CN101160418A - Golden ornament and its manufacturing method - Google Patents
Golden ornament and its manufacturing method Download PDFInfo
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- CN101160418A CN101160418A CN200680010467.8A CN200680010467A CN101160418A CN 101160418 A CN101160418 A CN 101160418A CN 200680010467 A CN200680010467 A CN 200680010467A CN 101160418 A CN101160418 A CN 101160418A
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000004429 atom Chemical group 0.000 claims abstract description 245
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 185
- 229910052737 gold Inorganic materials 0.000 claims abstract description 127
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 108
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 96
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 40
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 161
- 239000010931 gold Substances 0.000 claims description 155
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 76
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 76
- 230000008020 evaporation Effects 0.000 claims description 60
- 238000001704 evaporation Methods 0.000 claims description 60
- 238000002156 mixing Methods 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 230000015572 biosynthetic process Effects 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 27
- 230000008676 import Effects 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 38
- 238000000576 coating method Methods 0.000 abstract description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 68
- 239000007789 gas Substances 0.000 description 68
- 238000012360 testing method Methods 0.000 description 39
- 229910052786 argon Inorganic materials 0.000 description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 238000005299 abrasion Methods 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 14
- 238000007747 plating Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000006378 damage Effects 0.000 description 8
- 238000007733 ion plating Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 150000001485 argon Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910002710 Au-Pd Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 150000002829 nitrogen Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- -1 atoms metals Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000003353 gold alloy Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
A golden ornament comprising a base material; a Ti coating whose Ti atom content is constant in the direction of coating thickness, formed on the base material in an atmosphere of inert gas other than nitrogen; a TiN gradient coating whose N atom content is sloped in the direction of coating thickness, formed on the Ti coating; a TiN coating whose Ti atom and N atom contents are constant in the direction of coating thickness, formed on the TiN gradient coating; an Au-TiN mixture gradient coating whose Au atom content is sloped in the direction of coating thickness, formed on the TiN coating; and an Au-TiN mixture coating whose Au atom, Ti atom and N atom contents are constant in the direction of coating thickness, formed on the Au-TiN mixture coating. Further, on this Au-TiN mixture coating, there may be formed an Au coating or Au alloy coating whose Au atom content is constant in the direction of coating thickness.
Description
Technical field
The present invention relates to golden decorative part and manufacture method thereof.
Background technology
Extraneous adornment articles for use such as clock and watch, jewellery are required to have simultaneously as the wear resistant of the color harmony of decorating key element as functional imperative.Gold is suitable for this requirement most, raw material is directly processed, or the gold-plated coating of formation uses on other metal all the time.When solidity to corrosion is not had special requirement, even showing that the coating below 1 micron also can achieve the goal on the golden meaning, yet for Watchcase or band, jewellery, require sweat, water vapour etc. is had the patience of height, therefore the gold-plated thickness that has at least more than 10 microns.
But gold is very expensive metal, therefore can adopt the extraneous adornment articles for use of the golden coating of thick film to be restricted.Therefore need to obtain to have reduced the coating of golden usage quantity.But the hardness of gold is that scoring resistance is bad about 200Hv, and there are the problem of scraping damage easily in wrist-watch, jewellery when wearing.Therefore, wish to develop more cheap and bring into play the golden coating of abundant function.
Therefore, proposed to utilize dry type coating technologies such as ion plating or sputter to form the coating (for example, referring to Patent Document 1～3) that forms by titanium nitride and gold or au-alloy, to form solidity to corrosion and wear resistant is good, thickness thin, cheap coating metal.But, should compare with gold-plated coating in the past by the coating that titanium nitride and gold or au-alloy form, though improved adherence with the bottoming metal level that is formed by titanium, titanium nitride etc., this adherence still has the leeway of improvement.If particularly then there is the problem of peeling off easily in the thickness of the coating that is formed by titanium nitride and gold or au-alloy as thin as a wafer.
In addition, having proposed coating metal layer as the good coating metal layer of scoring resistance, wear resistant is titanium nitride layer and the extraneous adornment articles for use (with reference to patent documentation 1 and 2) of gold layer or the two-layer formation of gold alloy layer.But this gold coating is because titanium nitride layer and gold layer or the tone of gold alloy layer are different, if thereby surface abrasion or scratch then this part can be very showy.
Patent documentation 1: the Japanese Patent spy opens clear 54-2942 communique
Patent documentation 2: the Japanese Patent spy opens clear 58-104176 communique
Patent documentation 3: the Japanese Patent spy opens clear 60-67654 communique
Summary of the invention
The objective of the invention is to, solve the problem follow above-mentioned conventional art, provide to have more cheap and bring into play the ornament and the manufacture method thereof of the coating metal layer of abundant function.
The manufacture method of the golden decorative part that the present invention relates to is characterised in that, surface at base material, in the dry type plater, under the inert gas atmosphere except that nitrogen, make titanium with the evaporation of the certain state of the steam output of its time per unit, form Ti film (coating film);
Then, in this dry type plater, make titanium with the certain state evaporation of the steam output of its time per unit, simultaneously in this dry type plater, import nitrogen so that the nitrogen amount in this dry type plater through the time increase, above-mentioned Ti is filmed go up to form the N atom content and the TiN of gradient tilt to film (gradient coating film) is arranged at film thickness direction;
Follow, in this dry type plater, titanium is evaporated with the certain state of the steam output of its time per unit, make the interior nitrogen amount of this dry type plater keep certain simultaneously, formation TiN films to make above-mentioned TiN tilt to film upward;
Then, in this dry type plater, make titanium with the certain state evaporation of the steam output of its time per unit, and make the nitrogen amount in this dry type plater keep certain, simultaneously with the steam output of the gold of time per unit through the time state that increases make gold or gold and other evaporation of metal, above-mentioned TiN is filmed go up to form the Au atom content and on film thickness direction, have the Au-TiN of gradient to mix to tilt to film;
Again then, make the nitrogen amount in this dry type plater keep certain, make titanium and gold in this dry type plater, perhaps titanium, gold and other metal evaporate with the certain state of the steam output of their time per units, make above-mentioned Au-TiN mixing tilt to film to go up formation Au-TiN mixing and film.
Preferably, form above-mentioned Au-TiN mix film after, stop the evaporation of the titanium in the above-mentioned dry type plater, and stop in this dry type plater for nitrogen, make gold or gold and the evaporation of metal except that gold and titanium in this dry type plater, above-mentioned Au-TiN mixing is filmed, and the last Au of formation films or the Au alloy is filmed.
Mix when tilting to film forming Au-TiN, preferably make time per unit gold steam output through the time increase so that the Au atom content that this Au-TiN mixes in tilting to film increases at film thickness direction with the ratio of 2～10 atom %/0.001 μ m.
Form Au-TiN and mix when tilting to film, 2.5 times of nitrogen more than the amount of the nitrogen feed rate when preferably supply TiN films formation in the dry type plater.
Form Au-TiN and mix when filming, 2.5 times of nitrogen more than the amount of the nitrogen feed rate when preferably supply TiN films formation in the dry type plater.
When forming TiN and tilting to film, preferably make in this dry type plater the nitrogen amount through the time increase so that the N atom content of this TiN in tilting to film increases on film thickness direction with the ratio of 4～12 atom %/0.1 μ m.
Au-TiN mix film in and Au-TiN mix in filming the Au atom preferably with the atoms metal formation alloy that removes gold and the titanium, on this Au-TiN mixing is filmed, be formed with the Au alloy and film.
