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WO2008052378A2 - Timepiece - Google Patents

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Publication number
WO2008052378A2
WO2008052378A2 PCT/CH2007/000538 CH2007000538W WO2008052378A2 WO 2008052378 A2 WO2008052378 A2 WO 2008052378A2 CH 2007000538 W CH2007000538 W CH 2007000538W WO 2008052378 A2 WO2008052378 A2 WO 2008052378A2
Authority
WO
WIPO (PCT)
Prior art keywords
watch according
piece
oxide
glycerol
ruby
Prior art date
Application number
PCT/CH2007/000538
Other languages
French (fr)
Other versions
WO2008052378A3 (en
Inventor
Jean-Marc Bonard
Original Assignee
Rolex S.A.
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 S.A. filed Critical Rolex S.A.
Priority to EP07816221.1A priority Critical patent/EP2082014B1/en
Priority to CH00525/09A priority patent/CH698230B1/en
Publication of WO2008052378A2 publication Critical patent/WO2008052378A2/en
Publication of WO2008052378A3 publication Critical patent/WO2008052378A3/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/10Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M105/14Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms polyhydroxy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B15/00Escapements
    • G04B15/14Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • GPHYSICS
    • G04HOROLOGY
    • G04BMECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B31/00Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
    • G04B31/08Lubrication
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • C10M2207/0225Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/06Instruments or other precision apparatus, e.g. damping fluids

Definitions

  • the present invention relates to a watch, in particular to a mechanical watch, of which at least some of the moving parts are lubricated by agents with a very low coefficient of friction.
  • the lubrication is ensured between the parts in relative motion, generally steel and ruby, by oils well known in the technical field considered, which produce low coefficients of friction, for example ⁇ 0.1 at the temperature of 23 ° C.
  • oils well known in the technical field considered, which produce low coefficients of friction, for example ⁇ 0.1 at the temperature of 23 ° C.
  • PAO polyalphaolefin
  • Such a watch includes a first relatively sliding piece on a second piece, the first piece being formed of oxide or having an oxide layer on the surface, the sliding surface having a chemical affinity with hydrophilic groups, as well as, on the sliding surface of the first part, at least one compound containing one or more hydrophilic groups chosen from C 3 -C 8 polyols having at least one-third of -OH groups relative to the number of carbon atoms.
  • This compound may be a mixture and may contain, for example, another substance containing hydrophilic groups, such as water.
  • the C 3 -C 8 polyol may be chosen for example from the group comprising glycerol (C 3 H 8 O 3 ), propylene glycol (C 3 H 8 O 2 ), diethylene glycol (C 4 H 10 O 3 ) , 1,6-hexanediol (C 6 H 14 O 2 ), 1,2,6-hexanetriol (C 6 H 14 O 3 ), triethylene glycol (C 6 H 14 O 4 ), diglycerol (C 6 H 14 O 5 ), triglycerol (C 9 H 20 O 7 ), triethanolamine (C 6 H 15 NO 3 ).
  • the carbon chain of the polyol may comprise O or N.
  • Glycerol is a C 3 alcohol containing 3 -OH groups, propylene glycol a C 3 alcohol containing 2 -OH groups, diethylene glycol a C 4 alcohol comprising 2 -OH groups and 1 O atom in the chain, 1,6-hexanediol, a C 6 alcohol having 2 -OH groups, 1,2,6-hexanetriol, a C 6 alcohol comprising 3 -OH groups, triethylene glycol, a C 6 alcohol comprising 2 -OH groups, and two O atoms in the chain, the diglycerol a C 6 alcohol comprising 4 -OH groups and 1 O atom in the chain, the triglycerol a C 9 alcohol comprising 5 -OH groups and 2 O atoms in the chain and triethanolamine a C 6 alcohol comprising 3 -OH groups and an N atom.
  • the second surface may also have a chemical affinity with hydrophilic groups and be, for example formed of oxide or have on the surface an oxide layer, as well as the first surface. It can also be metallic or metal alloy.
  • one of the relative sliding parts may be ceramic, in particular alumina or zirconia, more particularly ruby or sapphire
  • the other relatively sliding parts may be made of iron, steel, for example steel 20AP , or other alloy of iron, or of brass, aluminum, titanium, cuproberyllium, silicon, nickel, nickel-phosphorus or their alloys.
