![]() Lubricated watch component.
专利摘要:
The invention relates to a watch component (1) comprising a contact surface (5) intended to be in dynamic contact with another watch component, at least a part of said contact surface (5) being provided with a layer of a lubricant (3) comprising a base comprising at least one oil and / or a grease and / or an ionic liquid and at least one additive having the structure: R comprises a lipophilic group if said base comprises an oil and / or a grease, or is an ionic group if said base comprises an ionic liquid, R1 comprises a group selected from phosphonic acids, silanes and thiols, and n is a positive integer. 公开号:CH713671A2 申请号:CH00458/17 申请日:2017-04-05 公开日:2018-10-15 发明作者:Huot-Marchand Sylvain;Lallemand Mélanie 申请人:Breitling Montres Sa; IPC主号:
专利说明:
Description TECHNICAL FIELD [0001] The present invention relates to the field of watchmaking. It relates more particularly to a watch component on which a lubricant is deposited. STATE OF THE ART [0002] In the field of watchmaking, effective lubrication of the surfaces subjected to friction is essential for the proper functioning of the movement in the long term. The service interval of a movement is typically between four and six years, five years being particularly common. Since it is only at the time of full service that the movement is cleaned and relubricated, the performance of the lubricant used must be ensured throughout this interval. Its performances concern not only the chemical and physical properties of the lubricant (decomposition, viscosity, tribological properties, etc.), but also its position on the contact surfaces. The affinity of the lubricant with the surface conditions this position. The larger it is, the less the lubricant will tend to migrate out of the contact surfaces. This affinity is a function of the energy of the surface on which the lubricant is deposited and the surface tension of the lubricant itself. On the other hand, certain contacts between components are subjected to relative forces and relative speeds of the relatively large parts, such as the contact surfaces between the anchor pallets and the escape wheel, the balance shaft and the stones of the bearings, etc. These high speeds can also cause the lubricant to migrate out of the contact surfaces. It is known to the person skilled in the art that a watch movement only works for a few weeks without lubrication, and that the migration of the lubricant can occur very quickly, even in the case of gears between teeth. Without lubrication, friction increases, and damage to the contact surfaces occurs quickly. Various attempts have been made to try to eliminate the entire lubrication, including depositing under vacuum and on the components of low friction layers, including layers of carbon adamantine (DLC), layers based on alumina, oxide, nitride or silicon carbide, and the like. However, this statement is relatively complicated and expensive, and does not always give satisfaction at the level of tribology. Indeed, these layers do not always eliminate any conventional lubrication on components made from conventional materials, that is to say, metals and alloys. They also have internal tensions that can lead to their destruction in operation. Their grip on the surfaces is also difficult to control. Therefore, lubrication via oil or grease is still relevant. In order to avoid lubricant migration, a process of epilamization is typically used. An epilame is a product deposited on the surface of a watch, which prevents the spreading of lubricants. The lipophobic character of this epilame is used to prevent migrations of lubricants. Typically, a soaking bath is prepared, which contains a solution of a perfluorinated polymer dissolved in a hydrofluoroether. The parts are soaked in this solution, and on their exit, the solvent evaporates and leaves the polymer on the surface of the parts. It is also possible to deposit by dipping self-assembled layers of the type described in the patents of Surfactis Technologies SA WO 2012 085 134 and WO 2015 177 229. So-called functionalization molecules are deposited and organized spontaneously on the surface. by an end having a chemical affinity with the surface to be coated. The other end of the molecule has a lipophobic character. It is also possible to deposit a layer of epilam by chemical vapor deposition, in particular under vacuum, but a dipping process is more often used since it does not require equipment under vacuum, and can be carried out in an installation standard wash, whose program has been adapted to the treatment. A vacuum deposit also has the disadvantage of not allowing the deposition on the entire surface of the part since said parts are in contact with another surface in the treatment chamber, unlike a soaking solution where there is still a liquid interface between the parts and where it is possible easily via a movement of the door parts to agitate said parts thus allowing their complete recovery. However, a dipping process has several drawbacks, [0009] The concentration of molecules for modifying the surface energy must be scrupulously respected so as not to have stains on the parts, such stains. not acceptable for aesthetic reasons. The epilamization process is relatively long at about 20 minutes duration. The cost of the products used is important because of the chemical nature of the solvent. In addition, the amounts of solvent are relatively high, especially because the parts must be rinsed when they leave the bath. Moreover, in order to guarantee the quality of the treatment, the epilame solutions must be changed regularly to guarantee their effectiveness and to avoid unacceptable stains for the aforementioned aesthetic