EP0844539A1 - Zierelement insbesondere Bauteil einer Uhr - Google Patents

Zierelement insbesondere Bauteil einer Uhr Download PDF

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Publication number
EP0844539A1
EP0844539A1 EP96118796A EP96118796A EP0844539A1 EP 0844539 A1 EP0844539 A1 EP 0844539A1 EP 96118796 A EP96118796 A EP 96118796A EP 96118796 A EP96118796 A EP 96118796A EP 0844539 A1 EP0844539 A1 EP 0844539A1
Authority
EP
European Patent Office
Prior art keywords
decorative element
substrate
element according
hard
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96118796A
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English (en)
French (fr)
Other versions
EP0844539B1 (de
Inventor
Michael Bach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rado Uhren AG
Original Assignee
Rado Uhren AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rado Uhren AG filed Critical Rado Uhren AG
Priority to DE69630792T priority Critical patent/DE69630792T2/de
Priority to EP96118796A priority patent/EP0844539B1/de
Priority to TW086115393A priority patent/TW346557B/zh
Priority to KR1019970055762A priority patent/KR100547850B1/ko
Priority to US08/966,481 priority patent/US6123450A/en
Priority to CNB971141363A priority patent/CN1161673C/zh
Priority to JP32085797A priority patent/JP4476371B2/ja
Priority to SG1997004122A priority patent/SG67443A1/en
Publication of EP0844539A1 publication Critical patent/EP0844539A1/de
Priority to HK98115089A priority patent/HK1013779A1/xx
Application granted granted Critical
Publication of EP0844539B1 publication Critical patent/EP0844539B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G04B37/223—Materials or processes of manufacturing pocket watch or wrist watch cases metallic cases coated with a nonmetallic layer