  • the part in question may be a part having a surface coating, obtained for example by galvanic deposition of gold, gold-copper-cadmium and gold, nickel, rhodium, tin-nickel. It may also have an anodized surface, as in the case of aluminum alloy parts or titanium. It can also be modified by a surface treatment such as oxidation, carburization or nitriding. Between the two relatively sliding parts can also be an intermediate layer called "epilame", well known in watchmaking and used to prevent the spreading of lubricants.
  • the compound comprising one or more hydrophilic groups is a low molecular weight polyol, for example glycerol or aqueous glycerol.
  • This compound acts as a lubricant forming a film or film between the two moving surfaces.
  • Examples 1 to 6 indicate the results obtained with aqueous glycerol on various pairs of surfaces, while Examples 7 to 17 give the results obtained with compounds other than glycerol for the same pair of 20AP steel-ruby surfaces.
  • the coefficient of friction a standard measure in watchmaking, expresses the dynamic friction and corresponds to the ratio between the tangential force exerted to maintain the relative movement between the two parts and the perpendicular force exerted on them.
  • 20AP steel is a hardening carbon steel made of 1% carbon, 0.4% manganese, 0.2% lead, 0.15% silicon, 0.05% sulfur, and iron for the balance.
  • the term "epilamed 20AP steel” is intended to denote a 20AP steel on which a conventional epilame has been deposited, in this case that sold under the trademark Fixodrop FK / BS-10 by Moebius et Fils in Allschwil (Switzerland).
  • Ruby is a synthetic ruby as commonly used in watchmaking and "85% glycerol" means a liquid composed of glycerol at 85% by weight and 15% by weight of water (mutatis mutandis for Examples 13, 14 and 16). ).
  • 941 Oil is a commercial oil manufactured by the same Moebius Company and is a mixture of one alkyl-aryl monooleate and two C 10 -C 13 diesters with anti-wear and extreme pressure additives; its viscosity, measured at 20 ° C., is 100 mm 2 / s.
  • PAO + GMO is a mixture of synthetic oils of polyalphaolefin type (PAO D)) having a carbon monoxide content at 20 ° C. of 100 mm 2 / s, and 1% of GMO additive (glycerol monooleate).
  • GMO additive glycerol monooleate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Sliding-Contact Bearings (AREA)

Abstract

The invention relates to a timepiece, mainly a mechanical timepiece, in which at least certain mobile parts are lubricated by agents or compounds having a very low friction coefficient. The timepiece includes a first part capable of relative sliding movement on a second part, the first part being made of an oxide or comprising an oxide surface layer. The timepiece also includes on the sliding surface of the first part at least one compound containing one or more hydrophilic groups selected from C3-C9 polyols having at least one third of -OH groups relative to the number of carbon atoms. The first part may consist of ruby or zirconia and the second part of steel or vice-versa, and the compound containing one or more hydrophilic groups may consist of glycerol or aqueous glycerol.

Description

MONTRE WATCH
La présente invention se rapporte à une montre, notamment à une montre mécanique, dont certaines des pièces mobiles au moins sont lubrifiées par des agents à très faible coefficient de frottement.The present invention relates to a watch, in particular to a mechanical watch, of which at least some of the moving parts are lubricated by agents with a very low coefficient of friction.
On sait que l'un des problèmes majeurs qui se pose en horlogerie, particulièrement dans le domaine de la montre-bracelet chronomètre, est d'assurer un frottement aussi bas que possible entre les pièces en mouvement relatif les unes par rapport aux autres, compte tenu de la faible réserve d'énergie dont on dispose.It is known that one of the major problems that arises in watchmaking, particularly in the field of the chronometer wristwatch, is to ensure as low a friction as possible between the moving parts relative to each other, account given the low energy reserve available.
Habituellement, la lubrification est assurée, entre les pièces en mouvement relatif, généralement en acier et en rubis, par des huiles bien connues dans le domaine technique considéré, qui produisent des coefficients de frottement bas, par exemple < 0,1 à la température de 23°C. On citera à cet égard l'huile connue sous le nom de Huile 941 , à côté d'autres lubrifiants qui peuvent être également utilisés, en particulier des mélanges d'huiles synthétiques de type polyalphaoléfine (PAO) comprenant comme additifs du monooléate de glycérolUsually, the lubrication is ensured between the parts in relative motion, generally steel and ruby, by oils well known in the technical field considered, which produce low coefficients of friction, for example <0.1 at the temperature of 23 ° C. In this respect, mention may be made of the oil known under the name of Oil 941, in addition to other lubricants which may also be used, in particular synthetic polyalphaolefin (PAO) type oil mixtures comprising as glycerol monooleate additives.
