JP3909092B2 - Golden decorative part and manufacturing method thereof - Google Patents
Golden decorative part and manufacturing method thereof Download PDFInfo
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- JP3909092B2 JP3909092B2 JP16910494A JP16910494A JP3909092B2 JP 3909092 B2 JP3909092 B2 JP 3909092B2 JP 16910494 A JP16910494 A JP 16910494A JP 16910494 A JP16910494 A JP 16910494A JP 3909092 B2 JP3909092 B2 JP 3909092B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 113
- 239000010936 titanium Substances 0.000 claims description 89
- 238000007747 plating Methods 0.000 claims description 82
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 50
- 229910052719 titanium Inorganic materials 0.000 claims description 50
- 239000010931 gold Substances 0.000 claims description 48
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 46
- 229910052737 gold Inorganic materials 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- 239000007789 gas Substances 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 239000011261 inert gas Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 13
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 13
- 150000004767 nitrides Chemical class 0.000 claims description 13
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims 3
- 239000010410 layer Substances 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- NPEWZDADCAZMNF-UHFFFAOYSA-N gold iron Chemical compound [Fe].[Au] NPEWZDADCAZMNF-UHFFFAOYSA-N 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000007733 ion plating Methods 0.000 description 9
- 229910000640 Fe alloy Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910017390 Au—Fe Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- 229910017392 Au—Co Inorganic materials 0.000 description 1
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 229910010977 Ti—Pd Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 1
- ZNKMCMOJCDFGFT-UHFFFAOYSA-N gold titanium Chemical compound [Ti].[Au] ZNKMCMOJCDFGFT-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
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 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
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 229910001258 titanium gold Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、金色装飾部品及びその製造方法に関し、特に色調を調節することのできる製造方法に関するものである。
【０００２】
【従来の技術】
従来、イオンプレーティング法による時計バンドなどの時計部品、指輪、ネックレス、イヤリング等の金色装飾部品は、その最外層に、金被膜を形成することにより、高級感あるいは優れた耐蝕性が付与されている。更に純金の被膜に変えて金−ニッケル、金−鉄、金−パラジウム、金−チタン合金膜等の合金膜が装飾部品の最外層に形成され装飾部品が提供されている。
【０００３】
【発明が解決しようとする課題】
之等の合金膜は淡い金色で、各々色調が微妙に異なる。またグリーン系になる傾向がある。更に赤味を帯びた金メッキ部品との色合わせが困難である。
【０００４】
本発明は、上記のような従来技術における問題点を解決しようとするものであって、色調を変えることができ、特に赤味を帯びた金色を呈する装飾部品及びその製造方法を提供することを目的としている。
【０００５】
【課題を解決するための手段】
本発明による第１の金色装飾部品は、基材と、この基材上に乾式メッキ法により、乾式メッキ装置内の圧力を８×１０-4〜５×１０-3Torrで窒素以外の不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有し形成されたＴｉ系被膜と、この被膜上に形成された最外層被膜とからなり、かつ、最外層被膜が金５０〜９９．８原子％と、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、不可避成分０．１〜２０原子％とを含有してなることを特徴としている。
【０００６】