Definitions

  • the present invention relates to a decorative element comprising a surface coated with a protective layer and decorative in hard material, more particularly a component of a timepiece having a layer of hard material which is not very rough and which can be if necessary, polished without undue difficulty.
  • patent EP-A-0 199 207 it has already been proposed to make decorative elements such as a box of watch, including parts of the visible outer surface, likely to come into contact with foreign bodies, for example the upper sides of the box, have a unalterable aspect, that is to say that they can neither be scratched in contact with such bodies, nor oxidize or tarnish on contact with air so that it is possible to give these parts of the box a fine appearance and neat.
  • the cited patent proposes the use of metal carbide inserts (carbide tungsten or titanium carbide) coated with polycrystalline diamond layer having a thickness typically between 0.4 and 0.8 mm, these plates being attached to the watch case by gluing or welding.
  • the platelets are obtained from pellets of maximum diameter equal to 51 mm.
  • the manufacture of such lozenges requires the use of the equivalent around 4000 diamonds, the equivalent of 16.5 carats. These diamonds are first processed into powder and the powder is sintered at around 1,500 ° C and at a pressure of around 5,000 MPa on a hard metal substrate (carbide metallic). The pellets are then sanded and planned using a discharge process electric, and finally polished during a long process of polishing with diamond wheels. Then the lozenges are carefully selected, especially when these pastilles are intended for the realization of parts or components of wristwatches, in order to control the thickness and appearance visual, in particular the homogeneity of the color of the layer diamond. The pellets obtained are then machined, to using methods known as EDM machining or laser machining, in their form final to obtain the desired plate or ring. Finally, the sharp edges of the insert are removed during a final chamfering operation using of a diamond wheel.
  • the quantity of diamond powder and the amount of energy required to transform the powder by sintering, polish the diamond layer obtained, machine and chamfer the pellet to obtain a wafer finished are such that the cost price of the pellet is very high and leads to increasing so prohibitive the cost of products in which are integrated such plates.
  • this process requires the use of a sintered hard metal substrate comprising cobalt as binder for reasons of adhesion with the powder diamond.
  • cobalt as a binder in the substrate makes the latter easily oxidizable, which requires the deposition of a protective layer on the substrate and further increases the cost price of the pastille.
  • the topography of the layer obtained according to this process presents a multitude of microcrystals of diamond with dimensions of the order of 5 ⁇ m, in shape parallelepipedic with extremely hard edges (of around 10,000 Vickers) and extremely resistant to wear.
  • This hardness and high wear resistance are due to the almost exclusive presence of type bond SP3 between the carbon atoms that form the layer diamond.
  • the multitude of well-defined edges on the surface of these diamond layers therefore forms a multitude of anchor points for rubbed material.
  • a stripe of a commonly used material, i.e. soft compared to diamond leaves traces visible on the surface of the hard layer, which cannot be eliminated completely, for example using a simple means, such as a damp cloth, available of all consumers.
  • the main aim of the invention is therefore to remedy the disadvantages of the aforementioned prior art in providing a decorative element, particularly a component of a timepiece, comprising a surface layer of a very large material hardness having a microcrystalline structure and having a very regular topography and very little abrasive.
  • the subject of the invention is an element decorative comprising at least one coated substrate partially with a protective and decorative layer in hard material, characterized in that the hard material of said layer has a microcrystalline structure and a outer surface with a regular topography of the cauliflower type.
  • the hard layer has the advantage not to have sharp edges or deep hollows, even before polishing the surface of this layer.
  • the marks left of softer material deposits at the surface of the coating following a scratch can thus be easily reduced or even eliminated by a means simple, such as a cloth or finger, available to any consumer. Note that we can advantageously use such unpolished coatings without fear of mark the surface of the coating almost indelibly as was the case in interior art.
  • the hard material layer is specularly polished.
  • the hard material is diamond or nitride cubic boron.
  • the surface hardness of covered surfaces is around 8,000 HV, which leads to abrasion resistance four times superior to that of diamond art coatings which have hardnesses of the order of 6,000 to 8,000 HV.
  • a decorative element according to the invention now goes be described in detail as part of an application to the production of a component part of watchmaking and more particularly of a bezel of a wristwatch shown in Figure 1 and designated by the general reference number 1.
  • Wristwatch 1 includes four pieces main: an inner middle 2, a bezel 4, a glass 6 and a back 8.
  • the inner middle 2 and the glasses 4 have shapes which are determined from so that the manufacturing operations are simplified and those of assembly facilitated.
  • the inner middle part 2 is made of a metal easily machinable, for example stainless steel.
  • the middle 2 which is intended to contain a movement 10 surmounted by a dial 12 includes an upper part 14 and a lower part 16.
  • the lower part 16 surrounds and carries movement 10 and dial 12 of a classic way which will not be described further in detail.
  • the bottom 8 is also fixed to the part lower 16 conventionally through a seal 18.
  • the middle part 2 is fixed to the bezel 4 by a ring 20 of deformable material engaged in a radial clearance provided between facing coaxial cylindrical surfaces 22, 24 case 2 and bezel 4 respectively.
  • the glass 6 is fixed in the opening of the bezel 4 by means of an intermediate seal 26 and is not supported on the upper face 28 of the middle part interior 2.
  • the outer surface 30 of the bezel 4, which is in the embodiment describes the surface to be coated of hard material, includes a first parallel face 32 on the dial plane.
  • the face 32 is extended by a second side 34 frustoconical, then by a third side lateral circular 36 perpendicular to the plane of the dial.
  • the sides 32, 34, and 36 of the bezel are coated according to the invention a thin layer 38 of material very hard such as a layer of diamond or boron nitride.
  • layer 38 has a thickness of between 1 and 20 micrometers and a hardness of the order of 8,000 to 10,000 HV.
  • a method will be described below for carrying out a component of a timepiece according to the invention such as the telescope 4 on a certain part of which we are going to deposit a layer of diamond having a microcrystalline structure and surface topography cauliflower type.
  • the substrate has a hardness greater than 800 HV, and typically a metal substrate hard sintered or ceramic is quite suitable. In effect if the substrate material is too soft, shock on the thin layer 38 will cause deformation of the substrate and in most cases a crack in the layer 38, due to poor properties elastic.
  • a metal substrate hard preferably a hard stainless metal such as than a sintered hard metal based on tungsten carbide or of titanium carbide, these carbides being bonded using metallic binders such as nickel, chromium, cobalt or molybdenum or a mixture thereof.
  • the surfaces to be coated are subjected to a surface treatment in order to reduce the concentration of binder on the surface (over a few tens of micrometers).
  • this surface treatment can consist of a vacuum heat treatment during which the binder on the surface evaporates, or alternatively a chemical treatment in a solution of H 2 SO 4 / H 2 O 2 at a respective concentration of 5% and 35%.
  • ceramics having high impact resistance based on carbide or nitride.
  • ceramic based on carbide silicon and / or silicon nitride will be appropriate.
  • Oxide-based ceramic substrates can also be used, however prior treatment to obtain a carbide on the surface which must be coated is required.
  • this treatment may consist of heat treatment in an atmosphere controlled, chemical or plasma treatment.
  • the substrate is introduced into the enclosure of a phase chemical deposition installation steam, the substrate being arranged on a suitable assembly to deposit a layer of diamond and obtain a layer having a topography or structure of the type cauliflower.
  • a method for obtaining such a layer is described in detail in the publication called “The role of hydrogen in diamond synthesis from carbon dioxide-hydrocarbon gases by micro wave plasma chemical vapor deposition "by Chia-Fu Chen and Tsao-Ming hong, published in 1992 in Surface and Coatings Technology 54/55, pages 368 to 373, which is incorporated here in its entirety by reference. It is understood that any other method for depositing layers of hard material having a structure or topography of the type cauliflower on a substrate are possible.
  • the surface of the diamond layer obtained has a topography comprising an agglomerate of microglobules, as shown in Figure 4 which represents a micrograph of the surface of a diamond layer of the type cauliflower at a magnification of 2,000 times.
  • Figure 4 represents a micrograph of the surface of a diamond layer of the type cauliflower at a magnification of 2,000 times.
  • the bonds between the carbon atoms are almost exclusively of type SP3 and having a hardness of around 10,000 HV
  • the cauliflower type diamond layers used in the decorative element according to the invention comprises a high proportion of carbon atoms linked by SP2 type bonds with a low proportion of bonds type SP3 and have a hardness of the order of 8,000 HV.
  • This mixture of carbon-carbon bonds of the type SP3 and SP2 is in fact a fault which appears during the growth formation on the substrate surface of the layer of diamond and which leads to a structure in slightly rough microglobules such as those shown in Figure 4.
  • the cauliflower-like layer therefore has a primary advantage in use on element constituting a timepiece, namely that the hard coat can be specularly polished using a diamond wheel without excessive difficulty.
  • the decorative element according to the invention is not limited to the production of an element constituting a timepiece described above and than other decorative elements such as the link bracelet 38 shown in Figure 2 can be considered.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Vapour Deposition (AREA)
  • Powder Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Physical Vapour Deposition (AREA)
  • Electric Clocks (AREA)
  • Adornments (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP96118796A 1996-11-22 1996-11-22 Zierelement insbesondere Bauteil einer Uhr Expired - Lifetime EP0844539B1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE69630792T DE69630792T2 (de) 1996-11-22 1996-11-22 Zierelement insbesondere Bauteil einer Uhr
EP96118796A EP0844539B1 (de) 1996-11-22 1996-11-22 Zierelement insbesondere Bauteil einer Uhr
TW086115393A TW346557B (en) 1996-11-22 1997-10-18 Decorative element, in particular an element forming a part of a timepiece
KR1019970055762A KR100547850B1 (ko) 1996-11-22 1997-10-29 장식요소, 특히 시계의 일부를 형성하는 장식요소
US08/966,481 US6123450A (en) 1996-11-22 1997-11-07 Decorative element, in particular an element forming a part of a timepiece
CNB971141363A CN1161673C (zh) 1996-11-22 1997-11-21 作为钟表部件的装饰部件
JP32085797A JP4476371B2 (ja) 1996-11-22 1997-11-21 装飾要素、特に時計の一部を形成する要素
SG1997004122A SG67443A1 (en) 1996-11-22 1997-11-22 Decorative element in particular an element forming a part of a timepiece
HK98115089A HK1013779A1 (en) 1996-11-22 1998-12-23 Decorative element, in particular an element forming a part of a timepiece.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96118796A EP0844539B1 (de) 1996-11-22 1996-11-22 Zierelement insbesondere Bauteil einer Uhr

