CN108239747B - 涂覆有黄色层的珍珠母基质 - Google Patents
涂覆有黄色层的珍珠母基质 Download PDFInfo
- Publication number
- CN108239747B CN108239747B CN201711390750.4A CN201711390750A CN108239747B CN 108239747 B CN108239747 B CN 108239747B CN 201711390750 A CN201711390750 A CN 201711390750A CN 108239747 B CN108239747 B CN 108239747B
- Authority
- CN
- China
- Prior art keywords
- titanium
- silicon nitride
- doped
- oxygen
- layer
- 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.)
- Active
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 178
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 170
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 90
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 84
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 83
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 79
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 137
- 230000000694 effects Effects 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000002845 discoloration Methods 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 239000000919 ceramic Substances 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910008482 TiSiN Inorganic materials 0.000 description 8
- 238000004040 coloring Methods 0.000 description 8
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910008484 TiSi Inorganic materials 0.000 description 3
- 235000019993 champagne Nutrition 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 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
- 150000002739 metals Chemical class 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- -1 silicon nitrides Chemical class 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000000763 evoking effect Effects 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
- G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/005—Coating layers for jewellery
- A44C27/007—Non-metallic coatings
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
- C23C14/0652—Silicon nitride
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/586—Nitriding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B19/00—Indicating the time by visual means
- G04B19/06—Dials
- G04B19/10—Ornamental shape of the graduations or the surface of the dial; Attachment of the graduations to the dial
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B19/00—Indicating the time by visual means
- G04B19/06—Dials
- G04B19/12—Selection of materials for dials or graduations markings
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