(GMO).(GMO).
Comme cela est décrit par ailleurs par Kano et al, Tribology Letters 18 (2) février 2005, il s'est avéré possible d'obtenir de meilleurs coefficients de frottement encore, typiquement ≤ 0,06, de préférence ≤ 0,05, à la température de 800C, en intercalant un film de carbone entre les surfaces en frottement, c'est-à- dire en combinant le dépôt d'un film de carbone dur sur au moins l'une des surfaces en glissement avec l'utilisation d'un additif à groupe -OH comme le GMO dans le lubrifiant. Dans cet article, il est question de glissement de surfaces contenant des groupes -OH et les auteurs font l'hypothèse, qu'ils indiquent immédiatement comme étant à vérifier par des travaux analytiques, que les groupes -OH glissent les uns contre les autres en étant accrochés sur la surface par l'intermédiaire du film contenant les groupes C.As described by Kano et al., Tribology Letters 18 (2) February 2005, it has been found possible to obtain even better friction coefficients, typically ≤ 0.06, preferably ≤ 0.05, at the temperature of 80 0 C, by interposing a carbon film between the friction surfaces, that is to say by combining the deposition of a hard carbon film on at least one of the sliding surfaces with the use of a -OH additive such as GMO in the lubricant. In this paper, it is question of sliding of surfaces containing -OH groups and the authors make the hypothesis, that they indicate immediately as being to verify by analytical works, that the -OH groups slide against each other by being hooked on the surface via the film containing groups C.
On a cependant vite remarqué que l'interposition d'un film contenant du carbone, si elle donnait d'excellents résultats pour le frottement de pièces travaillant à haute température, par exemple à 800C, en particulier dans des moteurs d'automobiles, ne convenait pas en revanche pour des pièces travaillant à basse température comme dans l'horlogerie. La lubrification obtenue ne montre aucun progrès par rapport à une lubrification de type traditionnel.However, it was quickly noticed that the interposition of a carbon-containing film, if it gave excellent results for the friction of parts working at high temperature, for example at 80 ° C., in particular in automobile engines, did not suit however for parts working at low temperature as in watchmaking. The lubrication obtained shows no progress compared with traditional lubrication.
De façon surprenante, on a alors constaté que l'on pouvait obtenir des résultats nettement meilleurs en supprimant la couche de carbone intermédiaire, et en associant directement une ou des surfaces d'oxyde ayant une affinité pour les groupes hydrophiles et un composé contenant un ou plusieurs groupes hydrophiles. C'est précisément l'objet de l'invention, qui concerne donc une montre, notamment une montre mécanique, dont certaines des pièces mobiles au moins sont lubrifiées par des agents à très faible coefficient de frottement. On parlera ici et dans la suite de l'exposé de "très faible coefficient de frottement" pour des valeurs de ce coefficient inférieures ou égales à 0,06.Surprisingly, it was found that much better results could be achieved by removing the intermediate carbon layer, and by directly associating one or more oxide surfaces having an affinity for the hydrophilic groups and a compound containing one or more several hydrophilic groups. This is precisely the subject of the invention, which therefore concerns a watch, in particular a mechanical watch, of which at least some of the moving parts are lubricated by agents with a very low coefficient of friction. We will discuss here and in the following the statement of "very low coefficient of friction" for values of this coefficient less than or equal to 0.06.
Une telle montre comprend une première pièce en glissement relatif sur une deuxième pièce, la première pièce étant formée d'oxyde ou comportant une couche d'oxyde en surface, la surface de glissement ayant une affinité chimique avec des groupes hydrophiles, ainsi que, sur la surface de glissement de la première pièce, au moins un composé contenant un ou plusieurs groupes hydrophiles choisis parmi les polyols en C3-Cg ayant un tiers au moins de groupes -OH par rapport au nombre d'atomes de carbone.Such a watch includes a first relatively sliding piece on a second piece, the first piece being formed of oxide or having an oxide layer on the surface, the sliding surface having a chemical affinity with hydrophilic groups, as well as, on the sliding surface of the first part, at least one compound containing one or more hydrophilic groups chosen from C 3 -C 8 polyols having at least one-third of -OH groups relative to the number of carbon atoms.
