromic acid and sulfuric acid.
- the metallic coating may be deposited on the activated substrate by immersing the substrate in a chemical plating bath containing nickel or copper ions and deposing the metal thereon from the bath by means of the chemical reduction of the metallic ions.
- the resulting metallic coating is useful for subsequent electroplating because of its electrical conductivity. It is also conventional to wash the substrate with water after each of the above steps.
- Typical plastic materials that have been rendered receptive to electroplating, and which may be subsequently electroplated include acrylonitrile-butadiene styrene (ABS) resins, polyesters, polyethers, polyacrylics, polycarbonates, polyamides, polyolefins, polyvinylchloride, polycarbonate (PC) resins/ABS alloy polymers and phenol-formaldehyde polymers.
- ABS acrylonitrile-butadiene styrene
- PC polycarbonate
- the process of this invention may be applied to these and other plastics.
- the layer of etchable metal is electroplated onto the article.
- a relatively thick layer of etchable metal is electroplated onto the treated surface of the plastic article.
- a suitable thickness of the etchable metal layer is typically from about 50 to about 500 micrometers. A thinner layer may be utilized, although this may limit the ability to provide a visually discernible, aesthetically acceptable relief pattern. Greater thicknesses may also be used, but are generally unnecessary to achieve an aesthetically acceptable textured or graphical relief pattern.
- a copper electroplate is preferred because of its relatively low cost and excellent etchability properties.
- the layer of etchable metal that is subsequently etched to form the desired relief pattern may be electroplated over any number of previous layers. Accordingly, as used herein, electroplating a layer of etchable metal on the article may be achieved by either electroplating directly on the plastic article treated with an electroless coating, or on one or more layers of material deposited on the surface of the plastic article.
- etching the relief pattern into the layer of etchable metal it is desirable to first activate the exposed surface of the etchable metal layer in order to form a thin layer of preservative film on the etchable metal surface. This may be achieved by contacting the exposed surface of the etchable metal layer with an activating solution comprising from about 1% to about 10% by weight hydrogen peroxide (H 2 O 2 ) and from about 5 to about 20% by volume of sulfuric acid (H 2 SO 4 ). A suitable contact time is from about 5 seconds to about 60 seconds, and contacting of the exposed surface of the etchable metal layer with the activating solution may be performed at ambient conditions (e.g., normal atmosphere pressure and normal facility or room temperatures).
- an activating solution comprising from about 1% to about 10% by weight hydrogen peroxide (H 2 O 2 ) and from about 5 to about 20% by volume of sulfuric acid (H 2 SO 4 ).
- a suitable contact time is from about 5 seconds to about 60 seconds, and contacting of the exposed surface of the etchable metal layer with the activating solution may
- aqueous corrosion inhibiting solution Before etching the etchable metal layer, it may be desirable to contact the exposed surface of the etchable metal layer with an aqueous corrosion inhibiting solution to prevent the etchable metal surface from tarnishing.
- a suitable contact time of the exposed surface of the etchable metal layer with the corrosion inhibitor solution is from about 1 second to about 10 minutes.
- corrosion inhibiting agents that may be employed in an aqueous corrosion inhibitor include benzotriazole, 2-mercaptobenzimidazole, 2-mercapatobenzothiazole, 2-mercaptobenzoxazole, their derivatives, or a combination of these corrosion inhibiting agents. Such agents are typically present in the aqueous corrosion inhibitor solution at a concentration of at least 10 mg/L.
- any of various etching techniques that are well known may be employed for etching the desired relief pattern into the surface of the etchable metal layer.
- the exposed surface of the etchable metal layer is coated with a material (typically a synthetic polymer material) that is either chemically resistant to the etchant used for etching the metal, or which can be rendered chemically resistant, such as by cross-linking.
- a material typically a synthetic polymer material
- Any of various masking techniques known in the art may be employed, including wax masking, etchable film masking, brush-coat masking, spray-coat masking, immersion-coat masking, UV cure photoresist masking, etc.
- sections of the coating are removed to expose sections of the underlying etchable metal layer.
- the patterned coating or mask and the exposed sections of the surface of the etchable metal layer are contacted with a chemical etchant that removes (e.g., dissolves) metal at the surface of the etchable metal layer, thereby forming a relief pattern into the metal that corresponds with the mask pattern.
- a chemical etchant that removes (e.g., dissolves) metal at the surface of the etchable metal layer, thereby forming a relief pattern into the metal that corresponds with the mask pattern.
- Conventional photoresist materials may be used for preparing the patterned coatings or masks. Typically, precise patterns can be formed into the photoresist materials by selective exposure of the photoresist material to ultraviolet radiation.
- ultraviolet radiation is used to either decompose the exposed areas of the photoresist resin coating or to cross link the exposed areas of the photoresist resin coating.