本発明による第２の金色装飾部品は、基材と、この基材上に乾式メッキ法により、乾式メッキ装置内の圧力を８×１０-4〜５×１０-3Torrで窒素以外の不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有し形成されたＴｉ系被膜と、この被膜上に形成された最外層被膜とからなり、かつ、最外層被膜が金５０〜９８．９原子％と、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、鉄、チタン、ニッケル、パラジウム、コバルトのうち少なくとも１元素が０．５〜２０原子％と、不可避成分０．５〜２０原子％とを含有してなることを特徴としている。
【０００７】
本発明による第３の金色装飾部品は、基材と、この基材上に乾式メッキ法により、乾式メッキ装置内の圧力を８×１０-4〜５×１０-3Torrで窒素以外の不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有し形成されたＴｉ系被膜と、この被膜上に形成されたチタン、又はタンタル、又はハフニウム、又はバナジウム、又はジルコニウムの窒化物よりなる被膜と、この被膜上に形成された最外層被膜とからなり、かつ、最外層被膜が、金５０〜９９．８原子％と、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、不可避成分０．１〜２０原子％とを含有してなることを特徴としている。
【０００８】
本発明による第４の金色装飾部品は、基材と、この基材上に乾式メッキ法により、乾式メッキ装置内の圧力を８×１０-4〜５×１０-3Torrで窒素以外の不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有し形成されたＴｉ系被膜と、この被膜上に形成されたチタン、又はタンタル、又はハフニウム、又はバナジウム、又はジルコニウムの窒化物よりなる被膜と、この被膜上に形成された最外層被膜とからなり、かつ、最外層被膜が、金５０〜９８．９原子％と、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、鉄、チタン、ニッケル、パラジウム、コバルトのうち少なくとも１元素が０．５〜２０原子％と、不可避成分０．５〜２０原子％とを含有してなることを特徴としている。
【０００９】
前記Ｔｉ系被膜の膜厚は、０．１〜０．５μｍであることを特徴とする。
【００１０】
前記チタン、又はタンタル、又はハフニウム、又はバナジウム、又はジルコニウムの窒化物よりなる被膜の膜厚は、０．１〜１０μｍであることを特徴とする。
【００１１】
前記最外層被膜の膜厚は、０．０５〜０．５μｍであることを特徴とする。
【００１２】
前記乾式メッキ法において、基材を含む、成膜前の乾式メッキ装置内の初期排気が、５×１０ -5 〜１．０×１０ -6 Torr まで行われていることを特徴とする。
【００１３】
前記Ｔｉ系被膜の膜厚は、基材を含む、成膜前の乾式メッキ装置内の初期排気を５×１０ -5 〜１．０×１０ -6 Torr まで行ない、該装置内に置かれた基材表面に窒素以外の不活性ガス中で乾式メッキ法で形成され、且つ、膜厚が０．０５〜０．５μｍであることを特徴とする。
【００１４】
本発明による金色装飾部品の第１の製造方法は、乾式メッキ法において、基材を含む、成膜前の乾式メッキ装置内を５×１０-5〜１．０×１０-6Torrまで初期排気後、乾式メッキ装置内に窒素以外の不活ガスを８×１０-4〜５×１０-3Torrまで導入し、基材上に不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有するＴｉ系被膜を形成させ、次に、この乾式メッキ装置内で、このＴｉ系被膜の上に窒素ガス、酸素ガス、炭化水素系ガス、又はそれらの混合ガス雰囲気下に、金５０〜９９．８原子％と、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、不可避成分０．１〜２０原子％とを含有してなる最外層被膜を形成することを特徴としている。
【００１５】
本発明による金色装飾部品の第２の製造方法は、乾式メッキ法において、基材を含む、成膜前の乾式メッキ装置内を５×１０-5〜１．０×１０-6Torrまで初期排気後、乾式メッキ装置内に窒素以外の不活ガスを８×１０-4〜５×１０-3Torrまで導入し、基材上に不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有するＴｉ系被膜を形成させ、次に、この乾式メッキ装置内で、このＴｉ系被膜の上に窒素ガス、酸素ガス、炭化水素系ガス、又はそれらの混合ガス雰囲気下に、金５０〜９８．９原子％と、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、鉄、チタン、ニッケル、パラジウム、コバルトのうち少なくとも１元素が０．５〜２０原子％と、不可避成分０．５〜２０原子％とを含有してなる最外層被膜を形成することを特徴としている。
【００１６】
本発明による金色装飾部品の第３の製造方法は、乾式メッキ法において、基材を含む、成膜前の乾式メッキ装置内を５×１０-5〜１．０×１０-6Torrまで初期排気後、乾式メッキ装置内に窒素以外の不活ガスを８×１０-4〜５×１０-3Torrまで導入し、基材上に不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有するＴｉ系被膜を形成させ、次に、この乾式メッキ装置内で、このＴｉ系被膜の上に、窒素ガス雰囲気下でチタン、又はタンタル、又はハフニウム、又はバナジウム、又はジルコニウムを蒸発させて、それぞれの元素の窒化物を形成させ、次に、これら窒化被膜の上に、窒素ガス、酸素ガス、炭化水素系ガス、又はそれらの混合ガス雰囲気下に、金５０〜９９．８原子％、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、不可避成分０．１〜２０原子％とを含有してなる最外層被膜を形成することを特徴としている。
【００１７】
本発明による金色装飾部品の第３の製造方法は、乾式メッキ法において、基材を含む、成膜前の乾式メッキ装置内を５×１０-5〜１．０×１０-6Torrまで初期排気後、乾式メッキ装置内に窒素以外の不活ガスを８×１０-4〜５×１０-3Torrまで導入し、基材上に不活性ガス雰囲気下でチタンを蒸発させて、乾式メッキ装置内に存在する不可避成分を含有するＴｉ系被膜を形成させ、次に、この乾式メッキ装置内でこのＴｉ系被膜の上に、窒素ガス雰囲気下でチタン、又はタンタル、又はハフニウム、又はバナジウム、又はジルコニウムを蒸発させて、それぞれの元素の窒化物を形成させ、次に、これら窒化被膜の上に窒素ガス、酸素ガス、炭化水素系ガス、又はそれらの混合ガス雰囲気下に、金５０〜９８．９原子％、窒素、酸素、炭素のうち少なくとも１元素が０．１〜３０原子％と、鉄、チタン、ニッケル、パラジウム、コバルトのうち少なくとも１元素が０．５〜２０原子％と、不可避成分０．５〜２０原子％とを含有してなる最外層被膜を形成することを特徴としている。