Ce composé peut être un mélange et peut contenir, par exemple, une autre substance contenant des groupes hydrophiles, telle que l'eau. Le polyol en C3-Cg peut être choisi par exemple dans le groupe comprenant le glycérol (C3H8O3), le propylène glycol (C3H8O2), le diéthylène glycol (C4H10O3), le 1 ,6-hexanediol (C6H14O2), le 1 ,2,6-hexanetriol (C6H14O3), le triéthylène glycol (C6H14O4), Ie diglycérol (C6H14O5), le triglycérol (C9H20O7), la triéthanolamine (C6H15NO3). Comme on le voit, la chaîne carbonée du polyol peut comprendre des atomes de O ou de N.This compound may be a mixture and may contain, for example, another substance containing hydrophilic groups, such as water. The C 3 -C 8 polyol may be chosen for example from the group comprising glycerol (C 3 H 8 O 3 ), propylene glycol (C 3 H 8 O 2 ), diethylene glycol (C 4 H 10 O 3 ) , 1,6-hexanediol (C 6 H 14 O 2 ), 1,2,6-hexanetriol (C 6 H 14 O 3 ), triethylene glycol (C 6 H 14 O 4 ), diglycerol (C 6 H 14 O 5 ), triglycerol (C 9 H 20 O 7 ), triethanolamine (C 6 H 15 NO 3 ). As can be seen, the carbon chain of the polyol may comprise O or N.
Le glycérol est un alcool en C3 contenant 3 groupes -OH, le propylène glycol un alcool en C3 contenant 2 groupes -OH, le diéthylène glycol un alcool en C4 comprenant 2 groupes -OH et 1 atome de O dans la chaîne, le 1 ,6- hexanediol un alcool en C6 comprenant 2 groupes -OH, le 1 ,2,6-hexanetriol un alcool en C6 comprenant 3 groupes -OH, le triéthylène glycol un alcool en C6 comprenant 2 groupes -OH et deux atomes de O dans la chaîne, le diglycérol un alcool en C6 comprenant 4 groupes -OH et 1 atome de O dans la chaîne, le triglycérol un alcool en C9 comprenant 5 groupes -OH et 2 atomes de O dans la chaîne et la triéthanolamine un alcool en C6 comprenant 3 groupes -OH et un atome de N.Glycerol is a C 3 alcohol containing 3 -OH groups, propylene glycol a C 3 alcohol containing 2 -OH groups, diethylene glycol a C 4 alcohol comprising 2 -OH groups and 1 O atom in the chain, 1,6-hexanediol, a C 6 alcohol having 2 -OH groups, 1,2,6-hexanetriol, a C 6 alcohol comprising 3 -OH groups, triethylene glycol, a C 6 alcohol comprising 2 -OH groups, and two O atoms in the chain, the diglycerol a C 6 alcohol comprising 4 -OH groups and 1 O atom in the chain, the triglycerol a C 9 alcohol comprising 5 -OH groups and 2 O atoms in the chain and triethanolamine a C 6 alcohol comprising 3 -OH groups and an N atom.
La deuxième surface peut avoir, elle aussi, une affinité chimique avec des groupes hydrophiles et être, par exemple formée d'oxyde ou comporter en surface une couche d'oxyde, au même titre que la première surface. Elle peut être également métallique ou en alliage métallique.The second surface may also have a chemical affinity with hydrophilic groups and be, for example formed of oxide or have on the surface an oxide layer, as well as the first surface. It can also be metallic or metal alloy.