The golden decorative part that the present invention relates to has base material; Form under the inert gas atmosphere outside the nitrogen at this substrate surface, Ti atom content certain Ti on film thickness direction films; Form on this Ti films, the N atom content has gradient on film thickness direction TiN tilts to film; Form on this TiN tilts to film, Ti atom and N atom content certain TiN on film thickness direction films; Form on this TiN films, the Au atom content has the Au-TiN of gradient to mix to tilt to film on film thickness direction; Form on this Au-TiN mixing tilts to film, the certain Au-TiN mixing on film thickness direction of Au atom, Ti atom and N atom content is filmed.
Preferred above-mentioned Au-TiN mixes and also has that Au atom content certain Au on film thickness direction films or the Au alloy is filmed on filming.
In the Au-TiN mixing tilted to film, the Au atom content was preferably mixed the film thickness direction of filming along filming from TiN to Au-TiN and is increased.
In the Au-TiN mixing that does not contain the atoms metal except that gold and titanium tilted to film, the Au atom content preferably increased with the ratio of 2～10 atom %/0.001 μ m.
Preferably, Au atom and the atoms metal except that gold and titanium form alloy in the Au-TiN mixing tilts to film, and the total content of Au atom and the atoms metal except that gold and titanium is with the ratio increase of 2～10 atom %/0.001 μ m.
Preferably, the Au atom that Au-TiN mixes in filming forms alloy with the atoms metal that removes gold and the titanium, and this Au-TiN mixes the formation Au alloy of filming upward and films.
In TiN tilted to film, preferably the N atom content increased along the film thickness direction of filming to TiN of filming from Ti.
In TiN tilted to film, the N atom content preferably increased with the ratio of 4～12 atom %/0.1 μ m.
First golden decorative part of the present invention preferably, the thickness that Ti films is 0.1～0.5 μ m, TiN tilts to film and total thickness that TiN films is 0.5～2.0 μ m, and the ratio of the thickness of filming with respect to the TiN inclination of this totals thickness is in 10～60% scope;
Preferably, Au-TiN mixes to film, and to mix the total thickness of filming with Au-TiN be 0.005～0.1 μ m, and Au-TiN mix thickness that inclination films with respect to the ratio of this total thickness in 10～90% scope.
In addition, second golden decorative part that the present invention relates to is preferably, and the thickness that Ti films is 0.1～0.5 μ m; The TiN total thickness of filming with TiN that tilts to film is 0.5～2.0 μ m, and the TiN thickness that tilts to film with respect to the ratio of this total thickness in 10～60% scope; Au-TiN mixes to film, and to mix the total thickness of filming with Au-TiN be 0.005～0.1 μ m, and Au-TiN mix thickness that inclination films with respect to the ratio of this total thickness in 10～90% scope; The thickness that Au films or the Au alloy is filmed is 0.005～0.1 μ m.
The adherence each other that respectively is coated with rete of first golden decorative part that the present invention relates to is good and mix the surface hardness height of filming, have solidity to corrosion, wear resistant and scoring resistance as outermost Au-TiN.Particularly because Au-TiN mixes to film Au-TiN mixed films and TiN films that this two films and shown good adherence, therefore, even mixing, Au-TiN tilts to film as thin as a wafer, peeling off that wearing away, fraying and film also appears in the surface of golden decorative part hardly.Therefore, the usage quantity of gold can be reduced, cheap golden decorative part can be obtained.
In addition, second golden decorative part that the present invention relates to is to form the ornament that Au films or the Au alloy is filmed again on the Au-TiN of above-mentioned first golden decorative part mixing is filmed, it is good respectively to be coated with rete adherence each other, and it is thin as the thickness that outermost Au films and the Au alloy is filmed, even therefore these abrasion of filming, scratch, tone can not change substantially yet.In addition, the lower floor that Au films or the Au alloy is filmed is the surface hardness height, and the Au-TiN with solidity to corrosion, wear resistant and scoring resistance mixes and to film, even therefore Au films, the Au alloy is filmed, and abrasion, scratch bigger abrasion, scratch can not occur yet.Moreover, because mixing to film Au-TiN mixed, Au-TiN films and TiN films that this two films and demonstrate good adherence, even therefore the Au-TiN mixing is filmed as thin as a wafer, can not occur Au-TiN yet and mix peeling off of filming, can be with the abrasion of golden decorative part, fraying is limited in Au-TiN and mixes and film.Therefore golden tone, the usage quantity that can reduce gold, cheap golden decorative part can be maintained.
In addition, by the manufacture method of the golden decorative part that the present invention relates to, can make this golden decorative part.
Description of drawings
Fig. 1: the floor map of wear testing machine that is used to illustrate the method for wear test.
The compositional analysis result's who films at film thickness direction of the Housing for a meter that Fig. 2: embodiment 1 makes diagrammatic sketch.
The diagrammatic sketch of the measurement result of the surface albedo under the wavelength 400～700nm of the Housing for a meter that makes among Fig. 3: embodiment 1 and the embodiment 3.
The compositional analysis result's who films at film thickness direction of the Housing for a meter that Fig. 4: embodiment 3 makes diagrammatic sketch.
The explanation of symbol
1 test film
2 test film pressing plates
3 test film thrust screws
4 test film treatment benches
5 emery wheels
Embodiment
Below, golden decorative part and the manufacture method thereof that the present invention relates to specifically described.
First golden decorative part that the present invention relates to can followingly make, forming Ti by the dry type plating method on the surface of base material films, forming TiN on this Ti films tilts to film, forming TiN on this TiN tilts to film films, on this TiN films, form the Au-TiN mixing and tilt to film, on this Au-TiN mixing tilts to film, form the Au-TiN mixing and film.
In addition, second golden decorative part that the present invention relates to can followingly make, and mixes forming that Au films or the Au alloy is filmed on filming at above-mentioned Au-TiN by the dry type plating method.
Dry type plating method as using in the present invention can exemplify as vacuum vapour deposition, sputtering method, ion plating method etc.Wherein preferably use ion plating method.
Below, describe the formation method of respectively filming in detail.
(1) the Ti formation of filming
At first, base material is placed in the dry type plater, after exhaust in the dry type plater, imports the rare gas element except that nitrogen.Then, making titanium under this inert gas atmosphere necessarily is constant evaporation with the steam output of the titanium of time per unit, forms Ti by the dry type plating method on the surface of base material and films.At this moment, the steam output of the titanium of time per unit preferably set the film forming speed that becomes to make Ti to film be preferably 0.005～0.05 μ m/ minute, more preferably 0.01～0.03 μ m/ minute.
At this moment, after being vented to common 5～0.1mPa in the dry type plater, being preferably 1～0.1mPa, the rare gas element of importing except that nitrogen is until 0.01 common～1.0Pa, preferably to 0.1～0.5Pa.As this rare gas element except that nitrogen, can exemplify as argon gas, helium, neon etc.Preferably make the exhaust pressure in the dry type plater low as far as possible, like this, can fully reduce the residual quantity of the inevitable composition (nitrogen, oxygen, carbon) of device inside, can obtain the high Ti of purity and film.
In addition, as the material of base material, can exemplify as stainless steel, titanium, titanium alloy, copper, copper alloy, wolfram varbide, pottery etc.This base material is placed on before the dry type plater, preferably with organic solvent with its surface clean, degreasing.