【００１８】
前記Ｔｉ系被膜は、０．１〜０．５μｍの膜厚で形成したことを特徴としている。
【００１９】
前記チタン、又はタンタル、又はハフニウム、又はバナジウム、又はジルコニウムの窒化物よりなる被膜は、０．１〜１０μｍの膜厚で形成したことを特徴としている。
【００２０】
前記最外層被膜は、０．０５〜０．５μｍの膜厚で形成したことを特徴としている。
【００２１】
具体的説明
以下、本発明に係わる金色装飾部品及びその製造方法について具体的に説明する。
【００２２】
本発明に係わる金色装飾部品は、基材と、この基材上に真空蒸着法、スパッタ法あるいはイオンプレーティング法等の乾式メッキ法により形成された最外層被膜とからなり、最外層被膜が金、又は金と他の金属との合金、窒素、酸素又は炭素による成分及び不可避成分とを特定の割合で含有してなる。他の金属は鉄、チタン、ニッケル、パラジウム、又はコバルトである。
【００２３】
また、本発明による金色装飾部品は、上記の基材の上にチタン、又はタンタル、又はハフニウム、又はジルコニウム被膜が形成され、その上に最外層被膜を形成してもよい。これらの窒化被膜を有する金色装飾部品は、最外層被膜と基材との密着性に優れている。
【００２４】
本発明で用いられる基材としては装飾部品の種類によって異なり、金属、プラスチック、セラミック等の材料である。
本発明に係わる金色装飾部品では、最外層被膜は金が５０〜９９．８又は９８．９原子％、好ましくは８１．５〜９６．５原子％、更に好ましくは８８〜９６．５原子％、他の金属が０．５〜２０原子％、好ましくは２．５〜７原子％、更に好ましくは３〜７原子％、窒素、酸素又は炭素が０．１〜３０原子％、不可避成分０．５〜２０原子％とを含有している。ここで不可避成分とは、装置内に存在する残留ガス成分であり、酸素、炭素、窒素等をさしている。従って被膜中に含まれる窒素、酸素、炭素が積極的に導入したガス成分なのか、それとも不可避成分なのかを区別することはできない。しかしながら被膜中に含まれる不可避成分の量は通常一定しており、導入したガス成分がどれ位被膜中に含まれたかは、ガスを導入した場合と導入しない場合の差としてみる事ができる。
【００２５】
例えば、表３において
膜中にとりこまれた酸素は▲１▼と▲２▼の差 １．１％
膜中にとりこまれた炭素は▲２▼と▲３▼の差 ８．４％
とみることができる。
【００２６】
次に、本発明による金色装飾部品の製造方法について説明する。
基材と最外層被膜とからなる金色装飾部品は、基材上に、乾式メッキ装置内で窒素ガス雰囲気下に金５０〜９８．９原子％と鉄０．５〜２０原子％の混合被膜を形成する。
【００２７】
また、基材と、Ｔｉ系被膜と、最外層被膜とからなる金色装飾部品は、基材上に、乾式メッキ装置内で窒素以外のアルゴン、ヘリウム、ネオンなどの不活性ガス雰囲気下にチタンを蒸発させて乾式メッキ装置内に存在する不可避成分を含有するＴｉ系被膜を形成させ、
次に、この乾式メッキ装置内で、Ｔｉ系被膜の上に、窒素ガス雰囲気下に金５０〜９８．９原子％と鉄０．５〜２０原子％の混合被膜を形成する。
【００２８】
更に、基材と、ＴｉＮ被膜と、最外層被膜とからなる金色装飾部品は、基材上に、乾式メッキ装置内で窒素ガス雰囲気下にチタンを蒸発させてＴｉＮ被膜を形成させ、次に、この乾式メッキ装置内で、ＴｉＮ被膜の上に、窒素ガス雰囲気下に金５０〜９８．９原子％と鉄０．５〜２０原子％の混合被膜を形成する。
【００２９】
更に基材と、Ｔｉ系被膜と、ＴｉＮ被膜と、最外層被膜とからなる金色装飾部品は、基材上に、窒素以外の不活性ガス雰囲気下にチタンを蒸発させて乾式メッキ装置内に存在する不可避成分を含有するＴｉ系被膜を形成させ、
次に、この乾式メッキ装置内で、Ｔｉ系被膜の上に窒素ガス雰囲気下にチタンを蒸発させてＴｉ系被膜の上に窒素ガス雰囲気下にチタンを蒸発させてＴｉＮ被膜を形成させ、
次いで、この乾式メッキ装置内で、このＴｉＮ被膜の上に、窒素ガス雰囲気下に金５０〜９８．９原子％と鉄０．５〜２０原子％の混合被膜を形成する。
【００３０】
上記方法以外の方法として、窒素以外のガスとして酸素及び炭化水素系ガスがあり、又鉄以外の金属として、チタン、ニッケル、パラジウム、及びコバルトがある。更にＴｉＮ被膜以外の被膜としてＴａＮ、ＨｆＮ、ＶＮ、ＺｒＮがある。
【００３１】
本発明においては、上記の最外層被膜は、スパッタ法、真空蒸着法またはイオンプレーティング法によって形成することができるが、特にイオンプレーティング法によって形成することが好ましい。
【００３２】
以下、本発明による金色装飾部品における各々の被膜、特にイオンプレーティング法により最外層被膜を金−鉄合金で形成した場合でより具体的に説明する。腕時計用バンドなどの基材は、予め有機溶剤等で洗浄しておくことが好ましい。また、イオンプレーティング装置内を５×１０-5〜１．０×１０-6Torr、好ましくは１．０×１０-5〜１．０×１０-6Torrまで排気した後、雰囲気ガスを８×１０-4〜５×-3Torr、好ましくは１．０×１０-3〜２．０×１０-3Torrまで導入する。
【００３３】
均一な金色調を有する最外層被膜を得るには、成膜前の装置内部の圧力は低い方がよく、１×１０-5Torr以下、好ましくは１×１０-6Torr以下に排気することが望ましい。すなわち、装置内部の圧力が低くなるにしたがって、装置内部の不可避成分の存在する量が減少し、金色調が均一化するからである。
【００３４】
本発明による金色装飾部品の最外層被膜は、厚みが通常０．０５〜０．５μｍ、好ましくは０．１〜０．３μｍである。
また、ＴｉＮ被膜の膜厚は、０．１〜１０μｍ、好ましくは０．１〜２μｍであり、不可避成分を多く含有するＴｉ系被膜の膜厚は、０．１〜０．５μｍ、好ましくは０．２〜０．３μｍ程度であることが望ましい。
【００３５】
前記のようにＴｉＮ被膜を形成することにより金−鉄合金膜の最外層被膜と基材との密着性を上げることができるが、ＴｉＮ被膜の代わりに、ＺｒＮ、ＨｆＮ等の金色系の窒化物被膜を形成してもよい。
【００３６】
本発明では、金−鉄混合物を蒸発源として用いてもよいが、蒸発源を２つ設け、一方の蒸発源として金を用い、他方の蒸発源として鉄を用い、金と鉄を別々に蒸発させてもよい。
【００３７】
本発明で蒸発源として金−鉄混合物を用いる場合には、得られる最外層被膜の組成が金５０〜９８．９原子％、鉄０．５〜２０原子％となるように金と鉄を用いるが、具体的には、金７５〜９０原子％、鉄１０〜２５原子％である金−鉄混合物、あるいは金−鉄合金を用いることが好ましい。
【００３８】
酸素を用いるときは酸素と不活性ガス、例えばアルゴンとの混合ガスを用いる。また炭素としては炭化水素、例えばエチレンガスを用いる。
【００３９】