- G04B45/0076—Decoration of the case and of parts thereof, e.g. as a method of manufacture thereof
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B47/00—Time-pieces combined with other articles which do not interfere with the running or the time-keeping of the time-piece
- G04B47/04—Time-pieces combined with other articles which do not interfere with the running or the time-keeping of the time-piece with attached ornaments or amusement apparatus
-
- G—PHYSICS
- G04—HOROLOGY
- G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
- G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
- G04D3/0069—Watchmakers' or watch-repairers' machines or tools for working materials for working with non-mechanical means, e.g. chemical, electrochemical, metallising, vapourising; with electron beams, laser beams
-
- G—PHYSICS
- G04—HOROLOGY
- G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
- G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
- G04D3/0074—Watchmakers' or watch-repairers' machines or tools for working materials for treatment of the material, e.g. surface treatment
- G04D3/0092—Watchmakers' or watch-repairers' machines or tools for working materials for treatment of the material, e.g. surface treatment for components of the time-indicating mechanism, e.g. dials
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/005—Coating layers for jewellery
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/005—Coating layers for jewellery
- A44C27/006—Metallic coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/02—Superimposing layers
-
- G—PHYSICS
- G04—HOROLOGY
- G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
- G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
- G04D3/0074—Watchmakers' or watch-repairers' machines or tools for working materials for treatment of the material, e.g. surface treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Physical Vapour Deposition (AREA)
- Adornments (AREA)
- Laminated Bodies (AREA)
Abstract
在包括预先在基质(1)上制备的至少一个可见表面的制表或珠宝外部部件上着色涂覆的方法，该方法包括钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的至少一个主层(3)的至少一个真空沉积步骤。
Description
发明领域
本发明涉及一种用于在包含预先在基质上制备的至少一个可见表面的制表或珠宝部件，特别是外部部件上着色涂覆的方法，所述方法包括钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的至少一个主层的至少一个真空沉积步骤。
本发明还涉及包含珍珠母基质的制表或珠宝结构部件。
本发明还涉及包含珍珠母基质的制表或珠宝外部部件。
本发明涉及制表和珠宝领域。
背景技术
美学外观在制表和珠宝领域是非常重要的，并且需要对一些部件着色。特别想到的是手表表盘，其理想的是以各种色相进行着色，其中包括淡黄色，以下称为“香槟”，和唤起与豪华印象联系在一起的发泡白葡萄酒的颜色。
使用薄的无机层使钟表表面着色是很好地建立和使用的。然而，所使用的大多数层(金属，氮化物，碳化物等)具有高吸收性并且几乎不透明，厚度仅为几十纳米。此外，它们极大地反射光，因此具有不总是期望的金属外观。这两个特征极大地限制了它们用于着色表面同时仍然保持其原始外观如珠光或干涉外观的可见性的使用，或者在豪华制表的情况下，具有斜面或具有扭索状装饰并且需要保持未机械抛光，没有抛光、打磨或类似的最少的机械处理。