- the ultraviolet radiation decomposes sections of the photoresist coating
- the decomposed areas are removed, typically by contacting these areas with a solvent, and the remaining portions, which constitute the mask, are chemically resistant to the etchant.
- the ultraviolet radiation cross links the exposed sections of the photoresist material
- the cross-linked sections are rendered chemically resistant to the etchant, and the unexposed sections are removed (such as with a solvent) to form the mask.
- Suitable etchants for etching the surface of a metal layer, such as copper include various acid solutions.
- metal (e.g., copper) etchants include a solution comprising from 50 g/L to 500 g/L ferric chloride (FeCl 3 ); a solution comprising from about 5% to about 20% by weight of hydrogen peroxide plus from about 15% to about 30% by volume of sulfuric acid (H 2 S 4 ); a solution comprising from about 15% to about 25% by weight of ammonium persulfate plus from about 15% to about 30% by volume of sulfuric acid; a solution comprising from 250 g/L to 380 g/L nitric acid, and a solution comprising from about 150 to about 350 g/L CrO 3 plus from about 200 to about 400 g/L of sulfuric acid (H 2 SO 4 ).
- contacting of the exposed surface of the etchable metal layer with the etchant solution is performed at ambient temperature (e.g., from about 50° F. to about 90° F.) for a period of from about 30 seconds to about 2 minutes to produce an etch depth of from about 20 to about 400 micrometers.
- ambient temperature e.g., from about 50° F. to about 90° F.
- the etch material is immediately contacted with water to remove the etchant and stop the etching process.
- the etching process can cause stains at the etch surfaces.
- the etched surfaces may be exposed to a hydrochloric acid solution (e.g., 25-50% HCl by volume) at ambient temperature for a relatively short period of time (e.g., from about 1 second to 60 seconds) to remove the stains.
- a hydrochloric acid solution e.g., 25-50% HCl by volume
- the surfaces are rinsed with water and dried (e.g., with compressed oil-free air).
- an organic stripping solvent such as denatured alcohol, heptane, etc.
- the chemical etching process may be repeated a plurality of times using different mask patterns, different depths, etc. to prepare various textured patterns, graphical designs, text, etc.
- sand blasting or other mechanical techniques may be employed, or laser or other ablative techniques may be employed.
- Cleaning solutions useful for removing residues from the surface of the etched metal layer generally contain at least one organic solvent and at least one surfactant.
- An example of a preferred cleaning solution contains 20-35% by weight ethyl ethanol, 10-40% by weight heptane, 2-10% by weight triethanolamine, 1-3% by weight non-ionic surfactant (such as butyl or hexyl cellosolve), 10-50% by weight p-mentha-1,8-diene, and up to 10% by weight isopropanol.
- the cleaning process is typically carried out at a temperature of from about 70° F. to about 110° F.
- Contacting of the etched metal layer with a cleaning solution may be accompanied with mechanical agitation or ultrasonic agitation for at least about 1 minute.
- Soft brushing may also be helpful to eliminate heavy contaminants on the surface of the etched metal layer.
- the cleaning solution is rinsed from the etched surface with a water-soluble solvent, such as ethanol, 1-propanol, 2-propanol, or mixtures of these solvents. Thereafter, the water-soluble solvents are immediately rinsed from the surface of the etched metal layer with water.
- a 5-10% commercial alkaline cleaner such as Polyprep Cleaner 2202 (Henkel), Gardoclean S 5206 (Oakite), etc.
- an acid solution such as a 20-50% by volume hydrochloric acid solution, or a 15-30% by volume sulfuric acid solution, etc.
- an acid solution such as a 20-50% by volume hydrochloric acid solution, or a 15-30% by volume sulfuric acid solution, etc.
- the surface of the textured (etched) metal layer may be activated by contact with an activating solution prior to subsequent electroplating.
- a suitable activating solution for subsequent acid copper electroplating is a solution comprising from about 1% to about 15% by weight hydrogen peroxide (H 2 O 2 ) and from about 10% to about 30% by volume sulfuric acid (H 2 SO 4 ).
- a suitable contact time with the activation solution is about 5 seconds to about 60 seconds at room temperature, followed by rinsing with water.
- the finish layer Before the finish layer is deposited on the surface of the plastic component, it may be desirable to electroplate one or more layers over the textured metal layer having the desired relief pattern. Specifically, it may be desirable to utilize a conventional acid copper electroplating process to level or fill light scratches left on the etched surface during prior texturing and cleaning operations. It may also be desirable to electroplate one or more layers of other metals, particularly nickel, on the relief patterned layer before depositing a finish layer on the relief patterned layer. For example, a semi-bright nickel layer may be electroplated onto the textured metal layer prior to electroplating chrome onto the component. In addition, or alternatively, a bright nickel layer may also be electroplated onto the textured metal layer prior to electroplating a chrome finish layer.