The Ti of the Xing Chenging Ti atom content of filming is roughly certain on film thickness direction like this.During this Ti films can be preferably 0.5～20 atom %, more preferably 0.5～12 atom %, the content that is preferably 0.5～5 atom % especially contain at least a kind of inevitable composition that forms by nitrogen, oxygen, carbon.At this moment, the Ti atom content is preferably 80～99.5 atom %, 88～99.5 atom % more preferably, 95～99.5 atom % more preferably again.
In addition, in above-mentioned Ti films, the content of Ti atom and inevitable composition add up to 100 atom %.
(2) the TiN formation of tilting and to film
Then above-mentioned (1) makes the constant evaporation of titanium keep the Ti nucleidic mass in the dry type plater certain, imports nitrogen simultaneously in this dry type plater.From the importing of this nitrogen, the nitrogen amount in the dry type plater, promptly the N nucleidic mass through the time increase.With the N nucleidic mass through the time state that increases, form on above-mentioned Ti films by the dry type plating method and to contain filming of Ti and N.N atom of filming of Xing Chenging and Ti atom content have gradient (below, this is filmed is called " TiN tilts to film ") on the film thickness direction like this.
At this moment, preferably through the time increase in the dry type plater the nitrogen amount so that the N atom content of the TiN that forms in tilting to film be preferably 4～12 atom %/0.1 μ m, more preferably 6～10 atom %/0.1 μ m, more preferably the ratio of 7～9 atom %/0.1 μ m increases on film thickness direction again.
For example, the mixed gas that uses rare gas elementes such as nitrogen and argon gas when importing gas, ratio that can be by making the nitrogen in the mixed gas through the time increase make in the dry type plater the nitrogen amount through the time increase.Can wait the importing condition of suitably selecting nitrogen to tilt to film according to dry type plater, plating condition with the TiN that formation has above-mentioned amount gradient.For example, the throughput ratio (nitrogen/rare gas element) that makes nitrogen and rare gas element is since 0, increases in preferred 1.5～3.0 the scope in preferred 10～60 minutes, more preferably 20～40 minutes, more preferably in 1.8～2.5 the scope.
The steam output of the titanium of time per unit preferably set the film forming speed that becomes to make TiN to tilt to film be preferably 0.005～0.05 μ m/ minute, more preferably 0.01～0.03 μ m/ minute.For example, preferably under the condition that the steam output of the titanium of the time per unit with formation that above-mentioned Ti films the time is identical, make the titanium evaporation.
Preferably, the amount of N atom increased along the film thickness direction of filming to TiN of filming from Ti during the TiN that forms tilted to film like this, the film thickness direction minimizing that the Ti atom content is filmed and filmed to TiN along Ti.Specifically, preferably with the ratio of above-mentioned scope, the film thickness direction of filming to TiN increases the N atom content along filming from Ti.In addition, preferably the Ti atom content with preferred 4～12 atom %/0.1 μ m, more preferably 6～10 atom %/0.1 μ m, more preferably the ratio of 7～9 atom %/0.1 μ m reduces along the Ti film thickness direction of filming to TiN of filming again.
The TiN that N atom and Ti atom increase with aforementioned proportion or reduce tilt to film film with Ti and TiN this two adherence of filming of filming good.
Can be during this TiN tilts to film with preferred 0.5～20 atom %, more preferably the ratio of 0.5～12 atom %, preferred especially 0.5～5 atom % contains the inevitable composition that forms by at least a kind in oxygen, the carbon.
In addition, during above-mentioned TiN tilts to film, the content of Ti atom, N atom and inevitable composition add up to 100 atom %.
(3) the TiN formation of filming
Then above-mentioned (2), supplying with nitrogen in the dry type plater consistently makes the nitrogen amount in this dry type plater keep certain, make the constant evaporation of titanium simultaneously so that the Ti nucleidic mass in this dry type plater is certain, on above-mentioned TiN tilts to film, form TiN by the dry type plating method and film.
At this moment, make nitrogen amount in the dry type plater keep certain so that TiN that forms N atom content in filming be preferably 10～60 atom %, more preferably 20～50 atom %, be preferably 30～45 atom % especially.At this moment, can suitably select to supply to the nitrogen amount in the dry type plater so that the nitrogen amount in the dry type plater keeps certain according to dry type plater, plating condition.
For example, when the mixed gas that uses rare gas elementes such as nitrogen and argon gas when importing gas, preferably the throughput ratio (nitrogen/rare gas element) with nitrogen and rare gas element keeps certain in preferred 1.5～3.0, more preferably 1.8～2.5 scope.
The steam output of the titanium of time per unit preferably set the film forming speed that becomes to make TiN to film be preferably 0.005～0.05 μ m/ minute, more preferably 0.01～0.03 μ m/ minute.For example, preferably under the condition that the steam output of the titanium of the time per unit with formation that above-mentioned Ti films the time is identical, make the titanium evaporation.
Ti atom and N atom content were almost certain on film thickness direction during the TiN of Xing Chenging filmed like this.The N atom content is in above-mentioned scope, the Ti atom content be preferably 30～80 atom %, more preferably 40～70 atom %, be preferably 45～60 atom % especially.
In addition, can be during this TiN films with preferred 0.5～20 atom %, more preferably 0.5～12 atom %, the amount that is preferably 0.5～5 atom % especially contain the inevitable composition that forms by at least a kind in oxygen, the carbon.
In addition, during above-mentioned TiN films, the content of Ti atom, N atom and inevitable composition add up to 100 atom %.
(4) Au-TiN mixes the formation of tilting to film
Then above-mentioned (3), constant supply nitrogen in above-mentioned dry type plater keeps the nitrogen amount in this dry type plater certain, makes the constant evaporation of titanium simultaneously so that the Ti nucleidic mass in this dry type plater keeps certain.At this moment, preferably supply with nitrogen with following nitrogen feed rate in the dry type plater, this nitrogen feed rate is preferably above-mentioned TiN film 2.5 times of the nitrogen feed rate supplied with when forming more than the amount, more preferably 2.8 times more than the amount in the dry type plater.By making nitrogen feed rate such as above-mentioned increase, maintenance, can form the ornament that presents more golden form and aspect.
The steam output of the titanium of time per unit preferably set into Au-TiN mix the film forming speed of filming be preferably 0.005～0.05 μ m/ minute, more preferably 0.01～0.03 μ m/ minute.For example, preferably under the condition that the steam output of the titanium of the time per unit with formation that above-mentioned Ti films the time is identical, make the titanium evaporation.
Keep above-mentioned state, simultaneously with the steam output of the gold of time per unit through the time state that increases make gold, perhaps gold with remove metal gold and the titanium (below, be called " other metals ") evaporation, importing Au atom or Au atom and other atoms metal in this dry type plater.Then, make time per unit gold steam output through the time increase, form on above-mentioned TiN films by the dry type plating method simultaneously and contain filming of Ti, N and Au and other metal as required.By as the steam output of the above-mentioned gold that makes time per unit through the time increase, the evaporation amount of the gold of time per unit through the time increase, can form the inclination film that the amount of gold increases at the film growth direction.Filming of forming like this has the Ti atom, the amount of N atom, Au atom and other atoms metal is the gradient of film thickness direction (below, film be called " Au-TiN mixes to tilt to film " with this).