为了实现这个目标，有必要使用一个层，其在同一时间：
-在可见光谱中非常有选择地吸收(这定义了该层透射的颜色)；这允许独立于视角的“固有颜色”；
-具有与介电氧化物(无金属外观)相当的最低可能反射度；
-与基质粘合良好；
-无毒；
-相对于涂覆制品的生产和使用条件而言是稳定的，例如洗涤，镶嵌应用，处理等；
-在不损害基质的条件下沉积；
-化学稳定，能够抵御制表业内部零件的正常测试：紫外线，湿热，热冲击等。
这些性质往往是矛盾的，难以同时满足所有这些条件。
浅黄色的特殊情况难以处理，因为所用的层通常不是很耐久，特别是非常不耐磨。实际上，通常用于产生黄色薄透明层的化学组合物通常含有铁氧化物，并且不能很好地耐磨和抗化学侵蚀。
通常用于产生黄色薄层的其它化学组合物非常有光泽并且不透明：这些化合物尤其是Ti和/或Zr的氮化物和碳氮化物，(Ti,Zr)Nx；(Zr,Hf)Nx。
即使可以想象通过介电层，特别是SiO2或Si3N4，通过干涉来产生颜色，该技术具有永久的缺点，这是由于表观颜色依赖于观察角度。此外，对于这种类型的层，反射的颜色总是非常强烈的，并且与传输的颜色互补。
有机颜料的着色也是可以实现的，但是在颜料的长期稳定性方面存在缺陷，并且耐磨性和抗化学侵蚀性低。
至今为止，市场上还没有一个符合上述要求的且具有很好的耐磨性的透明黄色层。
文献FR2425210A1Nishida Nobuo描述了在对热不敏感的基质上提供有金色涂层的珠宝部件，涂层具有0-1μm的厚度，由氮化钛形成，包括来自Al，Si，V，Cr，Fe，Co，Ni，Cu，Zn，Ge，Y，Zr，Nb，Mo，Ru，Rh，Pd，Ag，Cd，In，Sn，Sb，Ti，Hf，Ta，W，Ir，Pt和Au的元素。550μm和400μm的涂层外表面的光谱反射比在1.2/1至3.0/1之间。基质可以由钢和/或Ni和/或Ni-Ag，和/或合金如Al合金，和/或陶瓷物质，和/或耐热树脂制成。对于表壳，表带和戒指。涂层的颜色非常类似于金，而且方法经济。
文献EP 0 353 060 A2 NIPPON STEEL描述了一种金属板，其通过由在金属板上形成的彩色陶瓷层的层构成的多层涂层掺杂有优异的装饰性颜色，彩色陶瓷层由选自以下的至少一种化合物形成：钛，锆，铪，铬，铌和铝的氮化物和碳化物，厚度为0.1μm到1μm；以及形成在彩色陶瓷层上的透明陶瓷层，透明陶瓷层由氧化硅、氮化硅和氧化铝中的至少一种制成，并且具有0.1μm至5μm的厚度。彩色和透明陶瓷层的沉积通过干法进行，彩色和透明陶瓷层的沉积顺序可以颠倒。
文献US2014/037943A1Cao Da-Hua描述了一种涂层制品，其包括金属基质，直接形成在金属基质上的TiSiN层，TiSiN层基本上由元素Ti，Si和元素N组成，TiSiN层中的元素Si具有从基质附近的TiSiN层的底部到远离基质的TiSiN层的上部逐渐减小的质量百分比，元素N具有从基质附近的TiSiN层的底部到远离基质的TiSiN层的上部逐渐增加的质量百分比；和直接在TiSiN层上形成的TiN层，TiN层基本上由元素Ti和元素N形成。
文献JP2009213616A CTITIZEN描述了一种刚性层，其向该发明那样包含氮化物层，以及在透明表面层下的包含金或金合金的面层。
文献EP 1 672 436 A1 ROLEX描述了一种用于钟表的表盘的制造方法，该表盘的可见表面包括金属外观涂层，其表面状态具有珍珠母的形态特征，其特征在于，使珍珠母板经受砂磨操作以赋予它对应于珍珠母形态的表面状态，将该表面清洁并涂覆金属层或由氧化物、氮化物或金属碳化物制成的层。
由Jindrich Musil等人于2007年4月1日发表的文章涉及“具有高Si含量的Ti-Si-N膜”，Plasma process and polymers，第4卷，no.S1，第S574-578页，XP055397274，ISSN1612-8850，DOI 10.2012/ppap.200731408。
J.Pang等人于2013年11月1日公开的文章涉及“deposition of Ti-Si-N filmson Al substrates by magnetron sputtering”，Surface engineering，第29卷，no.10，第749-754页，XP055397272，ISSN 0267-0844，DOI 10.1179/1743294413Y.0000000178。
发明概述
本发明提出给制表或珠宝结构或外部部件，尤其是珍珠母部件如刻度盘或类似物，赋予黄色的“香槟”外观，同时保持这些部件的原始表面可见。
为此，本发明涉及在根据权利要求1的制表或珠宝结构部件或外部部件上的有色涂层的方法。
本发明还涉及包含珍珠母基质的制表或珠宝结构部件。
本发明还涉及包含珍珠母基质的制表或珠宝外部部件。
根据本发明，着色是通过至少一个非透明的主层来实现的，所述主层固有地透射黄色且是透明的。这种着色基于钛和硅氮化物(Ti，Sik)Nx或掺杂有氧的钛和硅氮化物(Ti，Sik)NxOy，由于其透明性，不掩盖涂层下方表面固有的视觉效果，特别是由刷涂、扭索状装饰等导致的，其能够产生特定的浮雕效果，或珠光般的外观，或干涉效果或其他效果。
层例如通过使用阴极(溅射-PVD)或离子(离子束-PVD)溅射的物理气相沉积，蒸发(蒸发-PVD)，激光烧蚀(脉冲激光沉积PVD)或其它类似的方法而真空沉积。
这种新的着色方法特别适用于珍珠母基质。
该方法允许沉积黄色层，其是透明的，并且更特别地具有金色光泽，同时具有足够的在薄层中的着色能力。
根据本发明的钛和硅氮化物基(Ti，Sik)Nx层或掺杂有氧的钛和硅氮化物基(Ti，Sik)NxOy层非常耐磨和抗化学侵蚀，并且是生物相容的。这些性能使该层与外部部件的要求兼容。
附图说明