- a microporous nickel layer may be electroplated onto the plastic article between the textured metal layer and the finish layer in order to retard corrosion.
- depositing a finish layer over the patterned metal layer refers to either depositing a finish layer directly on the etched or patterned metal layer, or depositing a finish layer on one or more layers previously applied to the etched metal layer.
- the finish layer may comprise a relatively thin chrome or other metal (e.g., nickel) layer deposited over the etched metal layer using known electroplating techniques.
- suitable finish layers include metals such as rhodium, gold, palladium, platinum, silver, black nickel, nickel, or other metals deposited over etched metal layer using any of various metal plating techniques, including vacuum deposition, physical vapor deposition, chemical vapor deposition, etc.
- a non-metallic material may be used as the finish layer, or may be applied over a metal finish layer. Examples of non-metallic finish or overcoat layers include clear or tinted organic (e.g., polymer) coating compositions, electrophoretic coatings, opaque paints, etc.
- a corrosion inhibitor may be applied to the surface of the relief patterned metal layer after cleaning the surface of the relief patterned layer. This facilitates storage and/or transportation of the article to another facility for subsequent processing.
- the corrosion inhibitor may be removed, such as with cleaning solvents or the like, prior to subsequent processing.
Abstract
A relatively inexpensive process for making plastic components having textured chrome finishes that may have fine, crisp, clean lines and intricate details includes steps of electroplating a layer of etchable metal on a surface of a plastic article, typically preserving the surface of the etchable metal, etching a desired relief pattern on the layer of etchable metal, typically cleaning and activating the surface of the relief patterned etched metal layer, and electroplating a layer of decorative metal on the relief patterned etched metal layer.
Description
- This invention relates to decorative finishes and more particularly to a process for creating a plated plastic article having a decorative relief pattern.
- Decorative chrome finishes on plastic components have long been popular in automotive, appliances, teletronics, and household applications. While chrome plated plastic articles having decorative relief patterns are known and desired, it is expected that the demand for more delicately textured or patterned chrome finishes will increase in the near future. A textured chrome finish on a plastic component can be achieved by applying a chrome plating over a pre-textured molded plastic component. However, this practice is not economically acceptable in the initial marketing phase of potential products, and is unacceptable for certain low volume or specialty products, because pre-textured molds are relatively expensive. Further, it is extremely difficult to consistently produce delicate and/or intricate textured patterns in a plastic molding process. In addition, because of the thicknesses of the multiple layers required for chrome plating a plastic substrate, much of the original detail in the molded relief pattern may be lost during the plating process.
- U.S. Pat. Nos. 3,843,763 and 3,869,535 disclose methods for modifying embossing rollers, plates or dies by subjecting machine engraved or electroformed roller to a combination of plating steps. The embossed roller is first subjected to a bright metal plating step with a metal characterized by a high or medium leveling effect to produce a combined brightening and smoothing effect on the roller. This step is followed by a second plating step used as a finishing coating for the roller. The second plating is suitably achieved using a metal having a relatively lower leveling effect such as chromium or nickel. The second plating step provides a hard coating surface which is resistant to corrosion and erosion while at the same time enhancing the textured pattern of the end desired product. The disclosed process starts with a substrate having the desired relief pattern.
- U.S. Pat. No. 4,278,739 discloses a method of metallizing materials by coating a substrate material with a hydrophilic composite material, electrolessly metal plating the hydrophilic composite material with a metal to render the surface conductive, and electroplating a metal onto the conductive surface. The method is said to be useful for producing metallized forms, embossing plates for reproduction of grains and textures, and decorative coatings for substrate materials.
- U.S. Pat. No. 4,600,480 discloses a method for plating selected surfaces of a plastic substrate without plating other selected surfaces. The disclosed method involves electrolessly plating the substrate to provide an electroless metal layer over all of the first selected surfaces and at least a portion of second selected surfaces, mounting the substrate on an electroplating rack so that the current density at the second selected surfaces is lower during electroplating than at the first selected surfaces, whereby the substrate is electroplated to provide intermediate metal layers which extend over at least all of the first selected surfaces, and then electroplating with a final metal different from the metals of the electroless and intermediate layers at a voltage whereby the final metal deposits over the first selected surfaces but not over the second selected surfaces. The electroplated substrate is then immersed in a stripping solution which dissolves the electroless and intermediate metals but not the final metal.
- U.S. Pat. No. 4,820,553 discloses a process for conditioning surfaces of a polyester or polyamide material for electroless plating. The method comprises exposing surfaces of the polyester and/or polyamide material to a composition which comprises a solvent system containing water, a water-soluble organic solvent and solvated hydroxyl ions to etch the surface of the substrate to improve adhesion of a metal coating with the substrate.