At this moment, when mixing, the Au-TiN that forms tilts to film when not containing other atoms metal, preferably make time per unit gold steam output through the time increase so that the amount of the Au atom of this inclination in filming be preferably 2～10 atom %/0.001 μ m, more preferably 4～9 atom %/0.001 μ m, the ratio that is preferably 6～8 atom %/0.001 μ m especially increase at film thickness direction.On the other hand, the Au-TiN that forms mixes to tilt to film when containing other atoms metal, the steam output of the gold of per unit is increased so that this inclination in filming the Au atom and the total amount of other atom be preferably 2～10 atom %/0.001 μ m, more preferably 4～9 atom %/0.001 μ m, the ratio that is preferably 6～8 atom %/0.001 μ m especially increase at film thickness direction.
For example, formed the Au-TiN do not contain other metal with film forming speed 0.02 μ m/ minute and mix the situation that tilts to film if be scaled, then preferably make gold evaporation so that the amount of the Au atom in whole atoms of time per unit evaporation with 1 second preferred 0.6～3.4 atom %, more preferably 1.3～3.0 atom %, the ratio that is preferably 2.0～2.7 atom % especially increase.Equally, be scaled when forming the Au-TiN contain other metal in film forming speed 0.02 μ m/ minute and mix the situation that tilts to film, preferably make gold and other evaporation of metal so that the total amount of the Au atom in whole atoms of time per unit evaporation and other atoms metal with 1 second preferred 0.6～3.4 atom %, more preferably 1.3～3.0 atom %, the ratio that is preferably 2.0～2.7 atom % especially increase.
The Au-TiN that forms mixes to tilt to film preferably like this, the total content of Au atom content or Au and other atoms metal mixes the film thickness direction of filming along filming from TiN to Au-TiN and increases, and Ti atom and N atom content are mixed the film thickness direction of filming along filming from TiN to Au-TiN and reduced.Specifically, Au atom content or Au atom preferably mix the film thickness direction increase of filming along filming from TiN to Au-TiN with the ratio of above-mentioned scope with the total content of other atoms metal.In addition, preferably, the Ti atom content is with preferred 1～10 atom %/0.001 μ m, more preferably 2～8 atom %/0.001 μ m, the ratio that is preferably 3～5 atom %/0.001 μ m are especially mixed the film thickness direction of filming along filming from TiN to Au-TiN and reduced.In addition, preferably the N atom content with preferred 1～10 atom %/0.001 μ m, more preferably 2～8 atom %/0.001 μ m, the ratio that is preferably 4～6 atom %/0.001 μ m are especially mixed the film thickness direction of filming along filming from TiN to Au-TiN and are reduced.
The Au-TiN that Au atom, Ti atom and N atom increase with aforementioned proportion or reduce mix tilt to film film with TiN and Au-TiN to mix this two adherence of filming of filming good.
This Au-TiN mixes to tilt to film when containing other atoms metal, and preferably Au atom and other atoms metal form au-alloy.Can exemplify as germanium, silicon, silver, copper, palladium, nickel, iron, platinum, niobium, chromium etc. as other atoms metal.The content of other atoms metals be preferably 1～20 atom %, more preferably 3～15 atom %, be preferably 5～10 atom % especially.
In addition, can be during Au-TiN mixes to film with preferred 0.5～20 atom %, more preferably 0.5～12 atom %, the amount that is preferably 0.5～5 atom % especially contain the inevitable composition that forms by at least a kind in oxygen, the carbon.
In addition, above-mentioned Au-TiN mixes to tilt to film, the content of Ti atom, Au atom, other atoms metal, N atom and inevitable composition add up to 100 atom %.
(5) Au-TiN mixes the formation of filming
Then above-mentioned (4), constant supply nitrogen makes the nitrogen amount in this dry type plater keep certain in the dry type plater, make titanium and gold simultaneously, perhaps titanium, gold and the constant evaporation of other metal form the Au-TiN mixing by the dry type plating method and film so that Ti nucleidic mass and Au nucleidic mass in this dry type plater are certain on above-mentioned Au-TiN mixing tilts to film.
At this moment, the nitrogen amount in the dry type plater is kept certain so that Au-Ti that forms mix N atom content in filming be preferably 5～50 atom %, more preferably 15～40 atom %, be preferably 20～30 atom % especially.At this moment, preferably in the dry type plater, supply with nitrogen with following nitrogen feed rate, this nitrogen feed rate is mixed when tilting to film formation same with above-mentioned Au-TiN, be preferably above-mentioned TiN and film 2.5 times of the nitrogen feed rate in the dry type plater, supplied with when forming more than the amount, more preferably 2.8 times more than the amount.Increase, keep as the above-mentioned nitrogen feed rate that makes, can obtain presenting the ornament of more golden form and aspect.The nitrogen amount of supplying with in the dry type plater is identical in the time of can filming formation with above-mentioned TiN, suitably selects so that the nitrogen amount in the dry type plater is kept certain according to dry type plater, plating condition.
The steam output of the titanium of time per unit preferably sets that the film forming speed that becomes to make Au-TiN to mix to film is preferably 0.005～0.05 μ m/ minute, 0.01～0.03 μ m more preferably.For example, make the titanium evaporation under the condition that preferably steam output of the titanium of the time per unit when filming formation with above-mentioned Ti is identical.
Make the steam output of the gold of time per unit keep certain, and make the Au-TiN of formation mix Au atom content in filming be preferably 10～60 atom %, more preferably 20～55 atom %, be preferably 25～45 atom % especially.
The Au-TiN that forms like this mix Au atom, Ti in filming former give and the N atom content almost certain on film thickness direction.Au atom and N atom content in above-mentioned scope, the Ti atom content be preferably 10～60 atom %, more preferably 20～50 atom %, be preferably 30～45 atom % especially.
Film when containing other atoms metals if this Au-TiN mixes, preferred Au atom forms with other atoms metal and forms au-alloy.As other atoms metal, can exemplify as germanium, silicon, silver, copper, palladium, nickel, iron, platinum, niobium, chromium etc.The content of other atoms metal be preferably 1～20 atom %, more preferably 3～15 atom %, be preferably 5～10 atom % especially.
In addition, this Au-TiN mix film in can be preferably 0.5～20 atom %, more preferably 0.5～12 atom %, the amount that is preferably 0.5～5 atom % especially contain the inevitable composition that forms by at least a kind in oxygen, the carbon.
In addition, mix at above-mentioned Au-TiN and to film, the content of Ti atom, Au atom, other atoms metal, N atom and inevitable composition add up to 100 atom %.
(6) formation that Au films or the Au alloy is filmed
For second golden decorative part of the present invention, then above-mentioned (5), stop the evaporation of the titanium in the dry type plater, stop the supply of the nitrogen in the dry type plater again, in the dry type plater, make gold or gold and other evaporation of metal under this state, mixing forming that Au films or the Au alloy is filmed as outermost layer on filming by the dry type plating method at above-mentioned Au-TiN.
At this moment, the steam output of the gold of time per unit preferably set become to make the film forming speed that Au films or the Au alloy is filmed be preferably 0.005～0.05 μ m/ minute, more preferably 0.01～0.03 μ m/ minute.For example, preferably under the condition that the steam output of the gold of the time per unit when mixing the formation of filming with above-mentioned Au-TiN is identical, make gold evaporation.