表１は窒素及び酸素の量の変化を示し、表２はそれに伴う色調の変化を示す。ここに、Ｌ* は国際照明委員会（ＣＩＥ）ＣＩＥ１９７６（L * ａ* ｂ* ）色空間における明度指数であり、ａ* 、ｂ* はクロマティクネス指数を表す。上記金色調のＬ* 、ａ* 及びｂ* の測定は０度視野ＸＹＺ系による物体色の測定方法に従って、鏡面光沢の試験片について、スガ試験機（株）製色差計ＳＭ−２−ＳＣＨ［積分球方式、測定方式：反射、測定口径：１２ｍｍ］を用いて行われた。
【００４０】
【表１】
【表２】
表２において、ａ* は赤味をｂ* は黄味を表し、数値が大きくなるに従って濃くなる。
【００４３】
【表３】
表３はＸ線光電子分光法で測定した、Ａｕ−Ｆｅ合金被膜の場合の成分分析を示し、表中の▲１▼は金成膜時アルゴンのみを導入しプラズマを発生させない場合、▲２▼は金成膜時酸素を導入しプラズマを発生させた場合、▲３▼は金成膜時エチレンを導入しプラズマを発生させた場合をそれぞれ示す。
【００４５】
本発明による部品においては、金（Ａｕ）又は金（Ａｕ）と他の金属によって形成された被膜中に、窒素（Ｎ）、酸素（Ｎ）、炭素（Ｃ）、又はそれらの混合ガス成分が入ることにより、金粒子及び他の金属の粒子の配列が乱され赤味を帯びた金色が発色するものと考える。
【００４６】
本発明によれば、ガスの種類及び導入量を変えることにより、自由に金の色調を変えることができる。製品としては、特に、最外層被膜の下にＴｉ系被膜を有する金色装飾部品は、均一な金色調とすることができる。またＴｉＮ被膜を有する金色装飾部品は最外層被膜と基材との密着性に優れている。
以下、本発明を実施例により説明するが、本発明は、これは実施例に限定するものではない。
【００４７】
実施例１
ステンレススチールにより加工した腕時計用ケースを有機溶剤で洗浄し、この腕時計用ケースをイオンプレティング装置に配置した。
【００４８】
次に、装置内を１．０×１０-5Torrまで排気した後、アルゴンガスを装置内が３×１０-3Torrになるまで導入した。
次に、装置内部に備えられた熱電子フィラメントとプラズマ電極を駆動させてアルゴンのプラズマを形成させた。同時に基材である腕時計用ケースに−５０Ｖの電位が印加され、１０分間ボンバードクリーニングが行われた。
【００４９】
次に、アルゴンガスの導入を止め、装置内に窒素ガスが２．０×１０-3Torrになるまで導入された。
次いで、装置内部に備えられたプラズマ銃でプラズマを発生させた後、チタンを１０分間蒸発させてＴｉＮ被膜を０．５μｍの膜厚に形成させた。
【００５０】
次に、チタンの蒸発と窒素ガスの導入を止め、装置内を１．０×１０-5Torrまで排気した。
次いで、装置内に窒素ガスを１．０×１０-3Torrまで導入してプラズマを発生させた後、金７５原子％と鉄２５原子％からなる金−鉄混合物を蒸発させ、金−鉄合金膜の厚みが０．３μｍになったところで金−鉄混合物の蒸発を止め、製品が得られた。
【００５１】
得られた腕時計ケースは、均一な金色調を有しており、得られた色調はL * １８．６、ａ* ３．２ｂ* ８．５であった。之は表１及び表２の試料１に対応する。
【００５２】
実施例２
ステンレススチールにより加工した腕時計ケースを有機溶剤で洗浄し、この腕時計用ケースをイオンプレーティング装置に配置した。
【００５３】
次に、装置内を１．０×１０-5Torrまで排気した後、アルゴンガスを装置内が３×１０-3Torrになるまで導入した。
次に、装置内部に備えられた熱電子フィラメントとプラズマ電極を駆動させてアルゴンのプラズマを形成させた。同時に基材である腕時計用ケースに−５０Ｖの電位が印加され、１０分間ボンバードクリーニングが行われた。
【００５４】
次に、アルゴンガスの導入を止め、装置内に窒素ガスが２．０×１０-3Torrになるまで導入された。
次いで、装置内部に備えられたプラズマ銃でプラズマを発生させた後、チタンを１０分間蒸発させてＴｉＮ被膜を０．５μｍの膜厚に形成させた。
【００５５】
次に、チタンの蒸発と窒素ガスの導入を止め、装置内を１．０×１０-5Torrまで排気した。
次いで、装置内に窒素ガスを２．０×１０-3Torrまで導入してプラズマを発生させた後、金７５原子％と鉄２５原子％からなる金−鉄混合物を蒸発させ、金−鉄合金膜の厚みが０．３μｍになったところで金−鉄混合物の蒸発を止め、製品が得られた。
【００５６】
得られた腕時計ケースは、均一な金色調を有しており、得られた色調はL * １８．３、ａ* ４．５ｂ* ８．４であった。之は表１及び表２の試料４に対応する。
【００５７】
実施例３
ステンレススチールにより加工した腕時計ケースを有機溶剤で洗浄し、この腕時計用ケースをイオンプレーティング装置に配置した。
【００５８】
次に、装置内を１．０×１０-5Torrまで排気した後、アルゴンガスを装置内が３×１０-3Torrになるまで導入した。
次に、装置内部に備えられた熱電子フィラメントとプラズマ電極を駆動させてアルゴンのプラズマを形成させた。同時に基材である腕時計用ケースに−５０Ｖの電位が印加され、１０分間ボンバードクリーニングが行われた。
【００５９】
次に、アルゴンガスの導入を止め、装置内に窒素ガスが２．０×１０-3Torrになるまで導入された。
次いで、装置内部に備えられたプラズマ銃でプラズマを発生させた後、チタンを１０分間蒸発させてＴｉＮ被膜を０．５μｍの膜厚に形成させた。
【００６０】
次に、チタンの蒸発と窒素ガスの導入を止め、装置内を１．０×１０-5Torrまで排気した。
次いで、装置内に酸素を２５％含有する酸素アルゴン混合ガスを１．０×１０-3Torrまで導入してプラズマを発生させた後、金７５原子％と鉄２５原子％からなる金−鉄混合物を蒸発させ、金−鉄合金膜の厚みが０．３μｍになったところで金−鉄混合物の蒸発を止め、製品が得られた。
【００６１】
得られた腕時計ケースは、均一な金色調を有しており、得られた色調はL * ９．２、ａ* ７．１ｂ* ５．２であった。之は表１及び表２の試料６に対応する。
【００６２】
尚、上記実施例においては、Ａｕ−Ｆｅ合金で行ったがＡｕ−Ｔｉ合金、Ａｕ−Ｎｉ合金、Ａｕ−Ｐｄ合金、Ａｕ−Ｃｏ合金で行っても同様の効果が得られることは言うまでもない。また、Ａｕ−Ｔｉ−Ｐｄ、Ａｕ−Ｔｉ−Ｎｉ等の３元合金や４元合金等の合金で行っても同様の効果が得られる。尚、この合金の使用方法については、必要とする耐食性、硬度等の機能品質や、必要とする色調等によって使いわける。また、ガスの種類とその量で色調の変化を出したが、このガスの種類及びその量に、プラズマの強度の変化をプラスすることにより、更に微妙な色調を出すことができる。[0001]
[Industrial application fields]
The present invention relates to a golden decorative part and a manufacturing method thereof, and more particularly to a manufacturing method capable of adjusting a color tone.