- U.S. Pat. No. 6,489,034 discloses a method of applying a metal onto a copper layer by steps of stabilizing a surface of a copper layer by applying an oxide layer to the copper layer, and vapor depositing a metal, such as chromium, directly onto the oxide surface of the copper layer.
- There remains a need for improved processes for preparing textured decorative plastic components, especially techniques that allow preparation of delicately, textured patterned finishes which have fine, crisp, clean lines and intricate details. Especially needed is a process of this type which is relatively inexpensive and/or provides greater flexibility in the preparation of low cost plastic articles having a textured finish.
- The invention provides an economically acceptable process for making plastic components having delicately textured or patterned finishes, and provides a flexible technology for producing decorative patterns having fine, crisp, clean lines and intricate details on a variety of plastic parts having a metal layer. The process includes steps of electroplating a layer of etchable metal on a surface of a plastic article; typically preventing the etchable metal surface from tarnishing; etching a desired relief pattern on the layer of etchable metal; typically cleaning and activating the surface of the relief patterned etched metal layer; and depositing a finish layer on the relief patterned etched metal layer.
- These and other features, advantages and objects of the present invention will be further understood and appreciated by those skilled in the art by reference to the following specification and claims.
- In accordance with an embodiment of the invention, a process for preparing a plastic article having a desired relief pattern in a plated surface generally involves depositing a relatively thick layer of etchable metal on a surface of the article; forming the desired relief pattern on an exposed surface of the etchable metal layer; and depositing a finish layer over the relief pattern.
- Generally, there are several preparation steps prior to the step of electroplating a layer of etchable metal on the surface of the article. Typically, an electrically conductive electroless coating is provided prior to electroplating of the layer of etchable metal. Electroless coating generally involves steps of cleaning and etching the substrate, neutralizing the etched surface, catalyzing the neutralized surface (e.g. in a solution that contains palladium chloride, stannous chloride and hydrochloric acid), followed by immersion in an accelerator solution (which is either an acid or a base), and forming a metallic coating on the activated substrate. The surface of the substrate is typically conditioned by cleaning with a detergent solution and etched by dipping the substrate in an etchant (e.g., a mixed solution of chromic acid and sulfuric acid). The metallic coating may be deposited on the activated substrate by immersing the substrate in a chemical plating bath containing nickel or copper ions and deposing the metal thereon from the bath by means of the chemical reduction of the metallic ions. The resulting metallic coating is useful for subsequent electroplating because of its electrical conductivity. It is also conventional to wash the substrate with water after each of the above steps. Other suitable techniques for pretreating a plastic substrate to provide an electrically conductive coating to render the substrate receptive to electroplating operations are well known in the art, and may be employed prior to electroplating a layer of etchable metal on a surface of the article in accordance with the principles of this invention.
- Typical plastic materials that have been rendered receptive to electroplating, and which may be subsequently electroplated include acrylonitrile-butadiene styrene (ABS) resins, polyesters, polyethers, polyacrylics, polycarbonates, polyamides, polyolefins, polyvinylchloride, polycarbonate (PC) resins/ABS alloy polymers and phenol-formaldehyde polymers. The process of this invention may be applied to these and other plastics.
- After electroless plating or coating of the substrate with an electrically conductive material, the layer of etchable metal is electroplated onto the article. In order to provide a visually perceivable and aesthetically acceptable relief pattern, a relatively thick layer of etchable metal is electroplated onto the treated surface of the plastic article. A suitable thickness of the etchable metal layer is typically from about 50 to about 500 micrometers. A thinner layer may be utilized, although this may limit the ability to provide a visually discernible, aesthetically acceptable relief pattern. Greater thicknesses may also be used, but are generally unnecessary to achieve an aesthetically acceptable textured or graphical relief pattern. While various metals may be used for electroplating a suitable etchable metal layer, including nickel, tin, zinc, cobalt, etc., a copper electroplate is preferred because of its relatively low cost and excellent etchability properties. Specifically, it is possible to chemically, mechanically (e.g., such as with sand blasting), or ablatively (e.g., such as with a laser) etch a desired relief pattern into a copper surface to produce relatively sharp, precise relief structures.
- While it is not necessary, the layer of etchable metal that is subsequently etched to form the desired relief pattern may be electroplated over any number of previous layers. Accordingly, as used herein, electroplating a layer of etchable metal on the article may be achieved by either electroplating directly on the plastic article treated with an electroless coating, or on one or more layers of material deposited on the surface of the plastic article.