Among the present invention, consider that from the good aspect of solidity to corrosion outermost layer is preferably the Au alloy and films.Other atoms metal as the Au alloy is filmed can exemplify as palladium, nickel, platinum, iron, niobium, chromium, titanium, zirconium, hafnium, silicon, boron.Wherein, consider to be preferably palladium, nickel from the good especially aspect of solidity to corrosion.The content of other atoms metal be preferably 3～30 atom %, more preferably 10～20 atom %, be preferably 12～18 atom % especially.If the content of other atoms metal, also presents the tone of the tone of reflection lower floor in above-mentioned scope when then solidity to corrosion is good.
In addition, can be during this Au films or the Au alloy is filmed with preferred 0.5～20 atom %, more preferably the amount of 0.5～12 atom %, preferred especially 0.5～5 atom % contains the inevitable composition that forms by at least a kind in nitrogen, oxygen, the carbon.
In addition, during above-mentioned Au films or the Au alloy is filmed, the content of Au atom, other atoms metal and inevitable composition add up to 100 atom %.
The golden decorative part that the present invention relates to can make by above-mentioned manufacture method.Because first and second golden decorative parts all are to mix to film Au-TiN mixed across Au-TiN to film and the TiN lamination of filming, so adherence is good.Like this, Au-TiN is mixed films as thin as a wafer.In addition, have high surface hardness because Au-TiN mixes to film in second golden decorative part, therefore Au is filmed or the Au alloy is filmed as thin as a wafer.In addition, because that Au films or the Au alloy is filmed is extremely thin, even therefore these film abrasion, scratches, tone does not change substantially yet, and the abrasion wound on golden decorative part surface, to scrape scratch also not obvious.
In addition,, film as thin as a wafer, therefore TiN is filmed and thicken, improve as stacked film strength because Au-TiN is mixed for above-mentioned any golden decorative part.
The preferred thickness of respectively filming that has below shown this golden decorative part.The thickness that Ti films be preferably 0.1～0.5 μ m, more preferably 0.2～0.5 μ m, be preferably 0.3～0.5 μ m especially.
TiN tilts to film and total thickness that TiN films be preferably 0.5～2.0 μ m, more preferably 0.7～1.8 μ m, be preferably 1.0～1.5 μ m especially.The thickness that TiN tilts to film tilts to film with respect to TiN and the ratio of the total thickness that TiN films is preferably 10～60%, more preferably 20～55%, is preferably 30～50% especially.The ratio that TiN films if the ratio of the thickness that TiN tilts to film surpasses the above-mentioned upper limit reduces, and film toughness reduces.
Au-TiN mix the thickness of filming mix with Au-TiN the total thickness of filming be preferably 0.005～0.1 μ m, more preferably 0.005～0.05 μ m, be preferably 0.01～0.02 μ m especially.The thickness that the thickness that the Au-TiN mixing tilts to film tilts to film with respect to the Au-TiN mixing mixes the total thickness of filming with Au-TiN ratio is preferably 10～90%, more preferably 20～70%, is preferably 30～50% especially.The ratio of the thickness of filming is in above-mentioned scope if Au-TiN mixes, and then Au-TiN mixes to film and has full intensity, and Au-TiN mixes and films and TiN does not produce between filming and peels off.In addition, first golden decorative part presents further golden form and aspect.
In second golden decorative part, the thickness that Au films or the Au alloy is filmed be preferably 0.005～0.1 μ m, more preferably 0.005～0.05 μ m, be preferably 0.005～0.02 μ m especially.If the thickness that Au films or the Au alloy is filmed is in above-mentioned scope, even then second golden decorative part presents bright golden tone and these film abrasion, scratch, the variation of tone is also few, can obtain the unconspicuous golden decorative part of wound on the surface of causing because of abrasion, scratch.If the thickness of each layer in above-mentioned scope, the good golden decorative part of splitting, adherence between each layer then can not occurred.
The outermost hardness of film height of first golden decorative part is for example measured the Vickers' hardness that converts with the nano hardness meter and is preferably 500～800Hv, more preferably 600～700Hv under the condition of loading 50 μ N.The Au-TiN of second golden decorative part mixes the hardness of film height of filming, and for example measures the Vickers' hardness that converts with the nano hardness meter under the condition of loading 50 μ N and is preferably 500～800Hv, more preferably 600～700Hv.Therefore, damage because of wearing away or abrading even outermost Au films or the Au alloy is filmed, the Au-TiN mixing that also this damage can be limited in lower floor is filmed.In addition, the outermost of golden decorative part in the past hardness layer by layer is about 370Hv.
[embodiment]
Below, by embodiment the present invention is described, but the present invention is not subjected to any restriction of this embodiment.Corrosion resistant test among the embodiment and wear test are implemented in accordance with the following methods in addition.
(1) corrosion resistant test
Carry out corrosion resistant test according to JIS H8502 (キ ャ ス (CASS) test).Test period is 96 hours, and the grade point in utilizing grade point (rating number) standard chart is 9.8 when above, and it is qualified that the solidity to corrosion of this test face is evaluated as.
(2) wear test
As shown in Figure 1, utilize test film pressing plate 2 and test film thrust screw 3, will be formed with the peristome that the test film 1 of filming is fixed on test film treatment bench 4, and its formation of filming is faced down.Then, the pouncing paper (not shown) is attached on the abrasion wheel 5.Utilizing not shown scale mechanism to apply loading upwards to this abrasion wheel 5 is attached on the test film 1 will grind letterweight.
Afterwards, utilize the mechanism that rotatablely moving of engine is changed into back and forth movement not shown in the figures, make test film treatment bench 4 back and forth movements, in addition, test film treatment bench 4 whenever comes and goes 1 time, and abrasion wheel 5 is rotated to the direction of arrow with 0.9 ° of angle.By this rotation, test film 1 always contacts with the abrasive new region that do not have in the pouncing paper that is attached to abrasion wheel 5.Round number of times that can automatic setting test film treatment bench 4, to the number of times wear testing machine set stop automatically.
In addition, use the grinding film (Al that has particle diameter 12 μ m on the film surface
2O
3Particle, #1200) as the pouncing paper that is attached on the abrasion wheel 5, the loading that contacts at this pouncing paper and test film 1 is that the back and forth movement number of times of 500g, test film treatment bench 4 is under 100 times the condition, (ス ガ trier Co., Ltd. system NUS-ISO-2) is carried out wear test to utilize wear testing machine.
[comparative example 1]
The wrist-watch of the polishing of stainless steel (SUS316L) mechanical workout gained with shell organic solvent cleaning and degreasing, is placed into this base material in the ion plating apparatus.
Then, be vented to after the 1.3mPa in will installing, import argon gas up to 0.13Pa.In this argon atmospher, produce after the plasma body by installing the inner plasma gun that is provided with, the constant evaporation of titanium 10 minutes is filmed at the Ti of wrist-watch with the surface formation thickness 0.2 μ m of base material.
Then, make the titanium evaporation under the identical condition when forming filming, will import gas is replaced by nitrogen and argon gas from argon gas mixed gas simultaneously with above-mentioned Ti.At this moment, gas flow is being kept with 300sccm under certain state, the throughput ratio (N of nitrogen and argon gas
2/ Ar) increased to 2.0 from 0 with 35 minutes.Like this, the TiN that forms thickness 0.6 μ m on above-mentioned Ti films tilts to film.
Then, filming when form finishing under the identical condition, continuing to carry out consistently the supply of the mixed gas of the evaporation of titanium and nitrogen and argon gas, the TiN of formation thickness 0.6 μ m on above-mentioned TiN tilts to film is filmed with above-mentioned Ti.