Ainsi, l'une des pièces en glissement relatif peut être en céramique, notamment en alumine ou en zircone, plus particulièrement en rubis ou saphir, et l'autre des pièces en glissement relatif peut être en fer, acier, par exemple en acier 20AP, ou autre alliage de fer, ou encore en laiton, aluminium, titane, cuprobéryllium, silicium, nickel, nickel-phosphore ou leurs alliages. La pièce en question peut être une pièce présentant un revêtement de surface, obtenu par exemple par dépôt galvanique d'or, d'or-cuivre-cadmium et or, de nickel, de rhodium, d'étain-nickel. Elle peut également présenter une surface traitée par anodisation, comme dans le cas des pièces en alliage d'aluminium ou de titane. Elle peut aussi être modifiée par un traitement de surface comme l'oxydation, la carburation ou la nitruration. Entre les deux pièces en glissement relatif peut aussi se trouver une couche intermédiaire dite "épilame", bien connue en horlogerie et utilisée pour éviter l'étalement des lubrifiants.Thus, one of the relative sliding parts may be ceramic, in particular alumina or zirconia, more particularly ruby or sapphire, and the other relatively sliding parts may be made of iron, steel, for example steel 20AP , or other alloy of iron, or of brass, aluminum, titanium, cuproberyllium, silicon, nickel, nickel-phosphorus or their alloys. The part in question may be a part having a surface coating, obtained for example by galvanic deposition of gold, gold-copper-cadmium and gold, nickel, rhodium, tin-nickel. It may also have an anodized surface, as in the case of aluminum alloy parts or titanium. It can also be modified by a surface treatment such as oxidation, carburization or nitriding. Between the two relatively sliding parts can also be an intermediate layer called "epilame", well known in watchmaking and used to prevent the spreading of lubricants.
On peut ainsi réaliser un excellent glissement entre une palette d'ancre en rubis ou zircone et une roue d'échappement en acier, ou encore entre un axe en acier et un palier en rubis ou zircone.It is thus possible to achieve excellent sliding between a pallet of ruby or zirconia anchor and a steel escapement wheel, or alternatively between a steel shaft and a ruby or zirconia bearing.
De préférence, le composé comprenant un ou plusieurs groupes hydrophiles est un polyol de bas poids moléculaire, par exemple du glycérol ou du glycérol aqueux. Ce composé agit comme lubrifiant en formant un film ou une pellicule entre les deux surfaces en mouvement.Preferably, the compound comprising one or more hydrophilic groups is a low molecular weight polyol, for example glycerol or aqueous glycerol. This compound acts as a lubricant forming a film or film between the two moving surfaces.
On explique les propriétés de glissement exceptionnelles obtenues par l'interaction entre les groupes hydrophiles et les groupes oxygène au moyen de liaisons hydrogène. Il est possible aussi que les forces de Van der Waals interviennent aussi dans le phénomène.The exceptional slip properties obtained by the interaction between hydrophilic groups and oxygen groups by means of hydrogen bonds are explained. It is also possible that the forces of Van der Waals also intervene in the phenomenon.
L'invention sera mieux comprise en référence aux exemples 1 à 16 qui suivent, donnés à titre non limitatif, ainsi qu'à la figure unique annexée. Ces exemples, pour meilleure lisibilité, sont repris sous forme d'un tableau unique qui est complété par un exemple 17 concernant l'éthylène glycol et une série d'exemples comparatifs 18 à 24.The invention will be better understood with reference to Examples 1 to 16 which follow, given in a non-limiting manner, and to the single appended figure. These examples, for better readability, are included in the form of a single table which is supplemented by an example 17 relating to ethylene glycol and a series of comparative examples 18 to 24.
Les exemples 1 à 6 indiquent les résultats obtenus avec le glycérol aqueux sur divers couples de surfaces, tandis que les exemples 7 à 17 donnent les résultats obtenus avec d'autres composés que le glycérol pour le même couple de surfaces rubis-acier 20AP.Examples 1 to 6 indicate the results obtained with aqueous glycerol on various pairs of surfaces, while Examples 7 to 17 give the results obtained with compounds other than glycerol for the same pair of 20AP steel-ruby surfaces.
Ces résultats ont été obtenus sur tribomètre rectiligne alternatif, à l'aide d'un pion et d'un disque pour une force normale de 1.5 N correspondant à une pression de Hertz de 0.8 GPa, et une vitesse de 61.2 mm/s, pour une dizaine de milliers de cycles (soit une course totale de 200 m) au moins. Chaque valeur est une moyenne de 3 essais au moins. La température est typiquement de 23°C et le taux d'humidité relative typiquement de 35%. La quantité de lubrifiant déposée est de 1 μl. Par cycle, on entend un frottement aller-retour d'une pièce contre l'autre.These results were obtained on an alternative rectilinear tribometer, using a pion and a disk for a normal force of 1.5 N corresponding to a Hertz pressure of 0.8 GPa, and a speed of 61.2 mm / s, for ten thousand cycles (ie a total stroke of 200 m) at least. Each value is an average of at least 3 trials. The temperature is typically 23 ° C and the relative humidity is typically 35%. The amount of lubricant deposited is 1 .mu.l. By cycle is meant a round-to-back rubbing of one piece against the other.