本发明的其它特征和优点将通过参照附图阅读下面的详细描述而显现，其中图1示意性地且部分地示出了通过根据本发明方法制造的钟表或珠宝外部部件在特定且非限制性的变型中包括在基质上的各层的叠层，包括钛和硅氮化物(Ti，Sik)Nx层或掺杂有氧的钛和硅氮化物(Ti，Sik)NxOy层。
优选实施方案的详细描述
本发明涉及用于在包括预先在基质1上制备的至少一个可见表面的制表或珠宝结构部件或外部部件上的着色涂层的方法。
这意味着结构部件，功能部件，履行机械功能，例如盘，夹板，轮，链扣，闭合件或类似物。
外部部件是指其功能更为直观的部件，特别是显示部件如刻度盘，moon等，或者表带或珠宝上的可见部件。
应该理解的是，如果根据本发明的方法适用于以相容材料选择的任何制表或珠宝部件，则其优选但非限制性地用于某些类型的部件，例如刻度盘或类似物。
更具体地说，该方法适用于珍珠母部件的涂覆。
根据本发明，该方法包括至少一个钛和硅氮化物(Ti，Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3的至少一个真空沉积步骤。
因此，着色通过沉积至少一个主层3而产生，所述主层3固有地透射黄色且是透明的。根据本发明，主层3由掺杂或不掺杂其它金属的钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy组成，以其透明度，不会抵消表面下方的视觉效果。根据基础基质1的制备：结构化，斜切，棱纹，扭索工作等，主层3为基质1的表面的原始颜色添加黄色外观。
可以结合基质1(特别是当其由珍珠母制成时)的虹彩光泽与纹理的光泽(包括刷涂或抛光)，或者甚至是通过在基质1和黄色主层3之间沉积附加中间层2而产生的干涉效果。
应该指出，黄色主层3也可以直接作为基质1的涂层。
给出足够饱和的黄色外观的薄主层3位于厚度为20nm至2000nm的范围内，并且在没有或有粘合层的情况下沉积在基质上。
在一个特定的非限制性实施方案中，主层3以叠层形式存在，其中钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy可以为纯形式或掺杂其他组分。
在另一个特定的非限制性实施方案中，钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy形成整体层。
可以在钛硅氮化物或掺杂有氧的钛硅氮化物的主层3之下或之上沉积电介的、透明或半透明的一层或多层附加中间层2或上层4，以调节通过干涉效果反射和/或透射的颜色。
在一个具体的实施方案中，寻求该层厚度的优化，以便除了该层的固有颜色之外还受益于干涉颜色。
在另一特定实施方案中，添加其他附加中间2或上部4透明层以：
-增加化学和机械抵抗力；
-改善叠层在基质上或着色层上的附着力；
-通过干涉优化更多颜色；
-根据需要给予光泽或无光泽的外观；
-给出深度的外观。
更具体地，给出良好结果的有利比例在1.5-4.0之间的k＝Si/Ti比范内，即(TiSi1.5)Nx直到(TiSi4)Nx或者甚至(Ti,Si1.5)NxOy至(Ti,Si4)NxOy类型的组合物。
没有测量式中x或y的值。主层3不具有金属外观，因此可以得出结论，它们在氮气水平上非常接近化学计量。这涉及“准化学计量”主层。
对于硅相对于钛的极端比例，在合适的范围内，可以计算主要100％化学计量层的值x：
-对于(Ti,Si1.5)Nx，最大值x＝3.00
-对于(Ti,Si4)Nx，最大值x＝6.33
因此可以定义x的值＝3.00至6.33的范围。
颜色的色调和饱和度是比k＝Si/Ti和层厚度的函数。为了获得黄色，选择比k＝Si/Ti的值在1.5和4.0之间。
厚度选择在20nm和2000nm之间，使得该层的黄色充分饱和。可能地，钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy可以掺杂其他金属，例如锂，以增加颜色的饱和度。
钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3可以通过物理气相沉积(PVD)使用分组在一起的技术(通用术语PVD)之一来真空沉积，即阴极溅射，离子束溅射，激光蒸发或消融。
在20nm至2,000nm的有用范围内，作为所需颜色的强度的函数，最佳层厚度在100nm至300nm的范围内：颜色越深，层越厚。
在掺杂中，用氧掺杂产生了良好的结果，尽管根据偏差它不用于为珍珠母提供的层中，但其合适的化学配制是这样的类型：
(Ti,Sim)NxOy，其中m＝1.5至4且x>y。
理论上，所有的氮原子都可以被氧原子取代。在一定浓度的氧之后，将失去极大选择性的吸收(即层损失有用的着色)，这导致系数y的值被限制，优选在y＝0和y＝2之间。
粘合层是可选的，并且在珍珠母上的涂层的特定情况下，粘合层不证明是必需的。根据基质1的性质，在为了改善基质1上的主层3的粘合而期望粘合层的情况下，通过真空沉积钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3之前可以进行等离子处理，或更特别地在氩和/或氧气下，特别是在纯氩气或纯氧气下等离子处理。
此外并且仍然可选地，可以在钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层之上和/或之下沉积透明或半透明的附加中间2层或上层4。
层的累积更多的是一种制造模式的结果，而不是一个有意的选择。
在根据本发明方法的特定顺序中，进行阴极溅射(优选)，或者通过离子束，Ti和Si的金属靶(但是也可以用期望比例的Ti/Si合金靶)，通过添加反应性气体(“反应性溅射”)。
其他可能的方法是：
-阴极溅射或通过离子束，基于(Ti,Sik)NxOy的陶瓷靶；
-通过加入反应性气体(“反应性蒸发”)，通过电子束，通过电弧或通过Ti和Si合金(优选TiSi2)的焦耳效应进行真空蒸发。