Afterwards, stop the evaporation of titanium and the supply of nitrogen, make gold evaporation when supplying with argon gas, in 30 seconds of film forming, the Au that forms thickness 0.01 μ m on above-mentioned TiN films filmed with 0.02 μ m/ minute film forming speed.
The wrist-watch of gained has the gold tone of homogeneous with shell.
Wrist-watch shell for gained carries out corrosion resistant test, and the value of grade point is 9.8 as a result.In addition, implement to utilize the aberration (Δ E*ab) of color colour-difference meter (ミ ノ Le corporate system) determination test front and back after the wear test, the result is 6.54.The visual inspection surface, visible abrasion damage.
Embodiment 1
The wrist-watch of the polishing of stainless steel (SUS316L) mechanical workout gained with shell organic solvent cleaning and degreasing, is placed into this base material in the ion plating apparatus.
Then, be vented to after the 1.3mPa in will installing, import argon gas up to 0.13Pa.In this argon atmospher, produce after the plasma body by installing the inner plasma gun that is provided with, the constant evaporation of titanium 10 minutes is filmed at the Ti of wrist-watch with the surface formation thickness 0.2 μ m of base material.
Then, make the titanium evaporation under the identical condition when forming filming, will import gas is replaced by nitrogen and argon gas from argon gas mixed gas simultaneously with above-mentioned Ti.At this moment, gas flow is being kept with 300sccm under certain state, the throughput ratio (N of nitrogen and argon gas
2/ Ar) increased to 2.0 from 0 with 35 minutes.Like this, the TiN that forms thickness 0.6 μ m on above-mentioned Ti films tilts to film.
Then, filming when form finishing under the identical condition with above-mentioned Ti, continuing to carry out consistently the supply of the mixed gas of the evaporation of titanium and nitrogen and argon gas, the TiN of formation thickness 0.6 μ m films on above-mentioned TiN tilts to film.
Afterwards, make the constant evaporation of titanium under the identical condition when forming filming with above-mentioned TiN, and with the flow supply flow rate of 680sccm than (N
2/ Ar) be 5.8 the nitrogen and the mixed gas of argon gas, make gold evaporation simultaneously, the Au-TiN that forms thickness 0.005 μ m on above-mentioned TiN films mixes to tilt to film.At this moment, through the time increase the steam output of the time per unit of gold so that the Au atom of time per unit increases 2.67 atom % with respect to the content of the evaporation amount of whole atoms in 1 second.Specifically, with 0.02 μ m/ minute film forming speed with 15 seconds of this Au-TiN mixing inclination coating film, at this moment, the steam output that makes gold through the time increase so that the Au content that Au-TiN mixes in tilting to film increases in the ratio of film growth direction with 8 atom %/0.001 μ m.
Then, form under the condition identical when finishing mixing to tilt to film with above-mentioned Au-TiN, continue to carry out consistently the evaporation of titanium and gold, and the supply of the mixed gas of nitrogen and argon gas, the Au-TiN mixing that forms thickness 0.01 μ m on above-mentioned Au-TiN mixing tilts to film is filmed.
The wrist-watch of gained has the gold tone of homogeneous with shell.
Wrist-watch for gained carries out corrosion resistant test with shell, and grade point is 9.9 as a result.In addition, carry out wear test, confirm only to have slight abrasion damage from the teeth outwards, wear resistant and scoring resistance are all desirable.In addition, do not see that Au-TiN mixes peeling off of filming.
Utilize x-ray photoelectron analytical equipment (ESCA) to analyze the composition of the wrist-watch of gained with shell, Au-TiN mixing is as a result filmed and is made of golden 40 atom %, titanium 38 atom %, nitrogen 20 atom %, oxygen 1 atom %, carbon 1 atom %.In addition, TiN films and is made of titanium 54 atom %, nitrogen 45 atom %, oxygen 0.5 atom %, carbon 0.5 atom %.In addition, during Au-TiN mixes to film the Au atom content with the ratio of 8 atom %/0.001 μ m increase, the Ti atom content with the ratio of 3.2 atom %/0.001 μ m reduce, the N atom content reduces with the ratio of 5 atom %/0.001 μ m.In addition, the N atom content reduced with the ratio of 7.7 atom %/0.1 μ m with ratio increase, the Ti atom content of 7.5 atom %/0.1 μ m during TiN tilted to film.In addition, this wrist-watch mixing the composition that the TiN that films films at film thickness direction from Au-TiN and change as shown in Figure 2 with shell.
In addition, in the scope of wavelength 400～700nm, measure the surface albedo of this wrist-watch with shell.The result as shown in Figure 3.
The wrist-watch of the polishing of stainless steel (SUS316L) mechanical workout gained with shell organic solvent cleaning and degreasing, is placed into this base material in the ion plating apparatus.
Then, be vented to after the 1.3mPa in will installing, import argon gas up to 0.13Pa.In this argon atmospher, produce after the plasma body by installing the inner plasma gun that is provided with, the constant evaporation of titanium 10 minutes is filmed at the Ti of wrist-watch with the surface formation thickness 0.2 μ m of base material.
Then, make the titanium evaporation under the identical condition when forming filming, will import gas is replaced by nitrogen and argon gas from argon gas mixed gas simultaneously with above-mentioned Ti.At this moment, gas flow is being kept with 300sccm under certain state, the throughput ratio (N of nitrogen and argon gas
2/ Ar) increased to 2.0 from 0 with 35 minutes.Like this, the TiN that forms thickness 0.6 μ m on above-mentioned Ti films tilts to film.
Then, filming when form finishing under the identical condition with above-mentioned Ti, continuing to carry out consistently the supply of the mixed gas of the evaporation of titanium and nitrogen and argon gas, the TiN of formation thickness 0.6 μ m films on above-mentioned TiN tilts to film.
Afterwards, make the constant evaporation of titanium under the identical condition when forming filming with above-mentioned TiN, and with the flow supply flow rate of 680sccm than (N
2/ Ar) be 5.8 the nitrogen and the mixed gas of argon gas, make gold evaporation simultaneously, the Au-TiN that forms thickness 0.005 μ m on above-mentioned TiN films mixes to tilt to film.At this moment, through the time increase the steam output of the time per unit of gold so that the Au atom of time per unit increases 2.67 atom % with respect to the content of the evaporation amount of whole atoms in 1 second.Specifically, with 0.02 μ m/ minute film forming speed with 15 seconds of this Au-TiN mixing inclination coating film, at this moment, the steam output that makes gold through the time increase so that the Au content that Au-TiN mixes in tilting to film increases in the ratio of film growth direction with 8 atom %/0.001 μ m.
Then, form under the condition identical when finishing mixing to tilt to film with above-mentioned Au-TiN, continue to carry out consistently the evaporation of titanium and gold, and the supply of the mixed gas of nitrogen and argon gas, the Au-TiN mixing that forms thickness 0.01 μ m on above-mentioned Au-TiN mixing tilts to film is filmed.
Afterwards, stop the evaporation of titanium and the supply of nitrogen, continue the evaporation of gold and the supply of argon gas mixing to film to form under the condition identical when finishing, mix the Au that forms 0.01 μ m on filming at above-mentioned Au-TiN and film with above-mentioned Au-TiN.
The wrist-watch of gained has the gold tone of homogeneous with shell.