- Before etching the relief pattern into the layer of etchable metal, it is desirable to first activate the exposed surface of the etchable metal layer in order to form a thin layer of preservative film on the etchable metal surface. This may be achieved by contacting the exposed surface of the etchable metal layer with an activating solution comprising from about 1% to about 10% by weight hydrogen peroxide (H2O2) and from about 5 to about 20% by volume of sulfuric acid (H2SO4). A suitable contact time is from about 5 seconds to about 60 seconds, and contacting of the exposed surface of the etchable metal layer with the activating solution may be performed at ambient conditions (e.g., normal atmosphere pressure and normal facility or room temperatures). Before etching the etchable metal layer, it may be desirable to contact the exposed surface of the etchable metal layer with an aqueous corrosion inhibiting solution to prevent the etchable metal surface from tarnishing. The expression “contacting” as used herein, unless otherwise indicated, refers to immersion, spraying or any other treatment that provides appropriate contact of the surface with a liquid treatment composition. A suitable contact time of the exposed surface of the etchable metal layer with the corrosion inhibitor solution is from about 1 second to about 10 minutes. Examples of corrosion inhibiting agents that may be employed in an aqueous corrosion inhibitor include benzotriazole, 2-mercaptobenzimidazole, 2-mercapatobenzothiazole, 2-mercaptobenzoxazole, their derivatives, or a combination of these corrosion inhibiting agents. Such agents are typically present in the aqueous corrosion inhibitor solution at a concentration of at least 10 mg/L.
- Any of various etching techniques that are well known may be employed for etching the desired relief pattern into the surface of the etchable metal layer. In the case of chemical etching, the exposed surface of the etchable metal layer is coated with a material (typically a synthetic polymer material) that is either chemically resistant to the etchant used for etching the metal, or which can be rendered chemically resistant, such as by cross-linking. Any of various masking techniques known in the art may be employed, including wax masking, etchable film masking, brush-coat masking, spray-coat masking, immersion-coat masking, UV cure photoresist masking, etc. After the coating has been applied to the exposed surface of the etchable metal layer, sections of the coating are removed to expose sections of the underlying etchable metal layer. The patterned coating or mask and the exposed sections of the surface of the etchable metal layer are contacted with a chemical etchant that removes (e.g., dissolves) metal at the surface of the etchable metal layer, thereby forming a relief pattern into the metal that corresponds with the mask pattern. Conventional photoresist materials may be used for preparing the patterned coatings or masks. Typically, precise patterns can be formed into the photoresist materials by selective exposure of the photoresist material to ultraviolet radiation. Typically ultraviolet radiation is used to either decompose the exposed areas of the photoresist resin coating or to cross link the exposed areas of the photoresist resin coating. In the case where the ultraviolet radiation decomposes sections of the photoresist coating, the decomposed areas are removed, typically by contacting these areas with a solvent, and the remaining portions, which constitute the mask, are chemically resistant to the etchant. In the case where the ultraviolet radiation cross links the exposed sections of the photoresist material, the cross-linked sections are rendered chemically resistant to the etchant, and the unexposed sections are removed (such as with a solvent) to form the mask.
- Suitable etchants for etching the surface of a metal layer, such as copper, include various acid solutions. Specific examples of metal (e.g., copper) etchants include a solution comprising from 50 g/L to 500 g/L ferric chloride (FeCl3); a solution comprising from about 5% to about 20% by weight of hydrogen peroxide plus from about 15% to about 30% by volume of sulfuric acid (H2S4 ); a solution comprising from about 15% to about 25% by weight of ammonium persulfate plus from about 15% to about 30% by volume of sulfuric acid; a solution comprising from 250 g/L to 380 g/L nitric acid, and a solution comprising from about 150 to about 350 g/L CrO3 plus from about 200 to about 400 g/L of sulfuric acid (H2SO4). Typically, contacting of the exposed surface of the etchable metal layer with the etchant solution is performed at ambient temperature (e.g., from about 50° F. to about 90° F.) for a period of from about 30 seconds to about 2 minutes to produce an etch depth of from about 20 to about 400 micrometers. After the exposed areas of the etchable metal layer have been contacted with an etchant for a suitable period of time to achieve a desired etch depth, the etch material is immediately contacted with water to remove the etchant and stop the etching process.
- The etching process can cause stains at the etch surfaces. In order to remove such stains the etched surfaces may be exposed to a hydrochloric acid solution (e.g., 25-50% HCl by volume) at ambient temperature for a relatively short period of time (e.g., from about 1 second to 60 seconds) to remove the stains. Immediately thereafter, the surfaces are rinsed with water and dried (e.g., with compressed oil-free air). Thereafter, the remainder of the photoresist material (mask) is removed with an organic stripping solvent, such as denatured alcohol, heptane, etc. The chemical etching process may be repeated a plurality of times using different mask patterns, different depths, etc. to prepare various textured patterns, graphical designs, text, etc.
- As an alternative to chemical etching, sand blasting or other mechanical techniques may be employed, or laser or other ablative techniques may be employed.