除了钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3之外，基质1还可以带有至少一个附加中间层2。该附加中间层2可以有几个功能。它可以用于促进钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3在基质1上的粘合。另一个功能可以是通过干涉效果调节反射颜色。为此，附加中间层2可以是单层的，或者由具有低折射率和高折射率的交替层的叠层形成，以获得期望的干涉效果，这些层中的一个或多个能够是吸收剂。
举例来说，特别是可以使用SiO2层：折射率1.46(低)和Si3N4层：折射率2(高)的叠层。优选地，层的厚度为在10nm和400nm之间选择每个层。这些层的折射率和厚度使得有可能控制干涉现象，即相长干涉和/或相消干涉的幅度和波长。
将会注意到，根据相同的干涉定律，钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3在叠层中类似地参与到其它层中。因此，可以使用钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3作为这些叠层的一部分，以产生额外的干涉效果。换句话说，可以产生(使用光学模拟软件)具有钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy以及具有低折射率和高折射率的层的叠层，其允许仅使用钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的层不能达到的光学性质。
根据本发明，附加中间层2的材料选自氮化物，氮氧化物和/或硅和/或金属氧化物，特别是选自以下金属：Ti，Al，Ta，Ce，Zr，Hf。
此外，涂层可以包括至少一个附加上层4，即沉积在与基质1的钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3相对的自由表面上的层。这个附加上层4同样可以实现一个或多个功能。它可以具有增加涂层的耐机械和化学性，赋予涂层光泽或无光泽外观和/或产生深度效果的功能。如附加中间层2的情况那样，它也可以具有通过干涉效果来调节颜色的功能。它可以是单层或多层(SiO2和Si3N4的交替层的叠层)，如对附加中间层2描述的那样，且同样地，由氮化物和/或各种材料的氧化物形成。
根据本发明，附加中间层2和附加上层4各自可以具有在20和2,000nm之间的厚度，如果沉积单层，则厚度是单层的厚度，或者如果沉积多层，则厚度是多层的厚度。
在制表和珠宝中，仍然存在在温暖和潮湿的环境中保持颜色的问题。为了解决这个问题，提出了层的叠层，特别是具有确定厚度的钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy和Al2O3的叠层，在恶劣的环境中可以抵抗变色的叠层。因此，为了保护部件免于在温暖或潮湿环境中变色，附加中间层2或上层4优选包括铝Al2O3层与至少一个钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3交替的叠层。
这种方法的一个特别有利的应用涉及这样的部件的情况，其中基质1由珍珠母制成。
本发明还涉及制表或珠宝外部部件，其包括珍珠母基质。
根据本发明，该部件包括在基质1上方的黄色涂层的至少一个表面，并且该涂层包括至少一个钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层3，优选根据后面进一步解释的制剂之一。
更特别地，基质1是刻度盘。
本发明还涉及包括至少一个这种制表或珠宝外部部件的手表。
本发明还涉及包括这种制表或珠宝外部部件的珠宝。
总的来说，根据本发明沉积在珍珠母基质上的黄色层具有几个优点：
-颜色是独立于视角的黄色。可以通过沉积干涉层并通过调节钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy或其组合物的层的厚度来调制该颜色的色调和强度。
-沉积之后，珍珠母的特定形态总是可见的。
-该层很好地粘附在基质上，由于等离子处理和干涉层的沉积，粘附力也能够得到改善。
-反射度低，与介电氧化物相当，以避免金属外观。
-涂层无毒。
-涂层相对于经涂覆制品的生产和使用条件(洗涤，贴花，处理等)是稳定的。
-涂层在不损害基质的条件下沉积。
-涂层具有化学稳定性，能够抵抗制表中内部零件的正常测试(紫外线，湿热，热冲击)。
总之，基于钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的本发明以称为“香槟”的色相产生黄色着色层，更具体地，金色光泽，该层非常耐久，尤其是耐磨，并且优于现有技术着色中已知的所有涂层。该层具有良好的透明性，并且被证明适用于高级制表或珠宝创作，以保护所考虑的部件和显示其优点。
Claims (14)
1.一种用于在包括预先在基质(1)上制备的至少一个可见表面的结构部件或者制表或珠宝外部部件上着色涂覆的方法，所述方法包括钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的至少一个主层(3)的至少一个真空沉积步骤(2)，其特征在于，在基质(1)与钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层(3)之间，和/或在钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层(3)的自由表面上沉积透明或半透明的附加中间层(2)和/或附加上层(4)，并且特征在于为了保护所述部件不在温暖或潮湿环境中变色，所述附加层(2,4)包括铝Al2O3层与钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的至少一个所述主层(3)交替的叠层，其中所述钛和硅氮化物(Ti,Sik)Nx或所述掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy具有1.5和4.0之间的系数k(比Si/Ti)以赋予所述主层(3)黄色，钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的所述至少一个主层(3)具有在3.00和6.33之间的系数x，钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的所述至少一个主层(3)具有在0.0和2.0之间的系数y。