Wrist-watch for gained carries out corrosion resistant test with shell, and grade point is 9.9 as a result.In addition, carry out wear test, confirm that the abrasion damage on surface is extremely slight, degree of injury is lighter than the foregoing description 1.In addition, do not see that Au-TiN mixes peeling off of filming.
The wrist-watch of the polishing of stainless steel (SUS316L) mechanical workout gained with shell organic solvent cleaning and degreasing, is placed into this base material in the ion plating apparatus.
Then, be vented to after the 1.3mPa in will installing, import argon gas up to 0.13Pa.In this argon atmospher, produce after the plasma body by installing the inner plasma gun that is provided with, make the constant evaporation of titanium that wrist-watch is filmed with the Ti of the surface formation thickness 0.2 μ m of base material.
Then, make the titanium evaporation under the identical condition when forming filming, will import gas is replaced by nitrogen and argon gas from argon gas mixed gas simultaneously with above-mentioned Ti.At this moment, gas flow is being kept with 300sccm under certain state, the throughput ratio (N of nitrogen and argon gas
2/ Ar) increased to 2.0 from 0 with 35 minutes.Like this, the TiN that forms thickness 0.6 μ m on above-mentioned Ti films tilts to film.
Then, filming when form finishing under the identical condition with above-mentioned Ti, continuing to carry out consistently the supply of the mixed gas of the evaporation of titanium and nitrogen and argon gas, the TiN of formation thickness 0.6 μ m films on above-mentioned TiN tilts to film.
Afterwards, make the constant evaporation of titanium under the identical condition when forming filming with above-mentioned TiN, and with the flow supply flow rate of 680sccm than (N
2/ Ar) be 5.8 the nitrogen and the mixed gas of argon gas, make gold evaporation simultaneously, the Au-TiN that forms thickness 0.005 μ m on above-mentioned TiN films mixes to tilt to film.At this moment, through the time increase the steam output of the time per unit of gold and palladium so that time per unit increase 2.67 atom % in 1 second with respect to the Au atom of the evaporation amount of whole atoms and the total content of Pd atom.Specifically, with 0.02 μ m/ minute film forming speed with 15 seconds of this Au-TiN mixing inclination coating film, at this moment, the steam output that makes gold through the time increase so that Au-TiN mixes Au in tilting to film and the total content of Pd increases in the ratio of film growth direction with 8 atom %/0.001 μ m.In addition, the ratio of Au and Pd is 85 atom %: 15 atom %.
Then, form under the condition identical when finishing mixing to tilt to film with above-mentioned Au-TiN, continue to carry out the evaporation of titanium, gold and palladium consistently, and the supply of the mixed gas of nitrogen and argon gas, the Au-TiN mixing that forms thickness 0.01 μ m on above-mentioned Au-TiN mixing tilts to film is filmed.In addition, the ratio of Au and Pd is 85 atom %: 15 atom %.
Afterwards, stop the evaporation of titanium and the supply of nitrogen, continue gold and the evaporation of palladium and the supply of argon gas mixing to film to form under the condition identical when finishing with above-mentioned Au-TiN, above-mentioned Au-TiN mix film on the Au-Pd alloy of formation 0.01 μ m film.In addition, the ratio of Au and Pd is 85 atom %: 15 atom %.
The wrist-watch of gained has the gold tone of homogeneous with shell.In addition, in the scope of wavelength 400～700, measure the surface albedo of this wrist-watch with shell.The results are shown in Fig. 3.By this result as can be known, be that Au-TiN mixes the wrist-watch film and compares with shell (embodiment 1) with outermost layer, lower floor be Au-TiN mix film, wrist-watch that outermost layer is filmed for the Au-Pd alloy is with the surface albedo height of shell, become clear.
Wrist-watch for gained carries out corrosion resistant test with shell, and grade point is 9.9 as a result.In addition, after carrying out wear test, utilize the aberration (Δ E*ab) of color colour-difference meter (ミ ノ Le corporate system) determination test front and back, the result is 2.94.In addition, the abrasion on surface damage similarly to Example 2, for extremely slight.From this result as can be known, even outermost layer is filmed for the Au-Pd alloy, be that the wrist-watch that TiN films is compared with shell (comparative example 1) with lower floor, it is few with the variable color before and after the wear test of shell that lower floor is that Au-TiN mixes the wrist-watch film, and wears away not obvious.In addition, confirm also not have Au-TiN to mix peeling off of filming.
Utilize x-ray photoelectron analytical equipment (ESCA) to analyze the composition of the wrist-watch of gained with shell, the Au alloy is filmed and is made of golden 85 atom %, palladium 15 atom % as a result.In addition, the Au-TiN mixing is filmed and is made of golden 40 atom %, palladium 7 atom %, titanium 31 atom %, nitrogen 20 atom %, oxygen 1 atom %, carbon 1 atom %.In addition, TiN films and is made of titanium 54 atom %, nitrogen 45 atom %, oxygen 0.5 atom %, carbon 0.5 atom %.In addition, Au-TiN mix film in Au atom and Pd atom total content with the ratio of 8 atom %/0.001 μ m increase, the Ti atom content with the ratio of 3.2 atom %/0.001 μ m reduce, the N atom content reduces with the ratio of 5 atom %/0.001 μ m.In addition, the N atom content reduced with the ratio of 7.7 atom %/0.1 μ m with ratio increase, the Ti atom content of 7.5 atom %/0.1 μ m during TiN tilted to film.In addition, this wrist-watch mixing the composition that the TiN that films films at film thickness direction from Au-TiN and change as shown in Figure 4 with shell.
The possibility of utilizing on the industry
The present invention can be applied to the wrist-watch extraneous adornment articles for use such as inner cap such as Watchcase, watchband, wrist-watch handle, wrist-watch, Belt fastener, ring, necklace, bracelet, earrings, pendicle, brooch, cuff button, tie clip, badge, spectacle-frame, camera machine Body, door handle etc.
Claims (17)
1. the manufacture method of golden decorative part is characterized in that,
On the surface of base material, in the dry type plater, under the inert gas atmosphere except that nitrogen, make titanium with the certain state evaporation of the steam output of its time per unit, form Ti and film;
Then, in this dry type plater, make titanium with the certain state evaporation of the steam output of its time per unit, simultaneously in this dry type plater, import nitrogen so that the nitrogen amount in this dry type plater through the time increase, above-mentioned Ti is filmed go up to form the N atom content and tilt to film at the TiN that film thickness direction has gradient;
Follow, in this dry type plater, titanium is evaporated with the certain state of the steam output of its time per unit, make the interior nitrogen amount of this dry type plater keep certain simultaneously, formation TiN films to make above-mentioned TiN tilt to film upward; Then, in this dry type plater, make titanium with the certain state evaporation of the steam output of its time per unit, and make the nitrogen amount in this dry type plater keep certain, simultaneously with the steam output of the gold of time per unit through the time state that increases make gold or gold and other evaporation of metal, above-mentioned TiN is filmed go up to form the Au atom content has gradient on film thickness direction Au-TiN and mix to tilt to film;
Again then, make the nitrogen amount in this dry type plater keep certain, make titanium and gold in this dry type plater, perhaps titanium, gold and other metal evaporate with the certain state of the steam output of their time per units, make above-mentioned Au-TiN mixing tilt to film to go up formation Au-TiN mixing and film.