Le coefficient de frottement, mesure standard en horlogerie, exprime Ie frottement dynamique et correspond au rapport entre la force tangentielle exercée pour maintenir le mouvement relatif entre les deux pièces et la force perpendiculaire exercée sur celles-ci.The coefficient of friction, a standard measure in watchmaking, expresses the dynamic friction and corresponds to the ratio between the tangential force exerted to maintain the relative movement between the two parts and the perpendicular force exerted on them.
L'acier 20AP est un acier au carbone trempable, composé de 1 % de carbone, 0.4% de manganèse, 0.2% de plomb, 0.15% de silicium, 0.05% de soufre, et de fer pour le solde. Par "acier 20AP épilamé", on entend désigner un acier 20AP sur lequel a été déposé un épilame horloger classique, en l'occurrence celui vendu sous la marque Fixodrop FK/BS-10 par la maison Moebius et Fils à Allschwil (Suisse).20AP steel is a hardening carbon steel made of 1% carbon, 0.4% manganese, 0.2% lead, 0.15% silicon, 0.05% sulfur, and iron for the balance. The term "epilamed 20AP steel" is intended to denote a 20AP steel on which a conventional epilame has been deposited, in this case that sold under the trademark Fixodrop FK / BS-10 by Moebius et Fils in Allschwil (Switzerland).
Le rubis est un rubis synthétique tel qu'utilisé habituellement en horlogerie et "glycérol à 85 %" signifie un liquide composé de glycérol à 85 % en poids et 15 % en poids d'eau (mutatis mutandis pour les exemples 13, 14 et 16).Ruby is a synthetic ruby as commonly used in watchmaking and "85% glycerol" means a liquid composed of glycerol at 85% by weight and 15% by weight of water (mutatis mutandis for Examples 13, 14 and 16). ).
"L'huile 941" est une huile commerciale, fabriquée par cette même maison Moebius, et correspond à un mélange d'un alkyl-aryl-monooléate et de deux diesters C10-C13, avec additifs anti-usure et extrême pression ; sa viscosité mesurée à 200C est de 100 mm2/s."941 Oil" is a commercial oil manufactured by the same Moebius Company and is a mixture of one alkyl-aryl monooleate and two C 10 -C 13 diesters with anti-wear and extreme pressure additives; its viscosity, measured at 20 ° C., is 100 mm 2 / s.
"PAO+GMO" est un mélange d'huiles synthétiques de type polyalphaoléfine (PAO D)) aavveecc uunnee vviissccoossiittéé mmeessurée à 200C de 100 mm2/s, et de 1% d'additif GMO (monooléate de glycérol). Enfin "DLC", pour "diamond like carbon", désigne une couche de carbone très dur de type diamant, déposée en phase vapeur, en référence à l'article de Kano cité précédemment."PAO + GMO" is a mixture of synthetic oils of polyalphaolefin type (PAO D)) having a carbon monoxide content at 20 ° C. of 100 mm 2 / s, and 1% of GMO additive (glycerol monooleate). Finally "DLC", for "diamond like carbon", denotes a layer of very hard diamond-like carbon deposited in the vapor phase, with reference to the Kano article cited above.
TableauBoard
Figure imgf000008_0001
A la lecture du tableau, on ne pourra que constater les excellents résultats obtenus et l'abaissement des valeurs de coefficient de frottement par rapport aux solutions des exemples comparatifs 18 à 24 servant de valeurs de référence, les exemples "à sec" correspondant au glissement direct pièce contre pièce, sauf l'exemple 20 où est présente une couche de DLC. Le glycérol est le polyol qui donne parmi les meilleurs résultats et il s'agit d'un produit courant et aisé de mise en œuvre. En revanche, on constatera à la lecture de l'exemple 17 que l'utilisation de l'éthylène glycol (C2) n'est pas satisfaisante.