[0002]
[Prior art]
Conventionally, watch parts such as watch bands by the ion plating method, and golden decorative parts such as rings, necklaces, earrings, etc. are given a high-class feeling or excellent corrosion resistance by forming a gold film on the outermost layer. Yes. Furthermore, an alloy film such as gold-nickel, gold-iron, gold-palladium, and gold-titanium alloy film is formed on the outermost layer of the decorative part instead of the pure gold film, and the decorative part is provided.
[0003]
[Problems to be solved by the invention]
These alloy films are light gold and each has a slightly different color tone. There is a tendency to become green. Furthermore, color matching with a reddish gold-plated part is difficult.
[0004]
The present invention is intended to solve the above-described problems in the prior art, and provides a decorative part that can change the color tone, and particularly exhibits a reddish gold color, and a method for manufacturing the decorative part. It is aimed.
[0005]
[Means for Solving the Problems]
The first golden decorative part according to the present invention comprises a substrate and an inert gas other than nitrogen at a pressure in the dry plating apparatus of 8 × 10 −4 to 5 × 10 −3 Torr by dry plating on the substrate. Titanium is evaporated under a gas atmosphere to contain a Ti-based film formed by containing inevitable components present in the dry plating apparatus, and an outermost layer film formed on this film. It is characterized by comprising 50 to 99.8 atomic% of gold, 0.1 to 30 atomic% of at least one element among nitrogen, oxygen and carbon and 0.1 to 20 atomic% of inevitable components. .
[0006]
The second golden decorative part according to the present invention comprises a base material and an inert gas other than nitrogen at a pressure in the dry plating apparatus of 8 × 10 −4 to 5 × 10 −3 Torr by dry plating on the base material. Titanium is evaporated under a gas atmosphere to contain a Ti-based film formed by containing inevitable components present in the dry plating apparatus, and an outermost layer film formed on this film. 50 to 98.9 atomic percent of gold, 0.1 to 30 atomic percent of at least one element of nitrogen, oxygen, and carbon, and 0.5 to 20 of at least one element of iron, titanium, nickel, palladium, and cobalt It is characterized by containing atomic% and inevitable components 0.5 to 20 atomic%.
[0007]
The third golden decorative part according to the present invention has a base material and an inert gas other than nitrogen at a pressure in the dry plating apparatus of 8 × 10 −4 to 5 × 10 −3 Torr by dry plating on the base material. Ti-based film formed by evaporating titanium under a gas atmosphere and containing inevitable components present in the dry plating apparatus, and titanium, tantalum, hafnium, vanadium, or zirconium formed on the film And an outermost layer film formed on this film, and the outermost layer film is composed of 50 to 99.8 atomic% of gold and at least one element of nitrogen, oxygen and carbon. It is characterized by containing 0.1 to 30 atomic% and unavoidable components of 0.1 to 20 atomic%.
[0008]
The fourth golden decorative part according to the present invention is a substrate and an inert gas other than nitrogen at a pressure in the dry plating apparatus of 8 × 10 −4 to 5 × 10 −3 Torr by dry plating on the substrate. Ti-based film formed by evaporating titanium under a gas atmosphere and containing inevitable components present in the dry plating apparatus, and titanium, tantalum, hafnium, vanadium, or zirconium formed on the film And an outermost layer film formed on the film, and the outermost layer film is composed of 50 to 98.9 atomic% of gold and at least one element of nitrogen, oxygen, and carbon. 0.1 to 30 atomic%, and at least one element of iron, titanium, nickel, palladium, and cobalt contains 0.5 to 20 atomic% and unavoidable components of 0.5 to 20 atomic%. It is a feature.
[0009]
The thickness of the Ti-based film is 0.1 to 0.5 μm.
[0010]
The titanium, or tantalum, or hafnium, or vanadium, or of a coating made of nitride of zirconium thickness, characterized 0.1~10μm der Rukoto.
[0011]
The thickness of the outermost coating is characterized 0.05~0.5μm der Rukoto.
[0012]
In the dry plating method, comprising a substrate, the initial evacuation of the dry plating apparatus before the film formation, characterized that you have been made up to 5 × 10 -5 ~1.0 × 10 -6 Torr.
[0013]
The film thickness of the Ti-based film was placed in the apparatus after initial evacuation from 5 × 10 −5 to 1.0 × 10 −6 Torr in the dry plating apparatus before film formation including the base material . It is formed by a dry plating method in an inert gas other than nitrogen on the surface of the substrate, and has a film thickness of 0.05 to 0.5 μm.
[0014]
The first method for producing a golden decorative part according to the present invention is an initial evacuation to 5 × 10 −5 to 1.0 × 10 −6 Torr in a dry plating apparatus including a base material before film formation, in a dry plating method. After that, an inert gas other than nitrogen is introduced into the dry plating apparatus up to 8 × 10 −4 to 5 × 10 −3 Torr, and titanium is evaporated on the base material in an inert gas atmosphere. Ti-based film containing inevitable components present in the substrate is formed, and then in this dry plating apparatus, nitrogen gas, oxygen gas, hydrocarbon-based gas, or a mixed gas atmosphere thereof is formed on the Ti-based film. And an outermost layer coating comprising 50 to 99.8 atomic percent of gold, 0.1 to 30 atomic percent of at least one element of nitrogen, oxygen and carbon and 0.1 to 20 atomic percent of inevitable components It is characterized by forming.
[0015]
The second method for producing a golden decorative part according to the present invention is an initial evacuation from 5 × 10 −5 to 1.0 × 10 −6 Torr in a dry plating apparatus including a base material before film formation in a dry plating method. After that, an inert gas other than nitrogen is introduced into the dry plating apparatus up to 8 × 10 −4 to 5 × 10 −3 Torr, and titanium is evaporated on the base material in an inert gas atmosphere. Ti-based film containing inevitable components present in the substrate is formed, and then in this dry plating apparatus, nitrogen gas, oxygen gas, hydrocarbon-based gas, or a mixed gas atmosphere thereof is formed on the Ti-based film. In addition, 50 to 98.9 atomic percent of gold, 0.1 to 30 atomic percent of at least one element of nitrogen, oxygen, and carbon, and 0.5 element of at least one of iron, titanium, nickel, palladium, and cobalt ~ 20 atomic% and inevitable component 0.5-20 atomic% It is characterized by forming an outermost layer coating comprising a.
[0016]
A third method for producing a golden decorative part according to the present invention is an initial evacuation from 5 × 10 −5 to 1.0 × 10 −6 Torr in a dry plating apparatus including a base material before film formation in a dry plating method. After that, an inert gas other than nitrogen is introduced into the dry plating apparatus up to 8 × 10 −4 to 5 × 10 −3 Torr, and titanium is evaporated on the base material in an inert gas atmosphere. to form a Ti-based coating containing inevitable ingredients present in, then, in the dry plating apparatus, on the Ti-based film, titanium in a nitrogen gas atmosphere, or tantalum, or hafnium, or vanadium, or Zirconium is evaporated to form nitrides of the respective elements, and then gold 50 to 99 is deposited on the nitride films in an atmosphere of nitrogen gas, oxygen gas, hydrocarbon gas, or a mixed gas thereof. .8 atomic% of nitrogen, oxygen, carbon At least one element is 0.1 to 30 atomic% Chi is characterized by forming an outermost layer coating comprising an unavoidable component 0.1 to 20 atomic%.
[0017]
A third method for producing a golden decorative part according to the present invention is an initial evacuation from 5 × 10 −5 to 1.0 × 10 −6 Torr in a dry plating apparatus including a base material before film formation in a dry plating method. After that, an inert gas other than nitrogen is introduced into the dry plating apparatus up to 8 × 10 −4 to 5 × 10 −3 Torr, and titanium is evaporated on the base material in an inert gas atmosphere. Then, a Ti-based film containing inevitable components is formed, and then, in this dry plating apparatus, titanium, tantalum, hafnium, vanadium, or zirconium is formed on the Ti-based film in a nitrogen gas atmosphere. Are vaporized to form nitrides of the respective elements, and then gold 50 to 98.9 is formed on these nitride films in an atmosphere of nitrogen gas, oxygen gas, hydrocarbon gas, or a mixed gas thereof. Out of atomic%, nitrogen, oxygen, carbon At least one element of 0.1 to 30 atomic%, at least one element of iron, titanium, nickel, palladium, and cobalt contains 0.5 to 20 atomic% and unavoidable components of 0.5 to 20 atomic% The outermost layer film is formed.
[0018]
The Ti-based film is formed with a film thickness of 0.1 to 0.5 μm .
[0019]
The film made of nitride of titanium, tantalum, hafnium, vanadium, or zirconium is formed with a film thickness of 0.1 to 10 μm .
[0020]
The outermost layer film is formed with a film thickness of 0.05 to 0.5 μm .
[0021]
Specific Description Hereinafter, the golden decorative part and the manufacturing method thereof according to the present invention will be described in detail.
[0022]
The golden decorative part according to the present invention comprises a base material and an outermost layer film formed on the base material by a dry plating method such as a vacuum deposition method, a sputtering method or an ion plating method. Or an alloy of gold and another metal, a component of nitrogen, oxygen or carbon and an unavoidable component in a specific ratio. The other metal is iron, titanium, nickel, palladium, or cobalt.
[0023]
In the golden decorative part according to the present invention, a titanium film, a tantalum film, a hafnium film, or a zirconium film may be formed on the substrate, and an outermost layer film may be formed thereon. The golden decorative part having such a nitride film is excellent in the adhesion between the outermost layer film and the substrate.
[0024]
The substrate used in the present invention varies depending on the type of decorative part, and is a material such as metal, plastic, or ceramic.
In the golden decorative part according to the present invention, the outermost layer coating has a gold content of 50 to 99.8 or 98.9 atomic%, preferably 81.5 to 96.5 atomic%, more preferably 88 to 96.5 atomic%, Other metal is 0.5 to 20 atomic%, preferably 2.5 to 7 atomic%, more preferably 3 to 7 atomic%, nitrogen, oxygen or carbon is 0.1 to 30 atomic%, inevitable component 0.5 ˜20 atomic%. Here, the unavoidable component is a residual gas component present in the apparatus, and refers to oxygen, carbon, nitrogen, or the like. Therefore, it cannot be distinguished whether nitrogen, oxygen, or carbon contained in the coating is a gas component actively introduced or an inevitable component. However, the amount of inevitable components contained in the coating is usually constant, and how much of the introduced gas component is contained in the coating can be seen as the difference between when the gas is introduced and when it is not introduced.
[0025]
For example, in Table 3, the oxygen incorporated in the film is 1.1% difference between (1) and (2)
The carbon incorporated in the film is 8.4% difference between (2) and (3)
Can be seen.
[0026]
Next, a method for manufacturing a golden decorative part according to the present invention will be described.
A golden decorative part composed of a base material and an outermost layer coating is obtained by applying a mixed coating of 50 to 98.9 atomic percent of gold and 0.5 to 20 atomic percent of iron in a nitrogen gas atmosphere in a dry plating apparatus. Form.
[0027]
In addition, a golden decorative part composed of a base material, a Ti-based film, and an outermost layer film is formed by applying titanium on a base material in an inert gas atmosphere such as argon, helium, neon other than nitrogen in a dry plating apparatus. Evaporate to form a Ti-based film containing inevitable components present in the dry plating apparatus,
Next, in this dry plating apparatus, a mixed film of 50 to 98.9 atomic% of gold and 0.5 to 20 atomic% of iron is formed on the Ti-based film in a nitrogen gas atmosphere.
[0028]
Further, the golden decorative part composed of the base material, the TiN film, and the outermost layer film is formed on the base material by evaporating titanium under a nitrogen gas atmosphere in a dry plating apparatus to form a TiN film. In this dry plating apparatus, a mixed film of 50 to 98.9 atomic% of gold and 0.5 to 20 atomic% of iron is formed on the TiN film in a nitrogen gas atmosphere.
[0029]
Furthermore, the golden decorative part consisting of the base material, Ti-based film, TiN film and outermost layer film exists in the dry plating equipment by evaporating titanium on the base material in an inert gas atmosphere other than nitrogen. To form a Ti-based film containing inevitable ingredients,
Next, in this dry plating apparatus, titanium is evaporated in a nitrogen gas atmosphere on the Ti-based film, and titanium is evaporated in a nitrogen gas atmosphere on the Ti-based film to form a TiN film,
Next, in this dry plating apparatus, a mixed film of 50 to 98.9 atomic% of gold and 0.5 to 20 atomic% of iron is formed on the TiN film in a nitrogen gas atmosphere.
[0030]
As a method other than the above method, there are oxygen and hydrocarbon gas as gas other than nitrogen, and there are titanium, nickel, palladium, and cobalt as metal other than iron. Further, there are TaN, HfN, VN, and ZrN as films other than the TiN film.
[0031]
In the present invention, the outermost layer coating can be formed by sputtering, vacuum deposition, or ion plating, but is preferably formed by ion plating.
[0032]
Hereinafter, the case where each coating in the golden decorative part according to the present invention, in particular, the outermost coating is formed of a gold-iron alloy by an ion plating method will be described more specifically. A base material such as a wristwatch band is preferably washed with an organic solvent or the like in advance. Further, after evacuating the inside of the ion plating apparatus to 5 × 10 −5 to 1.0 × 10 −6 Torr, preferably 1.0 × 10 −5 to 1.0 × 10 −6 Torr, the atmosphere gas is changed to 8 × 10 -4 ~5 × -3 Torr, preferably introduced to 1.0 × 10 -3 ~2.0 × 10 -3 Torr.
[0033]
In order to obtain an outermost layer coating film having a uniform gold color tone, the pressure inside the apparatus before film formation should be low, and evacuation to 1 × 10 −5 Torr or less, preferably 1 × 10 −6 Torr or less. desirable. That is, as the pressure inside the apparatus decreases, the amount of inevitable components inside the apparatus decreases, and the gold color tone becomes uniform.
[0034]
The outermost layer coating of the golden decorative part according to the present invention has a thickness of usually 0.05 to 0.5 μm, preferably 0.1 to 0.3 μm.
The film thickness of the TiN film is 0.1 to 10 μm, preferably 0.1 to 2 μm, and the film thickness of the Ti-based film containing many inevitable components is 0.1 to 0.5 μm, preferably 0. It is desirable to be about 2 to 0.3 μm.
[0035]
By forming the TiN film as described above, the adhesion between the outermost layer film of the gold-iron alloy film and the substrate can be improved. Instead of the TiN film, a golden nitride such as ZrN or HfN is used. A film may be formed.
[0036]
In the present invention, a gold-iron mixture may be used as an evaporation source. However, two evaporation sources are provided, gold is used as one evaporation source, iron is used as the other evaporation source, and gold and iron are evaporated separately. You may let them.
[0037]
When a gold-iron mixture is used as the evaporation source in the present invention, gold and iron are used so that the composition of the outermost layer coating obtained is 50 to 98.9 atomic% of gold and 0.5 to 20 atomic% of iron. However, specifically, it is preferable to use a gold-iron mixture or a gold-iron alloy containing 75 to 90 atomic% of gold and 10 to 25 atomic% of iron.
[0038]
When oxygen is used, a mixed gas of oxygen and an inert gas such as argon is used. Moreover, hydrocarbon, for example, ethylene gas is used as carbon.
[0039]
Table 1 shows the change in the amount of nitrogen and oxygen, and Table 2 shows the change in the color tone. Here, L * is the brightness index in the International Lighting Commission (CIE) CIE1976 (L * a * b * ) color space, and a * and b * represent the chromaticness index. The above-mentioned gold color L * , a *, and b * are measured on a specular gloss test piece according to the object color measurement method using a 0 degree visual field XYZ system, and the color difference meter SM-2-SCH [ Integrating sphere method, measurement method: reflection, measurement aperture: 12 mm].
[0040]
[Table 1]
[Table 2]
In Table 2, a * represents reddishness and b * represents yellowishness, which increases as the value increases.
[0043]
[Table 3]
Table 3 shows the component analysis in the case of the Au-Fe alloy film measured by X-ray photoelectron spectroscopy, and (1) in the table indicates that only argon is introduced during the gold film formation and no plasma is generated. (2) Indicates the case where oxygen is introduced during the gold film formation to generate plasma, and (3) indicates the case where ethylene is introduced during the gold film formation to generate plasma.
[0045]
In the component according to the present invention, nitrogen (N), oxygen (N), carbon (C), or a mixed gas component thereof is contained in a film formed of gold (Au) or gold (Au) and another metal. By entering, it is considered that the arrangement of gold particles and other metal particles is disturbed, and a reddish gold color is developed.
[0046]
According to the present invention, the color tone of gold can be freely changed by changing the type and amount of gas introduced. As a product, in particular, a golden decorative part having a Ti-based coating under the outermost coating layer can have a uniform golden tone. Further, the golden decorative part having the TiN film is excellent in the adhesion between the outermost layer film and the substrate.
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example.
[0047]
Example 1
The watch case processed with stainless steel was washed with an organic solvent, and this watch case was placed in an ion plating apparatus.
[0048]
Next, after evacuating the inside of the apparatus to 1.0 × 10 −5 Torr, argon gas was introduced until the inside of the apparatus reached 3 × 10 −3 Torr.
Next, the thermoelectron filament and plasma electrode provided inside the apparatus were driven to form argon plasma. At the same time, a potential of −50 V was applied to the watch case as the base material, and bombard cleaning was performed for 10 minutes.
[0049]
Next, the introduction of argon gas was stopped, and nitrogen gas was introduced into the apparatus until it reached 2.0 × 10 −3 Torr.
Next, plasma was generated by a plasma gun provided inside the apparatus, and then the titanium was evaporated for 10 minutes to form a TiN film having a thickness of 0.5 μm.
[0050]
Next, evaporation of titanium and introduction of nitrogen gas were stopped, and the inside of the apparatus was evacuated to 1.0 × 10 −5 Torr.
Next, nitrogen gas was introduced into the apparatus up to 1.0 × 10 −3 Torr to generate plasma, and then a gold-iron mixture consisting of 75 atomic% gold and 25 atomic% iron was evaporated to obtain a gold-iron alloy. When the thickness of the film reached 0.3 μm, the evaporation of the gold-iron mixture was stopped and a product was obtained.
[0051]
The obtained watch case had a uniform gold color tone, and the obtained color tone was L * 18.6, a * 3.2b * 8.5. This corresponds to Sample 1 in Tables 1 and 2.
[0052]
Example 2
The watch case processed with stainless steel was washed with an organic solvent, and this watch case was placed in an ion plating apparatus.
[0053]
Next, after evacuating the inside of the apparatus to 1.0 × 10 −5 Torr, argon gas was introduced until the inside of the apparatus reached 3 × 10 −3 Torr.
Next, the thermoelectron filament and plasma electrode provided inside the apparatus were driven to form argon plasma. At the same time, a potential of −50 V was applied to the watch case as the base material, and bombard cleaning was performed for 10 minutes.
[0054]
Next, the introduction of argon gas was stopped, and nitrogen gas was introduced into the apparatus until it reached 2.0 × 10 −3 Torr.
Next, plasma was generated by a plasma gun provided inside the apparatus, and then the titanium was evaporated for 10 minutes to form a TiN film having a thickness of 0.5 μm.
[0055]
Next, evaporation of titanium and introduction of nitrogen gas were stopped, and the inside of the apparatus was evacuated to 1.0 × 10 −5 Torr.
Next, nitrogen gas was introduced into the apparatus up to 2.0 × 10 −3 Torr to generate plasma, and then a gold-iron mixture composed of 75 atomic% gold and 25 atomic% iron was evaporated to obtain a gold-iron alloy. When the thickness of the film reached 0.3 μm, the evaporation of the gold-iron mixture was stopped and a product was obtained.
[0056]
The obtained watch case had a uniform gold color tone, and the obtained color tone was L * 18.3 and a * 4.5b * 8.4. This corresponds to Sample 4 in Tables 1 and 2.
[0057]
Example 3
The watch case processed with stainless steel was washed with an organic solvent, and this watch case was placed in an ion plating apparatus.
[0058]
Next, after evacuating the inside of the apparatus to 1.0 × 10 −5 Torr, argon gas was introduced until the inside of the apparatus reached 3 × 10 −3 Torr.
Next, the thermoelectron filament and plasma electrode provided inside the apparatus were driven to form argon plasma. At the same time, a potential of −50 V was applied to the watch case as the base material, and bombard cleaning was performed for 10 minutes.
[0059]
Next, the introduction of argon gas was stopped, and nitrogen gas was introduced into the apparatus until it reached 2.0 × 10 −3 Torr.
Next, plasma was generated by a plasma gun provided inside the apparatus, and then the titanium was evaporated for 10 minutes to form a TiN film having a thickness of 0.5 μm.
[0060]
Next, evaporation of titanium and introduction of nitrogen gas were stopped, and the inside of the apparatus was evacuated to 1.0 × 10 −5 Torr.
Next, after introducing oxygen argon mixed gas containing 25% oxygen up to 1.0 × 10 −3 Torr in the apparatus to generate plasma, a gold-iron mixture comprising 75 atomic% gold and 25 atomic% iron When the thickness of the gold-iron alloy film reached 0.3 μm, evaporation of the gold-iron mixture was stopped and a product was obtained.
[0061]
The obtained watch case had a uniform gold color tone, and the obtained color tone was L * 9.2, a * 7.1b * 5.2. This corresponds to Sample 6 in Tables 1 and 2.
[0062]
In the above embodiment, the Au—Fe alloy is used, but it goes without saying that the same effect can be obtained by using an Au—Ti alloy, Au—Ni alloy, Au—Pd alloy, or Au—Co alloy. Further, the same effect can be obtained even when the reaction is performed with a ternary alloy such as Au-Ti-Pd or Au-Ti-Ni or an alloy such as a quaternary alloy. In addition, about the usage method of this alloy, it uses properly by functional quality, such as required corrosion resistance and hardness, and a required color tone. Further, although the color tone changes depending on the type and amount of gas, a more subtle color tone can be obtained by adding a change in plasma intensity to the type and amount of gas.
Claims (16)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16910494A JP3909092B2 (en) | 1994-07-21 | 1994-07-21 | Golden decorative part and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16910494A JP3909092B2 (en) | 1994-07-21 | 1994-07-21 | Golden decorative part and manufacturing method thereof |
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| Publication Number | Publication Date |
|---|---|
| JPH0835055A JPH0835055A (en) | 1996-02-06 |
| JP3909092B2 true JP3909092B2 (en) | 2007-04-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP16910494A Expired - Fee Related JP3909092B2 (en) | 1994-07-21 | 1994-07-21 | Golden decorative part and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP3909092B2 (en) |
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1994
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| JPH0835055A (en) | 1996-02-06 |
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