2.如权利要求1所述的方法，其特征在于钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的所述至少一个主层(3)具有20纳米和2,000纳米之间的厚度。
3.如权利要求2所述的方法，其特征在于，钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的所述至少一个主层(3)具有30纳米和300纳米之间的厚度。
4.如权利要求1所述的方法，其特征在于，所述钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy还掺杂锂以使颜色饱和。
5.如权利要求1所述的方法，其特征在于在钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层(3)的真空沉积之前等离子处理以改善所述主层(3)在基质(1)上的结合。
6.如权利要求5所述的方法，其特征在于在钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的主层(3)的真空沉积之前在氩气和/或氧气下等离子处理来改善所述主层(3)在基质(1)上的结合。
7.如权利要求1所述的方法，其特征在于所述附加中间层(2)和/或所述附加上层(4)由单层或层的叠层形成。
8.如权利要求7所述的方法，其中所述附加层(2,4)由具有给定折射率的层和具有大于给定折射率的折射率的层交替的层的叠层形成以产生干涉效果。
9.如权利要求1所述的方法，其特征在于，所述附加层(2,4)由氮化物、氧氮化物和/或金属氧化物或硅组成。
10.如权利要求9所述的方法，其中氧化物和氮化物的金属选自钛、钽、铝、锆、铪和铈。
11.如权利要求1所述的方法，其特征在于所述方法应用于所述部件，所述部件的基质(1)由珍珠母制成。
12.制表或珠宝结构部件，包括珍珠母基质(1)，其特征在于所述部件具有在所述基质(1)上方具有黄色涂层的至少一个表面，并且包括钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的至少一个主层(3)。
13.制表或珠宝外部部件，包括珍珠母基质(1)，其特征在于所述部件具有在所述基质(1)上方具有黄色涂层的至少一个表面，并且包括钛和硅氮化物(Ti,Sik)Nx或掺杂有氧的钛和硅氮化物(Ti,Sik)NxOy的至少一个主层(3)。
14.如权利要求13所述的制表或珠宝外部部件，其特征在于，所述基质(1)是刻度盘。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16206568.4A EP3339983B1 (fr) | 2016-12-23 | 2016-12-23 | Substrat en nacre revêtu d'une couche jaune |
| EP16206568.4 | 2016-12-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108239747A CN108239747A (zh) | 2018-07-03 |
| CN108239747B true CN108239747B (zh) | 2020-04-03 |
Family
ID=57590426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711390750.4A Active CN108239747B (zh) | 2016-12-23 | 2017-12-21 | 涂覆有黄色层的珍珠母基质 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US11022945B2 (zh) |
| EP (1) | EP3339983B1 (zh) |
| JP (1) | JP6499264B2 (zh) |
| CN (1) | CN108239747B (zh) |
| CH (1) | CH713310B1 (zh) |
| HK (1) | HK1256650A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108375892B (zh) * | 2017-01-30 | 2022-02-01 | 精工爱普生株式会社 | 钟表用部件以及钟表 |
| CN108375893A (zh) * | 2017-01-30 | 2018-08-07 | 精工爱普生株式会社 | 钟表用部件以及钟表 |
| CN108375894A (zh) * | 2017-01-30 | 2018-08-07 | 精工爱普生株式会社 | 钟表用部件以及钟表 |
| EP3764167A1 (fr) * | 2019-07-10 | 2021-01-13 | Patek Philippe SA Genève | Procede d'obtention d'un composant horloger dont la surface est au moins partiellement revêtue d'une couche coloree |