Figure imgf000008_0001
On reading the table, we can only see the excellent results obtained and the lowering of the coefficient of friction values compared to the solutions of comparative examples 18 to 24 serving as reference values, the "dry" examples corresponding to the sliding Direct piece against piece, except the example 20 where is present a layer of DLC. Glycerol is the polyol that gives some of the best results and it is a common product and easy to implement. On the other hand, it will be seen from reading example 17 that the use of ethylene glycol (C 2 ) is not satisfactory.
On se rapportera également à la figure unique annexée qui permet d'apprécier les résultats obtenus sur la durée et démontre que ceux-ci sont stables, même après de nombreux cycles. We will also refer to the appended single figure that allows us to assess the results obtained over time and shows that they are stable, even after many cycles.

Claims

REVENDICATIONS
1. Montre dont certaines des pièces mobiles au moins sont lubrifiées par des agents à très faible coefficient de frottement, caractérisée en ce qu'elle comprend : une première pièce en glissement relatif sur une deuxième pièce, la première pièce étant formée d'oxyde ou présentant une couche d'oxyde en surface, la surface de glissement ayant une affinité chimique avec des groupes hydrophiles, ainsi que, sur la surface de glissement de la première pièce, au moins un composé contenant un ou plusieurs groupes hydrophiles choisis parmi les polyols en C3-Cg ayant un tiers au moins de groupes -OH par rapport au nombre d'atomes de carbone.1. Watch which at least some of the moving parts are lubricated by agents with a very low coefficient of friction, characterized in that it comprises: a first relative sliding part on a second part, the first part being formed of oxide or having an oxide layer on the surface, the sliding surface having a chemical affinity with hydrophilic groups, as well as, on the sliding surface of the first part, at least one compound containing one or more hydrophilic groups selected from polyols; C 3 -Cg having at least one third of -OH groups relative to the number of carbon atoms.
2. Montre selon la revendication 1 , caractérisée en ce que la deuxième pièce est, elle aussi, formée d'oxyde ou présente une couche d'oxyde en surface, la surface de glissement ayant, elle aussi, une affinité chimique avec des groupes hydrophiles.2. Watch according to claim 1, characterized in that the second piece is also formed of oxide or has an oxide layer on the surface, the sliding surface also having a chemical affinity with hydrophilic groups .
3. Montre selon la revendication 1 , caractérisée en ce que la deuxième pièce est métallique ou en alliage métallique.3. Watch according to claim 1, characterized in that the second piece is metal or metal alloy.
4. Montre selon la revendication 1 à 3, caractérisée en ce que le polyol en C3-Cg est choisi dans le groupe comprenant le glycérol, le propylène glycol, le diéthylène glycol, le 1 ,6-hexanediol, le 1 ,2,6-hexanetriol, le triethylène glycol, le diglycérol, le triglycérol, la triéthanolamine.4. Watch according to claim 1 to 3, characterized in that the C 3 -C 8 polyol is chosen from the group comprising glycerol, propylene glycol, diethylene glycol, 1,6-hexanediol, 1,2 6-hexanetriol, triethylene glycol, diglycerol, triglycerol, triethanolamine.
5. Montre selon la revendication 1 ou 4, caractérisée en ce que le polyol contient de l'eau. 5. Watch according to claim 1 or 4, characterized in that the polyol contains water.
6. Montre selon la revendication 5, caractérisée en ce que Ie polyol est du glycérol ou du glycérol aqueux.6. Watch according to claim 5, characterized in that the polyol is glycerol or aqueous glycerol.
7. Montre selon l'une des revendications 1 à 6, caractérisée en ce que l'une des pièces au moins contient de l'oxyde d'aluminium ou de l'oxyde de zirconium.7. Watch according to one of claims 1 to 6, characterized in that at least one of the pieces contains aluminum oxide or zirconium oxide.
8. Montre selon la revendication 7, caractérisée en ce que l'une des pièces est en rubis ou en zircone.8. Watch according to claim 7, characterized in that one of the pieces is ruby or zirconia.