2. the manufacture method of golden decorative part as claimed in claim 1, it is characterized in that, form above-mentioned Au-TiN mix film after, stop the evaporation of the titanium in the above-mentioned dry type plater, and stop in this dry type plater for nitrogen, make gold or gold and the evaporation of metal except that gold and titanium in this dry type plater, above-mentioned Au-TiN mixing is filmed, and the last Au of formation films or the Au alloy is filmed.
3. the manufacture method of golden decorative part as claimed in claim 1 or 2, it is characterized in that, forming Au-TiN mixes when tilting to film, make time per unit gold steam output through the time increase so that the Au atom content that this Au-TiN mixes in tilting to film increases at film thickness direction with the ratio of 2～10 atom %/0.001 μ m.
4. the manufacture method of golden decorative part as claimed in claim 1 or 2 is characterized in that, forms Au-TiN and mixes when tilting to film, 2.5 times of nitrogen more than the amount of the nitrogen feed rate when supply TiN films formation in the dry type plater.
5. the manufacture method of golden decorative part as claimed in claim 1 or 2 is characterized in that, forms Au-TiN and mixes when filming, 2.5 times of nitrogen more than the amount of the nitrogen feed rate when supply TiN films formation in the dry type plater.
6. the method for making method of golden decorative part as claimed in claim 1 or 2, it is characterized in that, when forming TiN and tilting to film, make in this dry type plater the nitrogen amount through the time increase so that the N atom content of this TiN in tilting to film increases on film thickness direction with the ratio of 4～12 atom %/0.1 μ m.
7. the manufacture method of golden decorative part as claimed in claim 2, it is characterized in that, the Au atom and the atoms metal except that golden and titanium that mix in filming with Au-TiN during the Au-TiN mixing tilts to film form alloy, form the Au alloy and film on this Au-TiN mixing is filmed.
8. golden decorative part is characterized in that, has
Base material;
Form under the inert gas atmosphere except that nitrogen at this substrate surface, Ti atom content certain Ti on film thickness direction films;
The TiN that forms on this Ti films, the N atom content has a gradient on film thickness direction tilts to film; On this TiN tilts to film, form, Ti atom and N atom content certain TiN on film thickness direction film;
On this TiN films, form, the Au atom content has the Au-TiN of gradient to mix to tilt to film on film thickness direction;
Form on this Au-TiN mixing tilts to film, the certain Au-TiN mixing on film thickness direction of Au atom, Ti atom and N atom content is filmed.
9. golden decorative part as claimed in claim 8 is characterized in that, above-mentioned Au-TiN mixes and also has that Au atom content certain Au on film thickness direction films or the Au alloy is filmed on filming.
10. golden decorative part as claimed in claim 8 or 9 is characterized in that, mixes to tilt to film at Au-TiN, and the Au atom content mixes the film thickness direction of filming along filming from TiN to Au-TiN and increase.
11. golden decorative part as claimed in claim 10 is characterized in that, in the Au-TiN mixing that does not contain the atoms metal except that gold and titanium tilted to film, the Au atom content increased with the ratio of 2～10 atom %/0.001 μ m.
12. golden decorative part as claimed in claim 10, it is characterized in that, in the Au-TiN mixing tilted to film, Au atom and the atoms metal except that gold and titanium formed alloy, and the total content of Au atom and the atoms metal except that gold and titanium is with the ratio increase of 2～10 atom %/0.001 μ m.
13. golden decorative part as claimed in claim 9 is characterized in that, Au atom and the atoms metal except that gold and titanium that Au-TiN mixes in filming form alloy, are formed with the Au alloy on this Au-TiN mixing is filmed and film.
14. golden decorative part is characterized in that as claimed in claim 8 or 9, in TiN tilted to film, the N atom content increased along the film thickness direction of filming to TiN of filming from Ti.
15. golden decorative part as claimed in claim 14 is characterized in that, during TiN tilted to film, the N atom content increased with the ratio of 4～12 atom %/0.1 μ m.
16. golden decorative part as claimed in claim 8 is characterized in that,
The thickness that Ti films is 0.1～0.5 μ m,
TiN tilts to film and total thickness that TiN films is 0.5～2.0 μ m, and the TiN thickness that tilts to film with respect to the ratio of this total thickness in 10～60% scope,
Au-TiN mixes, and mixes the total thickness of filming with Au-TiN be 0.005～0.1 μ m for the thickness of filming, and the Au-TiN mixing inclination thickness of filming with respect to the ratio of this total thickness in 10～90% scope.
17. golden decorative part as claimed in claim 9 is characterized in that,
The thickness that Ti films is 0.1～0.5 μ m,
TiN tilts to film and total thickness that TiN films is 0.5～2.0 μ m, and the TiN thickness that tilts to film with respect to the ratio of this total thickness in 10～60% scope,
The thickness that the Au-TiN mixing tilts to film mixes the total thickness of filming with Au-TiN be 0.005～0.1 μ m, and Au-TiN mix the thickness of filming with respect to the ratio of this total thickness in 10～90% scope, the thickness that Au films or the Au alloy is filmed is 0.005～0.1 μ m.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP103446/2005 | 2005-03-31 | ||
| JP2005103446A JP2006283088A (en) | 2005-03-31 | 2005-03-31 | Golden ornament and its manufacturing method |
| JP2006087940A JP2007262472A (en) | 2006-03-28 | 2006-03-28 | Golden ornament and process for producing the same |
| JP087940/2006 | 2006-03-28 | ||
| PCT/JP2006/306955 WO2006106981A1 (en) | 2005-03-31 | 2006-03-31 | Golden ornament and process for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210454466XA Division CN102994949A (en) | 2005-03-31 | 2006-03-31 | Golden ornament and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101160418A true CN101160418A (en) | 2008-04-09 |
| CN101160418B CN101160418B (en) | 2012-12-12 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680010467.8A Expired - Fee Related CN101160418B (en) | 2005-03-31 | 2006-03-31 | Golden ornament and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP2006283088A (en) |
| CN (1) | CN101160418B (en) |
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| JP5370808B2 (en) * | 2008-06-13 | 2013-12-18 | Ｎｔｎ株式会社 | Abrasion resistant TiN film and formed body thereof |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH643421B (en) * | 1980-04-10 | Asu Composants Sa | DEPOSIT PROCESS FOR A HARD COATING OF A GOLD COMPOUND, DEPOSIT TARGET FOR SUCH A PROCESS AND JEWELERY INCLUDING SUCH A COATING. | |
| JPS58120777A (en) * | 1982-01-11 | 1983-07-18 | Seiko Epson Corp | External parts for timepieces |
| JPS6067654A (en) * | 1983-09-22 | 1985-04-18 | Seiko Instr & Electronics Ltd | Preparation of hard gold alloy plating |
| JPH0331471A (en) * | 1989-06-28 | 1991-02-12 | Daido Steel Co Ltd | Golden exterior parts and production thereof |
| JP3179648B2 (en) * | 1993-02-19 | 2001-06-25 | シチズン時計株式会社 | Golden decorative component and method of manufacturing the same |
| JPH07157869A (en) * | 1993-12-08 | 1995-06-20 | Aomori Pref Gov | Coating method of titanium nitride film by ion plating method |
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2005
- 2005-03-31 JP JP2005103446A patent/JP2006283088A/en active Pending
-
2006
- 2006-03-31 CN CN200680010467.8A patent/CN101160418B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2006283088A (en) | 2006-10-19 |
| CN101160418B (en) | 2012-12-12 |
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