- Because the etching process may leave invisible masking material and etching agent residue on surfaces of the etched metal layer, it is usually necessary to further clean and activate the surfaces of the etched metal layer for subsequent electroplating. Cleaning solutions useful for removing residues from the surface of the etched metal layer generally contain at least one organic solvent and at least one surfactant. An example of a preferred cleaning solution contains 20-35% by weight ethyl ethanol, 10-40% by weight heptane, 2-10% by weight triethanolamine, 1-3% by weight non-ionic surfactant (such as butyl or hexyl cellosolve), 10-50% by weight p-mentha-1,8-diene, and up to 10% by weight isopropanol. The cleaning process is typically carried out at a temperature of from about 70° F. to about 110° F. Contacting of the etched metal layer with a cleaning solution may be accompanied with mechanical agitation or ultrasonic agitation for at least about 1 minute. Soft brushing may also be helpful to eliminate heavy contaminants on the surface of the etched metal layer. After cleaning masking and etchant residues from the surface with the cleaning solution, the cleaning solution is rinsed from the etched surface with a water-soluble solvent, such as ethanol, 1-propanol, 2-propanol, or mixtures of these solvents. Thereafter, the water-soluble solvents are immediately rinsed from the surface of the etched metal layer with water. In some cases, it may be desirable to further remove inorganic contaminants from the textured (etched) metal layer by immersion in or spraying with a 5-10% commercial alkaline cleaner, such as Polyprep Cleaner 2202 (Henkel), Gardoclean S 5206 (Oakite), etc. at a temperature of from about 140° F. to about 180° F. for at least 30 seconds, and immediately thereafter rinsing with water. After the cleaning and rinsing steps, it may be necessary to remove corrosion or tarnish stains by immersion in an acid solution, such as a 20-50% by volume hydrochloric acid solution, or a 15-30% by volume sulfuric acid solution, etc., at ambient temperature for a period of from about 10 seconds to about 120 seconds, and immediately thereafter rinsing the acid from the textured (etched) metal layer with demineralized water, and drying (such as with compressed, oil-free air).
- The surface of the textured (etched) metal layer may be activated by contact with an activating solution prior to subsequent electroplating. For example, a suitable activating solution for subsequent acid copper electroplating is a solution comprising from about 1% to about 15% by weight hydrogen peroxide (H2O2) and from about 10% to about 30% by volume sulfuric acid (H2SO4). A suitable contact time with the activation solution is about 5 seconds to about 60 seconds at room temperature, followed by rinsing with water.
- Before the finish layer is deposited on the surface of the plastic component, it may be desirable to electroplate one or more layers over the textured metal layer having the desired relief pattern. Specifically, it may be desirable to utilize a conventional acid copper electroplating process to level or fill light scratches left on the etched surface during prior texturing and cleaning operations. It may also be desirable to electroplate one or more layers of other metals, particularly nickel, on the relief patterned layer before depositing a finish layer on the relief patterned layer. For example, a semi-bright nickel layer may be electroplated onto the textured metal layer prior to electroplating chrome onto the component. In addition, or alternatively, a bright nickel layer may also be electroplated onto the textured metal layer prior to electroplating a chrome finish layer. In addition, or alternatively, a microporous nickel layer may be electroplated onto the plastic article between the textured metal layer and the finish layer in order to retard corrosion. Accordingly, the expression “depositing a finish layer over the patterned metal layer” refers to either depositing a finish layer directly on the etched or patterned metal layer, or depositing a finish layer on one or more layers previously applied to the etched metal layer.
- The finish layer may comprise a relatively thin chrome or other metal (e.g., nickel) layer deposited over the etched metal layer using known electroplating techniques. Other suitable finish layers include metals such as rhodium, gold, palladium, platinum, silver, black nickel, nickel, or other metals deposited over etched metal layer using any of various metal plating techniques, including vacuum deposition, physical vapor deposition, chemical vapor deposition, etc. A non-metallic material may be used as the finish layer, or may be applied over a metal finish layer. Examples of non-metallic finish or overcoat layers include clear or tinted organic (e.g., polymer) coating compositions, electrophoretic coatings, opaque paints, etc.
- To facilitate different processing steps at different facilities, it may be desirable to apply a corrosion inhibitor to the surface of the relief patterned metal layer after cleaning the surface of the relief patterned layer. This facilitates storage and/or transportation of the article to another facility for subsequent processing. The corrosion inhibitor may be removed, such as with cleaning solvents or the like, prior to subsequent processing.
- The above description is considered that of the preferred embodiments only. Modifications of the invention will occur to those skilled in the art and to those who make or use the invention. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and not intended to limit the scope of the invention, which is defined by the following claims as interpreted according to the principles of patent law, including the doctrine of equivalents.
Claims (60)
1. A process for preparing a metal plated plastic article having a desired relief pattern in a surface of the article, comprising:
electroplating a layer of etchable metal on the plastic article;
etching the desired relief pattern on the layer of etchable metal; and
depositing a finish layer over the patterned metal layer.