| EP4001458A1 (fr) * | 2020-11-17 | 2022-05-25 | The Swatch Group Research and Development Ltd | Procede de depot d'un revetement sur un article, tel qu'un composant horloger et article revetu par un tel procede |
| EP4060386A1 (fr) * | 2021-03-18 | 2022-09-21 | Omega SA | Pièce d'habillage d'horlogerie ou de bijouterie comprenant un revêtement de couleur interférentielle et procédé de fabrication de ladite pièce |
| EP4079713A1 (fr) * | 2021-04-21 | 2022-10-26 | Comadur S.A. | Procédé de réalisation d'une pièce en céramique à effet nacré, notamment pour l'horlogerie |
| CN114032502B (zh) * | 2021-11-23 | 2022-05-03 | 江西省科学院应用物理研究所 | 一种耐磨耐蚀复合层及其制备方法 |
| EP4184255A1 (fr) * | 2021-11-23 | 2023-05-24 | The Swatch Group Research and Development Ltd | Boîte de montre comprenant un composant d'habillage sur lequel est déposé un empilement de couches minces |
| CN114635115B (zh) * | 2022-03-21 | 2023-03-31 | 山东大学 | 一种与润滑油摩擦改性添加剂强协同作用的减摩耐磨涂层 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2825513C2 (zh) * | 1977-06-10 | 1987-04-09 | Citizen Watch Co., Ltd., Tokio/Tokyo, Jp | |
| EP0353060A2 (en) * | 1988-07-28 | 1990-01-31 | Nippon Steel Corporation | Multi ceramic layer-coated metal plate and process for manufacturing same |
| WO2005122820A1 (ja) * | 2004-06-15 | 2005-12-29 | Phild Co., Ltd. | シリコーンエラストマーを用いた健康装身具とその製造方法 |
| EP1672436A1 (fr) * | 2004-12-20 | 2006-06-21 | Rolex S.A. | Cadran pour pièce d'horlogerie et procédés de fabrication de ce cadran |
| EP1888809A2 (en) * | 2005-05-25 | 2008-02-20 | Istituto Nazionale Di Fisica Nucleare (INFN) | Process for production of jewels |
| JP2009213616A (ja) * | 2008-03-10 | 2009-09-24 | Citizen Holdings Co Ltd | 装飾部品 |
| EP2135972A1 (en) * | 2007-03-02 | 2009-12-23 | Citizen Tohoku Co., Ltd. | Gold alloy coating, gold alloy coating clad laminate and gold alloy coating clad member |
| CN103572207A (zh) * | 2012-08-03 | 2014-02-12 | 深圳富泰宏精密工业有限公司 | 镀膜件及其制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54148182A (en) * | 1978-05-13 | 1979-11-20 | Tsuneo Nishida | Golddcolor outer decorating part and its manufacture |
| JPS5690971A (en) * | 1979-12-25 | 1981-07-23 | Glory:Kk | Watch case and band having hard film and their production |
| JP2003322330A (ja) * | 2002-04-30 | 2003-11-14 | Nippon Electric Glass Co Ltd | 燃焼装置窓用材料 |
| DE102012109254A1 (de) * | 2012-09-28 | 2014-04-03 | Walter Ag | Werkzeug mit TiAlCrSiN-PVD-Beschichtung |
-
2016
- 2016-12-23 CH CH01719/16A patent/CH713310B1/fr unknown
- 2016-12-23 EP EP16206568.4A patent/EP3339983B1/fr active Active
-
2017
- 2017-12-05 US US15/831,453 patent/US11022945B2/en active Active