Publications (2)

Publication Number Publication Date
EP0844539A1 true EP0844539A1 (de) 1998-05-27
EP0844539B1 EP0844539B1 (de) 2003-11-19

Family

ID=8223430

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96118796A Expired - Lifetime EP0844539B1 (de) 1996-11-22 1996-11-22 Zierelement insbesondere Bauteil einer Uhr

Country Status (9)

Country Link
US (1) US6123450A (de)
EP (1) EP0844539B1 (de)
JP (1) JP4476371B2 (de)
KR (1) KR100547850B1 (de)
CN (1) CN1161673C (de)
DE (1) DE69630792T2 (de)
HK (1) HK1013779A1 (de)
SG (1) SG67443A1 (de)
TW (1) TW346557B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3330808A1 (de) * 2016-11-24 2018-06-06 Seiko Epson Corporation Uhrenteil und uhr

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69630792T2 (de) * 1996-11-22 2004-09-23 Montres Rado S.A. Zierelement insbesondere Bauteil einer Uhr
EP1378805B1 (de) * 2002-07-02 2007-01-17 CSEM Centre Suisse d'Electronique et de Microtechnique SA Recherche et Développement Uhrwerk mit Antenne
EP1548525B2 (de) * 2003-12-23 2017-08-16 Rolex Sa Keramisches Element für Uhrengehäuse und Verfahren zu seiner Herstellung
KR20040072581A (ko) 2004-07-29 2004-08-18 (주)제이씨 프로텍 전자기파 증폭중계기 및 이를 이용한 무선전력변환장치
DE07405187T1 (de) * 2007-07-02 2008-12-04 Rolex Sa Wasserdichtes Armbanduhrgehäuse
EP3246767B1 (de) * 2016-05-19 2019-01-09 The Swatch Group Research and Development Ltd. Herstellungsverfahren einer uhr, die mit einem hohlen oder reliefartigen verkleidungselement ausgestattet ist
EP3923088A1 (de) * 2020-06-12 2021-12-15 Comadur S.A. Verfahren zur herstellung eines verzierungsteils aus hartem material, das mit einer polymerbeschichtung versehen ist

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH2962A (de) * 1891-02-04 1891-08-15 Baumgartner J J Bohrerschärfungsapparat für Stickmaschinen
WO1985003364A1 (fr) * 1984-01-26 1985-08-01 C.R. Spillmann S.A. Piece d'horlogerie, de bijouterie, de joaillerie ou element d'une telle piece
EP0199207A1 (de) 1985-04-16 1986-10-29 Montres Rado S.A. Armbanduhr mit von einem extraharten Material überzogenen Teilen
DE3706818A1 (de) * 1986-03-03 1987-09-10 Nippon Musical Instruments Mfg Verfahren zur herstellung eines dekorativen materials
US4734339A (en) 1984-06-27 1988-03-29 Santrade Limited Body with superhard coating

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
CH296274A (fr) * 1949-11-09 1954-01-31 Cellophane Sa Appareil pour la production d'articles enveloppés en matière se ramollissant à la chaleur.
JPS59197559A (ja) * 1983-04-21 1984-11-09 Sumitomo Electric Ind Ltd 被覆型時計枠
KR930000141Y1 (ko) * 1987-11-25 1993-01-09 주식회사 금성사 영상 출력 리미터 회로
US5433977A (en) * 1993-05-21 1995-07-18 Trustees Of Boston University Enhanced adherence of diamond coatings by combustion flame CVD
US5560839A (en) * 1994-06-27 1996-10-01 Valenite Inc. Methods of preparing cemented metal carbide substrates for deposition of adherent diamond coatings and products made therefrom
US5650059A (en) * 1995-08-11 1997-07-22 Credo Tool Company Method of making cemented carbide substrate
DE69630792T2 (de) * 1996-11-22 2004-09-23 Montres Rado S.A. Zierelement insbesondere Bauteil einer Uhr

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH2962A (de) * 1891-02-04 1891-08-15 Baumgartner J J Bohrerschärfungsapparat für Stickmaschinen
WO1985003364A1 (fr) * 1984-01-26 1985-08-01 C.R. Spillmann S.A. Piece d'horlogerie, de bijouterie, de joaillerie ou element d'une telle piece
US4734339A (en) 1984-06-27 1988-03-29 Santrade Limited Body with superhard coating
EP0199207A1 (de) 1985-04-16 1986-10-29 Montres Rado S.A. Armbanduhr mit von einem extraharten Material überzogenen Teilen
DE3706818A1 (de) * 1986-03-03 1987-09-10 Nippon Musical Instruments Mfg Verfahren zur herstellung eines dekorativen materials

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CH-A-2962/74 (JEAN SINGER ET CIE, S.A.) *
CHIA-FU CHEN AND TSAO-MING HONG: "THE ROLE OF HYDROGEN IN DIAMOND SYNTHESIS FROM CARBON DIOXIDE-HYDROCARBON GASES BY MICROWAVE PLASMA CHEMICAL VAPOR DEPOSITION", SURFACE AND COATINGS TECHNOLOGY, vol. 54/55, 1992, SWITZERLAND, pages 368 - 373, XP000646098 *
CHIA-FU CHEN, TSAO-MING HONG: "The role of hydrogen in diamond synthesis from carbon dioxyde-hydrocarbon gases by micro wave plasma chemical vapor deposition", REVUE SURFACE AND COATINGS TECHNOLOGY, vol. 54/55, 1992, pages 368 - 373
COPPERTHWAITE R.G. AND WITCOMB M.J.: "ELECTRON MICROSCOPY AND ESCA STUDIES OF NIOBIUM FILMS SPUTTER DEPOSITED ON STAINLESS STEEL", ELECTRON MICROSCOPY SOCIETY OF SOUTHERN AFRICA,15TH ANNUAL CONFERENCE, vol. 6, December 1976 (1976-12-01), JOHANNESBURG, SOUTH AFRICA, pages 99 - 100, XP000646518 *
GANGOPADHYAY A.K. AND TAMOR M.A.: "FRICTION AND WEAR BEHAVIOR OF DIAMOND FILMS AGAINST STEEL AND CERAMICS", WEAR, vol. 169, no. 2, 15 October 1993 (1993-10-15), SWITZERLAND, pages 221 - 229, XP000645949 *
SAITOH H., YOSHIDA K. AND YARBROUGH W.A.: "PREPARATION AND CHARACTERIZATION OF BORON RICH BORON NITRIDE MICROCRYSTALS BY HOT FILAMENT ASSISTED CHEMICAL VAPOR DEPOSITION", JOURNAL OF CHEMICAL VAPOR DEPOSITION, vol. 1, no. 1, July 1992 (1992-07-01), USA, pages 59 - 72, XP000646093 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3330808A1 (de) * 2016-11-24 2018-06-06 Seiko Epson Corporation Uhrenteil und uhr

Also Published As

Publication number Publication date
JP4476371B2 (ja) 2010-06-09
DE69630792T2 (de) 2004-09-23
CN1185599A (zh) 1998-06-24
SG67443A1 (en) 1999-09-21
KR100547850B1 (ko) 2006-04-14
CN1161673C (zh) 2004-08-11
EP0844539B1 (de) 2003-11-19
HK1013779A1 (en) 1999-09-10
DE69630792D1 (de) 2003-12-24
KR19980041971A (ko) 1998-08-17
US6123450A (en) 2000-09-26
TW346557B (en) 1998-12-01
JPH10160863A (ja) 1998-06-19

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