2. The process of claim 1 , further comprising cleaning the surface of the article before electroplating an etchable metal layer on the article.
3. The process of claim 1 , further comprising conditioning the surface of the article before electroplating an etchable metal layer on the article.
4. The process of claim 1 , further comprising etching the surface of the plastic article before electroplating the etchable metal layer on the article.
5. The process of claim 1 , further comprising neutralizing the surface of the plastic article before electroplating the etchable metal layer on the article.
6. The process of claim 1 , further comprising catalyzing the surface of the plastic article before electroplating the etchable metal layer on the article.
7. The process of claim 1 , further comprising contacting the surface of the plastic article with an accelerator solution before electroplating the etchable metal layer on the article.
8. The process of claim 1 , further comprising electroless plating the surface of the plastic article before electroplating the etchable metal layer on the article.
9. The process of claim 1 , wherein the etchable metal layer is electroplated onto the article to a thickness of from about 50 micrometers to about 500 micrometers.
10. The process of claim 1 , wherein the etchable metal layer on the surface of the article is activated before the desired relief pattern is etched on the etchable metal layer.
11. The process of claim 10 , wherein the etchable metal layer is activated by contacting an exposed surface of the etchable metal layer with an activation solution comprising from about 1% by weight to about 10% by weight hydrogen peroxide (H2O2) and from about 5% by volume to about 20% by volume sulfuric acid (H2SO4).
12. The process of claim 11 , wherein the etchable metal layer is contacted with the activation solution for about 5 seconds to about 60 seconds.
13. The process of claim 1 , wherein an exposed surface of the etchable metal layer is contacted with an aqueous corrosion inhibitor solution before the desired relief pattern is etched on the etchable metal layer.
14. The process of claim 13 , wherein the surface of the etchable metal layer is contacted with the aqueous corrosion inhibitor solution for a period of from about 1 second to about 10 minutes.
15. The process of claim 13 , wherein the aqueous corrosion inhibitor solution comprises at least one corrosion inhibiting agent selected from the group consisting of benzotriazole, 2-mercaptobenzimidazole, 2-mercapatobenzothiazole, 2-mercaptobenzoxazole and their derivatives.
16. The process of claim 13 , wherein the aqueous corrosion inhibitor solution comprises benzotriazole at a concentration of at least 10 mg/L.
17. The process of claim 1 , wherein the etching of the desired relief pattern on the etchable metal layer is achieved by selectively masking sections of the surface of the etchable metal while exposing other sections of the surface of the etchable metal, and contacting the masked surface with an etchant, the mask being resistant to the etchant, whereby only the exposed sections of the surface of the etchable metal are etched.
18. The process of claim 17 , wherein the etching of the sections of the etchable metal layer that are exposed through mask is achieved by contacting the etchable metal layer with a chemical etchant.
19. The process of claim 18 , wherein the etchant is a solution comprising from 50 g/L to 500 g/L ferric chloride (FeCl3).
20. The process of claim 18 , wherein the etchant is a solution comprising from about 5% by weight to about 20% by weight hydrogen peroxide (H2O2) by weight and from about 15% by volume to about 30% by volume sulfuric acid (H2SO4).
21. The process of claim 18 , wherein etchant is a solution comprising from about 15% by weight to about 25% by weight ammonium persulfate and from about 15% by volume to about 30% by volume sulfuric acid (H2SO4).
22. The process of claim 18 , wherein etchant is a solution comprising from about 250 g/L to about 380 g/L nitric acid (HNO3).
23. The process of claim 18 , wherein etchant is a solution comprising from about 150-350 g/L of CrO3 and from about 200 to about 400 g/L of H2SO4.
24. The process of claim 19 , wherein the contacting of the exposed surface of the etchable metal layer with the etching solution is for a period of from about 30 seconds to about 2 minutes.
25. The process of claim 20 , wherein the contacting of the exposed surface of the etchable metal layer with the etching solution is for a period of from about 30 seconds to about 2 minutes.
26. The process of claim 21 , wherein the contacting of the exposed surface of the etchable metal layer with the etching solution is for a period of from about 30 seconds to about 2 minutes.
27. The process of claim 22 , wherein the contacting of the exposed surface of the etchable metal layer with the etching solution is for a period of from about 30 seconds to about 2 minutes.
28. The process of claim 23 , wherein the contacting of the exposed surface of the etchable metal layer with the etching solution is for a period of from about 30 seconds to about 2 minutes.
29. The process of claim 18 , wherein the contacting of the exposed surface of the etchable metal layer with the etchant solution is sufficient to etch to a depth of from about 20 micrometers to about 400 micrometers.
30. The process of claim 29 , further comprising rinsing the etched metal layer with water, and contacting the etched metal layer with a solution containing from about 25% to about 50% HCl by volume.