- 2017-12-13 JP JP2017238317A patent/JP6499264B2/ja active Active
- 2017-12-21 CN CN201711390750.4A patent/CN108239747B/zh active Active
-
2018
- 2018-12-10 HK HK18115805.3A patent/HK1256650A1/zh unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2825513C2 (zh) * | 1977-06-10 | 1987-04-09 | Citizen Watch Co., Ltd., Tokio/Tokyo, Jp | |
| EP0353060A2 (en) * | 1988-07-28 | 1990-01-31 | Nippon Steel Corporation | Multi ceramic layer-coated metal plate and process for manufacturing same |
| WO2005122820A1 (ja) * | 2004-06-15 | 2005-12-29 | Phild Co., Ltd. | シリコーンエラストマーを用いた健康装身具とその製造方法 |
| EP1672436A1 (fr) * | 2004-12-20 | 2006-06-21 | Rolex S.A. | Cadran pour pièce d'horlogerie et procédés de fabrication de ce cadran |
| EP1888809A2 (en) * | 2005-05-25 | 2008-02-20 | Istituto Nazionale Di Fisica Nucleare (INFN) | Process for production of jewels |
| EP2135972A1 (en) * | 2007-03-02 | 2009-12-23 | Citizen Tohoku Co., Ltd. | Gold alloy coating, gold alloy coating clad laminate and gold alloy coating clad member |
| JP2009213616A (ja) * | 2008-03-10 | 2009-09-24 | Citizen Holdings Co Ltd | 装飾部品 |
| CN103572207A (zh) * | 2012-08-03 | 2014-02-12 | 深圳富泰宏精密工业有限公司 | 镀膜件及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018104814A (ja) | 2018-07-05 |
| CH713310B1 (fr) | 2020-08-14 |
| JP6499264B2 (ja) | 2019-04-10 |
| EP3339983A1 (fr) | 2018-06-27 |
| US20180181071A1 (en) | 2018-06-28 |
| EP3339983B1 (fr) | 2020-07-01 |
| HK1256650A1 (zh) | 2019-09-27 |
| CH713310A2 (fr) | 2018-06-29 |
| CN108239747A (zh) | 2018-07-03 |
| US11022945B2 (en) | 2021-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108239747B (zh) | 涂覆有黄色层的珍珠母基质 | |
| JPH0397865A (ja) | セラミックスコーティング金属板 | |
| FR2497833A1 (zh) | ||
| JP7297031B2 (ja) | 時計仕掛けの構成要素などのアイテムにコーティングを堆積するための方法、およびそのような方法によってコーティングされたアイテム | |
| JP2010228307A (ja) | 装飾部材 | |
| JPS6362867A (ja) | 有色物品 | |
| JP7051885B2 (ja) | 干渉顔料 | |
| CN102427938A (zh) | 涂覆铝合金部件的方法以及由该方法获得的部件 | |
| CN206791844U (zh) | 首饰或钟表的零件 | |
| JP2022008477A (ja) | 時計用部品および時計 | |
| CN111663100B (zh) | 一种不锈钢基材的装饰性涂层 | |
| CN102046394B (zh) | 装饰用基材,特别是具有颜色效果的人造首饰石,和用于获得装饰用透明基材的颜色效果的方法 | |
| KR102640464B1 (ko) | 간섭 컬러 코팅을 포함하는 타임피스 또는 보석류의 피스용 외부 부품 및 상기 부품의 제조 방법 | |
| CN108375893A (zh) | 钟表用部件以及钟表 | |
| JP2023538281A (ja) | 黒色構成要素およびその製造方法 | |
| JP6950474B2 (ja) | 時計用部品および時計 | |
| CN113549872B (zh) | 黑色涂层 | |
| JPH0387352A (ja) | 透明保護膜形成方法およびその物品 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1256650 Country of ref document: HK |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |