EP1512765B1 - Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration - Google Patents

Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration Download PDF

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Publication number
EP1512765B1
EP1512765B1 EP03405645A EP03405645A EP1512765B1 EP 1512765 B1 EP1512765 B1 EP 1512765B1 EP 03405645 A EP03405645 A EP 03405645A EP 03405645 A EP03405645 A EP 03405645A EP 1512765 B1 EP1512765 B1 EP 1512765B1
Authority
EP
European Patent Office
Prior art keywords
alloy
copper
gold
platinum
color
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.)
Expired - Lifetime
Application number
EP03405645A
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German (de)
English (en)
French (fr)
Other versions
EP1512765A1 (fr
Inventor
Jacques Baur
Frédéric Oulevey
Michèle Saudan
Denis Vincent
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.)
Rolex SA
Original Assignee
Rolex SA
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 Rolex SA filed Critical Rolex SA
Priority to DE60310555T priority Critical patent/DE60310555T2/de
Priority to EP03405645A priority patent/EP1512765B1/fr
Priority to DE03405645T priority patent/DE03405645T1/de
Priority to US10/916,853 priority patent/US7311876B2/en
Priority to EP04104165A priority patent/EP1512766A1/fr
Priority to JP2004252708A priority patent/JP4813028B2/ja
Priority to CNB2004100751416A priority patent/CN100344780C/zh
Publication of EP1512765A1 publication Critical patent/EP1512765A1/fr
Application granted granted Critical
Publication of EP1512765B1 publication Critical patent/EP1512765B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • 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

Definitions

  • the invention relates to a timepiece, jewelery or jewelery made of an alloy comprising by weight at least 75% gold and at least 6% copper.
  • the color of such gold alloys depends on their copper and silver contents. A copper content greater than 18% and a silver content of around 4% give them a red color. The color changes to pink and then yellow if the copper content decreases from 18% to 15% then from 15% to 6% and if the silver content increases from 4% to 15%.
  • the color is conventionally defined by a point in the CIELAB space consisting of a green-red axis on the abscissa, a blue-yellow axis on the y-axis and an axis representative of the contrast (see ISO 7724 standard). by the International Commission on Illumination).
  • the colors of the gold alloys are defined in the tri-chromatic space according to the ISO 8654 standard.
  • Document DE-A-19958900 discloses a timepiece or jewelery made of an alloy comprising between 40% and 80% of gold, between 0% and 15% of copper, between 1% and 40% of silver, between 1% and 15% of iron and between 0% and 15% of palladium. Iron is combined with these elements to replace the nickel considered as allergen, to limit the content of palladium considered as expensive and to give the alloy a white gold color.
  • the alloy may contain between 0% and 0.5% of any of the following: platinum, ruthenium, rhodium, iridium, tungsten or tantalum to refine grain size.
  • the specialized literature reports an accelerated tarnishing study performed on an alloy intended for the manufacture of jewelery pieces and comprising 75% gold, 12% copper and 12% silver.
  • the tests take place in the gas phase or in the liquid phase. Tarnishing is quantitatively determined by the color difference of the alloy before and after the test.
  • the reactants in contact with which the alloy is exposed comprise essentially pure sulfur or sulfur compounds.
  • the tarnishing observed is attributed to the formation of silver sulphide Ag 2 S. (See “Tarnishing of AuAgCu alloys", 43, pp. 48-55, 1992, Werkstoffe und Korrosion ).
  • Document CH-219 711 discloses an alloy intended for the manufacture of dental prostheses and comprising between 65% and 75% of a mixture of gold and platinum in which platinum is between 2% and 5%, between 1% and 6% silver, between 8% and 14% copper, between 8% and 14% cadmium and between 0.1% and 1% zinc. Platinum is alloyed with these elements to give this yellow gold alloy good resistance to tarnishing and corrosion in the mouth.
  • GB-A-2,279,662 discloses an alloy intended for watchmaking, jewelery or jewelery, comprising between 33% and 90% of gold, between 0.1% and 2.5% of iron, between 0% and , 01% and 62.5% silver, between 0.01% and 62.5% copper, between 0.01% and 62.5% zinc and having a hardness of between 100 and 280 Hv.
  • the iron is combined with the other elements of the alloy to give it greater hardness and to prevent grain growth during a welding operation. In addition, a better resistance to color loadings is observed during heat treatments.
  • the alloy may contain between 0.01% and 25% of palladium, nickel or cadmium, between 0.01% and 10% of indium, tin, gallium, cobalt, platinum, rhodium, between 0.01% and 3% of iridium, ruthenium, silicon or boron. Alloys provided as examples include all 37.53% gold, 8.70% or 9.20% silver, 42.40% copper, 10.87% or 10.67% or 10.57% 10.37% zinc and 0.5% or 0.7% or 0.8% or 1% iron.
  • a timepiece, jewelery or jewelery made of an alloy comprising at least 75% of gold and between 15% and 23% of copper is known of Japanese Patent Application JP 10245646 published in 1998.
  • the alloy further comprises between 0.3% and 5% of palladium to exhibit greater resistance to cracking during molding of the workpiece.
  • One of the aims of the invention is to improve the resistance to a color change of a timepiece, jewelery or jewelery made in a gold alloy and subjected, in use, to weakly aggressive aqueous media.
  • the invention relates to a timepiece, jewelery or jewelery made of an alloy comprising by weight at least 75% of gold, characterized in that the alloy also comprises between 0.5% and 4% platinum and at least 18% copper.
  • the platinum content increases the resistance to a change in the color of the room subjected to the action of tap water, sea water, swimming pool water, salt water or soapy water
  • the timepiece, jewelery or jewelry can be made of an alloy further comprising not more than 4% of palladium to enhance the effect of resistance to a color change. This is for example the case for a yellow-colored alloy comprising between 6% and 15% copper.
  • FIG. 1 shows two experimental decolorization curves respectively obtained on a red alloy according to the invention, curve (b), and on a 5N red alloy according to the prior art, curve (a).
  • FIGS. 2a and 2b show two concentration profiles respectively obtained on the two alloys having undergone the fading test illustrated in FIG. 1
  • Table I reports the results of discoloration tests obtained on different alloys according to the invention.
  • a red 5N reference alloy comprising 75% gold, 21% copper and 4.5% silver is subjected to a bleaching test.
  • the alloy is immersed in a saturated neutral solution of sodium chloride at a temperature of 40 degrees C for several tens of days.
  • the color is measured according to the ISO 7724 standard.
  • the kinetics of discoloration is illustrated by the curve (a) of FIG. 1.
  • the immersion time is plotted in the day and on the ordinate, the vector standard ⁇ Elab connecting the points representative of the color of the alloy in the CIELAB space, between the initial moment and the different immersion times. In relation to the time range explored, the discoloration appears continuous and monotonous with the immersion time.
  • a red-colored alloy comprising according to the invention 76% gold, 21% copper and 3% platinum is tested under the same conditions as those of the reference alloy.
  • the kinetics of discoloration is illustrated by curve (b).
  • the latter shows that the standard of the vector connecting the points representative of the color of the alloy according to the invention between the initial moment and the different immersion times is less than it is for the reference alloy without platinum. In other words, the presence of platinum increased the fade resistance of the alloy according to the invention.
  • an improvement factor is defined by the ratio between the color changes of the reference alloy and the alloy according to the invention, considered after the same immersion time. In this case, the improvement factor is about 3 after a 60-day immersion time.
  • FIGS. 2a and 2b show the concentration profiles obtained respectively on the reference 5N alloy and on the alloy according to the invention, after 60 days of immersion in the test solution.
  • FIG. 2a shows a decrease in the copper concentration in proportion to that of gold over a material depth of between the first 10 and 20 nanometers as well as the maintenance of the concentration. in silver on the same depth.
  • Figure 2b the copper concentration in proportion to that of gold decreases less strongly and less deeply for the alloy according to the invention.
  • Table I reports the results of the discoloration test carried out on alloys of different compositions numbered from 1 to 15. A row of the table indicates the content of the alloy in gold, copper, platinum and palladium and the limiting value of discoloration ⁇ ELab and the fading enhancement factor after a 60-day immersion test.
  • the experimental conditions are identical to those experimented previously: immersion in a saturated solution of sodium chloride at neutral pH and at a temperature of 40 degrees Celsius.
  • alloys according to the invention whose compositions are referenced from 15 to 9 in Table I attest to a factor for improving the resistance to fading typically between 2 and 4.
  • the improvement factor depends on the weight content of the copper in the alloys according to the invention. Preferably, this content is between 15% and 18%. More preferably, it is greater than 18% and more especially between 20% and 22% for a platinum content of between 1.5% and 3%.
  • platinum content between 0.5% and 4% gives the timepieces, jewelery or jewelry according to the invention a color that was impossible to obtain until now. While copper has a blushing effect and silver has a greening effect, platinum has a whitening effect.
  • the addition of platinum or palladium to the graying effect makes it possible to gradually move from warm, discreet and velvety colors for the lowest levels to more technical colors and colder for the highest levels.
  • a timepiece, jewelery or jewelery made of an alloy comprising by weight at least 75% of gold, between 20% and 22% of copper, between 1.5% and 3% of platinum and at more than 0.5% of any of the elements selected from silver, cadmium, chromium, cobalt, iron, indium, manganese, nickel or zinc has a nominal color having in the CIELAB space, an abscissa equal to 7.41 along the green-red axis, an ordinate equal to 15.67 along the blue-yellow axis and a contrast value equal to 86.75.
  • these coordinates can vary between 5.71 and 8.51 along the green-red axis and between 13.67 and 16.67 depending on the blue-yellow axis for a value of contrast L varying between 76.75 and 96, 75.
  • the invention applies to any timepiece, jewelery or jewelery made from an alloy according to the usual methods like the machining or lost wax molding.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Adornments (AREA)
EP03405645A 2003-09-04 2003-09-04 Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration Expired - Lifetime EP1512765B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE60310555T DE60310555T2 (de) 2003-09-04 2003-09-04 Entfärbungsbestängdige Uhr oder Schmuck
EP03405645A EP1512765B1 (fr) 2003-09-04 2003-09-04 Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration
DE03405645T DE03405645T1 (de) 2003-09-04 2003-09-04 Entfärbungsbeständige Uhr oder Schmuck
US10/916,853 US7311876B2 (en) 2003-09-04 2004-08-12 Discoloration-resistant timepiece or jewelry part
EP04104165A EP1512766A1 (fr) 2003-09-04 2004-08-31 Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration
JP2004252708A JP4813028B2 (ja) 2003-09-04 2004-08-31 耐変色性時計又は貴金属装飾部品
CNB2004100751416A CN100344780C (zh) 2003-09-04 2004-09-03 耐变色性的时计或珠宝部件