31. The process of claim 30 , further comprising immediately rinsing the exposed surface of the etched metal layer with water after contacting the etched metal layer with a solution containing HCl, and drying the rinsed surface.
32. The process of claim 30 , wherein the rinsed surface is dried with compressed, oil-free air.
33. The process of claim 17 , further comprising removing the remaining sections of the inorganic chemical resistant material from the etched metal layer by contact with a stripping solvent.
34. The process of claim 33 , further comprising cleaning and activating the surface of the etched metal layer before electroplating chrome on the etched metal layer.
35. The process of claim 34 , wherein the cleaning of the etched metal layer comprises removing organic residues with a cleaning solution containing at least one organic solvent and at least one surfactant; rinsing the cleaning solution from the etched metal layer with a water-soluble organic solvent; and rinsing the water-soluble organic solvent from the etched metal layer with water.
36. The process of claim 35 , wherein the cleaning solution comprises 20-30% by weight ethyl ethanol, 10-40% by weight heptane, 2-10% by weight triethanolamine, 1-3% by weight non-ionic surfactant, and 10-50% by weight p-mentha-1,8-diene.
37. The process of claim 35 , wherein the cleaning further comprises mechanical agitation, ultrasonic agitation, or brushing.
38. The process of claim 35 , wherein the water-soluble solvent is selected from the group consisting of ethanol, 1-propanol, 2-propanol and combinations thereof.
39. The process of claim 35 , further comprising supplemental removal of inorganic contaminants from the etched metal surface by contact with an alkaline cleaning solution, and rinsing of the alkaline cleaning solution from the etched metal surface with water.
40. The process of claim 35 , further comprising removal of corrosion or tarnish stains by contacting the etched metal layer with an acid solution and rinsing the acid solution and rinsing the acid solution from the etched metal layer.
41. The process of claim 40 , wherein the acid solution comprises 20-50% by volume HCl or 15-30% by volume H2SO4.
42. The process of claim 34 , wherein activating the surface of the etched metal layer comprises contacting the surface of the etched metal layer with an activating solution containing 1-15% by weight of hydrogen peroxide (H2O2) and 10-30% by volume sulfuric acid (H2SO4) at about ambient temperature for about 5-60 seconds, and then rinsing the activating solution from the surface of the etched metal layer with water.
43. The process of claim 1 , further comprising acid copper electroplating a thin layer of copper on the etched metal layer before electroplating a finish layer on the etched metal layer, whereby light scratches left on the surface of the etched metal layer during etching, cleaning or activating are leveled.
44. The process of claim 1 , further comprising electroplating at least one layer of nickel on the etched metal layer before electroplating a finish layer on the etched metal layer.
45. The process of claim 1 , further comprising electroplating a layer of bright nickel on the etched metal layer before electroplating a finish layer on the etched metal layer.
46. The process of claim 1 , further comprising electroplating a layer of semi-bright nickel on the etched metal layer before electroplating a finish layer on the etched metal layer.
47. The process of claim 1 , further comprising electroplating a layer of microporous nickel on the etched metal layer before electroplating a finish layer on the etched metal layer.
48. The process of claim 1 , further comprising electroplating a layer of semi-bright nickel, a layer of bright nickel, and a layer of microporous nickel on the etched metal layer before electroplating the finish layer on the etched metal layer.
49. The process of claim 1 , further comprising electroplating a layer of satin nickel on the etched metal layer before electroplating the finish layer on the etched metal layer.
50. The process of claim 1 , further comprising applying a chrome activator to the surface of the etched metal layer or to a surface of a metal layer electroplated directly on or indirectly on the etched metal layer.
51. The process of claim 1 , wherein etching of the desired pattern is achieved using a laser.
52. The process of claim 1 , wherein the etching of the desired pattern is achieved using mechanical abrasion.
53. The process of claim 52 , wherein the mechanical abrasion is sanding-blasting.
54. The process of claim 1 , wherein the layer of etchable metal is a layer of copper.
55. The process of claim 34 , further comprising applying a corrosion inhibitor to a surface of the etched metal layer, transporting or storing the article after applying the corrosion inhibitor, and removing the corrosion inhibitor after transporting or storing the article and before activating the surface of the etched metal layer.
56. The process of clam 1, wherein the finish layer is a metal layer.
57. The process of claim 56 , wherein the finish metal layer is selected from the group consisting essentially of chrome, rhodium, gold, platinum, palladium, silver, nickel and black nickel.
58. The process of claim 56 , wherein an organic overcoat is deposited over the finish metal layer.
59. The process of claim 1 , wherein the finish layer is an organic coating.
60. A plastic article having a decorative relief pattern, comprising:
a plastic substrate;
an etched metal layer disposed on the substrate; and
a finish layer disposed over the etched metal layer.
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US10/970,018 US20060086620A1 (en) | 2004-10-21 | 2004-10-21 | Textured decorative plating on plastic components |
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