9. Montre selon l'une des revendications 1 à 6, caractérisée en ce que l'autre pièce est en fer, acier, laiton, aluminium, titane, cuprobéryllium, silicium, nickel, nickel-phosphore ou leurs alliages, avec un revêtement de surface galvanique ou non, avec un traitement de surface anodique, d'oxydation, de carburation ou de nitruration ou non, ou une couche épilame intercalaire.9. Watch according to one of claims 1 to 6, characterized in that the other piece is iron, steel, brass, aluminum, titanium, cuproberyllium, silicon, nickel, nickel-phosphorus or their alloys, with a coating of galvanic surface or not, with anodic surface treatment, oxidation, carburetion or nitriding or not, or an interlayer epilame layer.
10. Montre selon l'une des revendications 1 , 8 et 9, caractérisée en ce que la pièce en rubis ou en zircone est une palette d'ancre et la pièce en acier est une roue d'échappement.10. Watch according to one of claims 1, 8 and 9, characterized in that the ruby piece or zirconia is an anchor pallet and the steel piece is an escape wheel.
11. Montre selon l'une des revendications 1 , 8 et 9, caractérisée en ce que la pièce en rubis ou en zircone est un palier et la pièce en acier est un axe. 11. Watch according to one of claims 1, 8 and 9, characterized in that the ruby piece or zirconia is a bearing and the steel piece is an axis.
PCT/CH2007/000538 2006-11-02 2007-10-31 Timepiece WO2008052378A2 (en)

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EP2120105A1 (en) * 2008-05-13 2009-11-18 Sigatec SA Improved micromechanical part comprising lubrication elements
EP2226689A1 (en) * 2009-03-02 2010-09-08 Montres Breguet SA Bridge or plate for a timepiece movement
EP2687580A1 (en) * 2012-07-19 2014-01-22 Breitling AG Clock piece
EP2865737A1 (en) * 2013-10-28 2015-04-29 The Swatch Group Research and Development Ltd. Fine epilame product
CH708998A1 (en) * 2013-12-16 2015-06-30 Tgm Développement Sa C O Etude Tissot Timepiece and method for reducing the coefficient of friction of a timepiece.
EP3968096A1 (en) * 2020-09-15 2022-03-16 ETA SA Manufacture Horlogère Suisse Micromechanical component, in particular a timepiece mobile, in particular an escapement mobile, with optimised contact surface
EP3968095A1 (en) * 2020-09-15 2022-03-16 ETA SA Manufacture Horlogère Suisse Method for manufacturing a micromechanical component, in particular of a timepiece mobile, with optimised contact surface

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EP4075205A1 (en) * 2021-04-16 2022-10-19 ETA SA Manufacture Horlogère Suisse Method for manufacturing a timepiece mobile and timepiece mobile obtained by implementing same

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EP2120105A1 (en) * 2008-05-13 2009-11-18 Sigatec SA Improved micromechanical part comprising lubrication elements
EP2226689A1 (en) * 2009-03-02 2010-09-08 Montres Breguet SA Bridge or plate for a timepiece movement
EP2687580A1 (en) * 2012-07-19 2014-01-22 Breitling AG Clock piece
EP2865737A1 (en) * 2013-10-28 2015-04-29 The Swatch Group Research and Development Ltd. Fine epilame product
EP2865738A1 (en) * 2013-10-28 2015-04-29 The Swatch Group Research and Development Ltd. Fine epilame product
CH708998A1 (en) * 2013-12-16 2015-06-30 Tgm Développement Sa C O Etude Tissot Timepiece and method for reducing the coefficient of friction of a timepiece.
EP3968096A1 (en) * 2020-09-15 2022-03-16 ETA SA Manufacture Horlogère Suisse Micromechanical component, in particular a timepiece mobile, in particular an escapement mobile, with optimised contact surface
EP3968095A1 (en) * 2020-09-15 2022-03-16 ETA SA Manufacture Horlogère Suisse Method for manufacturing a micromechanical component, in particular of a timepiece mobile, with optimised contact surface
WO2022058160A1 (en) * 2020-09-15 2022-03-24 Eta Sa Manufacture Horlogère Suisse Method for manufacturing a micromechanical component, in particular a timepiece mobile having an optimised surface
WO2022058159A1 (en) * 2020-09-15 2022-03-24 Eta Sa Manufacture Horlogère Suisse Micromechanical component, in particular a timepiece wheel, in particular an escapement wheel, the surface of which is optimised
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WO2008052378A3 (en) 2008-08-14
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EP2082014A2 (en) 2009-07-29

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