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP03405645A EP1512765B1 (fr) 2003-09-04 2003-09-04 Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration

Publications (2)

Publication Number Publication Date
EP1512765A1 EP1512765A1 (fr) 2005-03-09
EP1512765B1 true EP1512765B1 (fr) 2006-12-20

Family

ID=34130407

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03405645A Expired - Lifetime EP1512765B1 (fr) 2003-09-04 2003-09-04 Pièce d'horlogerie, de bijouterie ou de joaillerie résistant à la décoloration

Country Status (5)

Country Link
US (1) US7311876B2 (enrdf_load_stackoverflow)
EP (1) EP1512765B1 (enrdf_load_stackoverflow)
JP (1) JP4813028B2 (enrdf_load_stackoverflow)
CN (1) CN100344780C (enrdf_load_stackoverflow)
DE (2) DE60310555T2 (enrdf_load_stackoverflow)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2893813A1 (fr) * 2006-04-26 2007-05-25 Samsung Electro Mech Substrat conducteur, moteur, moteur a vibrations et borne metallique pour contact electrique ayant une couche d'or et de cuivre.
EP2175272B1 (en) * 2007-05-23 2011-11-09 Applied Biosystems, LLC Reagents, kits and methods for detecting biological molecules by energy transfer from an activated chemiluminescent substrate to an energy acceptor dye
CN101629253B (zh) * 2009-07-29 2010-08-18 深圳市金福珠宝首饰有限公司 一种金合金及其制备方法
DE102010026930A1 (de) * 2010-07-12 2012-01-12 C. Hafner Gmbh + Co. Kg Ideal-weiße, anlaufbeständige Edelmetall-Schmucklegierung
DE202011102731U1 (de) 2011-06-08 2011-12-05 C. Hafner Gmbh + Co. Kg Goldlegierung
IN2014CN04166A (enrdf_load_stackoverflow) * 2011-11-08 2015-07-17 Swatch Group Res & Dev Ltd
EP3428295A1 (en) 2012-12-03 2019-01-16 Argor-Heraeus S.A. Discoloration-resistant gold alloy
EP2954079B1 (fr) * 2013-02-06 2020-08-19 Rolex Sa Piece d'horlogerie en alliage d'or rose
JP6206872B2 (ja) * 2013-08-30 2017-10-04 国立大学法人東京工業大学 超弾性合金
CN104046829A (zh) * 2014-06-27 2014-09-17 张家港市佳威机械有限公司 一种首饰金基合金
EP3106930A1 (fr) * 2015-06-16 2016-12-21 Nivarox-FAR S.A. Procédé de fabrication comportant une étape d'usinage modifiée
WO2018178998A1 (en) 2017-03-27 2018-10-04 Pethe Subodh Hard gold alloy with zirconium, titanium and magnesium for jewelry manufacture
CH714785B1 (it) 2018-03-15 2022-05-13 Argor Heraeus Sa Lega d'oro resistente alla decolorazione e metodo di produzione della medesima.
CH714786B1 (it) * 2018-03-15 2022-05-13 Argor Heraeus Sa Lega d'oro con colore compatibile allo standard 5N e metodo di produzione della medesima.
CN109022890A (zh) * 2018-09-20 2018-12-18 张家港市勇峰精密机械有限公司 一种耐腐蚀金基精密五金材料
CH716501A1 (fr) * 2019-08-15 2021-02-15 Mft Dhorlogerie Audemars Piguet Sa Matériau composite, composant hétérogène pour pièce d'horlogerie et procédé de fabrication.
CN110468298B (zh) * 2019-09-19 2020-08-18 深圳市罗斯高德贵金属新材料股份有限公司 用于首饰和钟表行业的淡蓝色金合金的制备方法
EP3812477B1 (en) * 2019-10-21 2023-01-11 Richemont International SA Metal alloy comprising gold
DE102020121225A1 (de) 2020-08-12 2022-02-17 Egf - Eduard G. Fidel Gmbh Schmuckkörper
DE102020132870A1 (de) 2020-12-09 2022-06-09 Egf - Eduard G. Fidel Gmbh Schmuckkörper
US11268174B1 (en) * 2021-06-10 2022-03-08 Chow Sang Sang Jewellery Company Limited Jewelry alloy
EP4257265A1 (fr) * 2022-04-06 2023-10-11 Patek Philippe SA Genève Procédé de fabrication d'un composant horloger ou de bijouterie et ledit composant horloger ou de bijouterie
CN115896527B (zh) * 2022-12-16 2024-05-03 深圳市华悦珠宝科技有限公司 一种16k金、弹簧的制作方法、弹簧及首饰

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Publication number Priority date Publication date Assignee Title
IT384094B (enrdf_load_stackoverflow) * 1939-07-20 1940-11-25
JPS54132425A (en) 1978-04-06 1979-10-15 Ishifuku Metal Ind Gold alloy
GB9314292D0 (en) * 1993-07-10 1993-08-25 Johnson Matthey Plc Gold alloy
JPH08325656A (ja) * 1995-06-01 1996-12-10 Kuwayama Kikinzoku:Kk 装飾用ピンク系金合金
JPH09184033A (ja) * 1996-01-08 1997-07-15 Tanaka Kikinzoku Kogyo Kk ホワイト・ゴールド合金
JPH10245646A (ja) * 1997-03-07 1998-09-14 Seiko Epson Corp 金合金、装飾部材、携帯時計及び装飾部材の製造方法
EP0904765A2 (en) * 1997-09-25 1999-03-31 Ivoclar Ag Gold coloured dental alloy
DE19958800A1 (de) * 1999-06-30 2001-01-04 Wieland Edelmetalle Weißgold-Schmucklegierung
JP3548797B2 (ja) * 2000-12-25 2004-07-28 独立行政法人産業技術総合研究所 緑色の金合金宝飾品の製造方法とその製品
ATE466115T1 (de) 2001-01-26 2010-05-15 Metalor Technologies Int Graue goldlegierung

Also Published As

Publication number Publication date
US7311876B2 (en) 2007-12-25
US20050053514A1 (en) 2005-03-10
JP2005120465A (ja) 2005-05-12
DE60310555T2 (de) 2007-12-27
EP1512765A1 (fr) 2005-03-09
CN1605645A (zh) 2005-04-13
DE60310555D1 (de) 2007-02-01
DE03405645T1 (de) 2005-09-01
JP4813028B2 (ja) 2011-11-09
CN100344780C (zh) 2007-10-24

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