reasons. For this reason, the safety factor is often deliberately comfortable, resulting in wasted products and relatively high costs. In the case of so-called functionalization molecules and vacuum deposition, the resistance of the epilame solutions is not identical on all materials, which requires the use of different epilame molecules for each family of basic material of the parts. If the grip on copper or ferrous materials requires a type of epilame solution, the attachment on surfaces on which are deposited Rhodium or Gold, for aesthetic reasons, require another type of epilame. The application of these solutions requires an almost perfect surface state, so a perfect preparation / la-vage quality. For example, the slightest trace of oil or grease on the surface will not allow the epilame molecule to deposit or graft on this part of the surface. The layerless area will not be functionalized, will not retain the lubricant properly, and will appear as a stain. The latter is not acceptable for a high added value part. The epilame solutions are not content to act on the parts, but also act on the baskets and parts of the machine in contact with the baths. It is therefore necessary to attribute the epilamination material to this use, which increases the cost of this operation. In the case of epilam in a polymer layer, its resistance to washing is low. When going for after-sales service, for preventive maintenance or repair, it is often necessary to re-lay a layer of epilame. As the working conditions and the equipment are not the same, the performance of epilame can be below specification, which has repercussions on the performance of the movement because of a possible migration or on its aesthetics because the appearance of spots. In the case of so-called functionalization molecules or deposition of epilam by vacuum process, it is very difficult and expensive to remove the epilame once deposited on a part, or on baskets or machine parts affected. . These elements of the equipment are therefore difficult to clean. The object of the invention is therefore to provide a watch component on which a lubricant is deposited and wherein the aforementioned defects are at least partially overcome. Disclosure of the invention [0018] More precisely, the invention relates to a watch component comprising a contact surface intended to be in dynamic contact with another watch component, that is to say that this surface is intended for rub against the surface of another component. On at least a portion of said contact surface is deposited a lubricant comprising at least one oil and / or grease and / or ionic liquid, which serves as a base for the lubricant and therefore represents the majority of the composition. According to the invention, the lubricant further comprises at least one additive having the structure: -) nR1 wherein R comprises a lipophilic group if the base of the lubricant is an oil or a fat or is an ionic group in the case where the base is an ionic liquid. R1 comprises a group selected from phosphonic acids, silanes and thiols, and n is a positive integer. The R group may be branched to provide the molecule with other functions lubricant or improve the anchoring of said molecule lubricant. In other words, the R group can start with one or more carbon atoms having a first branch to a lipophilic group, and a second branch that has a group having another functionality. Still other branches are also possible. For this purpose, there may be mentioned a fluorescent group, a group that has an affinity for another component of the lubricant base, or any other desirable functionality. Moreover, the group R 1 may be branched in the same way, for example by also including a second functional group of any kind. Surprisingly, the use of such a molecule makes it possible to eliminate any epilamization of the component, since the indicated R 1 groups have a hook tenacity which is sufficient to anchor the lubricant on the surface without modification of the latter. . Therefore, any surface treatment operation other than polishing and cleaning can be eliminated. Therefore, the component can be lubricated and mounted in the movement in a conventional manner, and without epilamming step. The elimination of the long and expensive steps of epilamization presents significant savings in the method of manufacturing the component, and therefore the final timepiece. Advantageously, the group R may comprise a pentafluorophenol group, or a silane group, or a fluorocarbon group, or a methyl group, or a hydroxyl group, or an N-dimethyl-N-octadecyl ammonium group. These R groups attract the base component of the lubricant, and generate stability of the positioning of the lubricant in the long term due to the grip on the surface made by R1. Examples of additives corresponding to the above definitions are: 11-Pentafluorophenoxyundecyltrimethoxysilane; • 1,10-bis (trimethoxysilyl) decane; • 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoronadecanethiol; • n-octadecylphosphonic acid; • 11-hydroxyundecylphosphonic acid; • (12-phosphonododecyl) phosphonic acid; • 12-dodecylphosphonic acid chloride or bromide N, N-Dimethyl-N-octadecyl ammonium; and • 12-pentafluorophenoxydodecylphosphonic acid. Advantageously, the value of n is in the range between 1 and 22, which means that the length of the total carbon chain between the R and R1 groups is between 1 and 22 carbon atoms. Advantageously, the proportion of said additive in said lubricant is between 0.01% and 5% by weight, preferably between 0.01% and 2.5%, more preferably between 0.25% and 0.75%, which generates the desired performance of the lubricant. The watch component in question may, for example, be a balance shaft, an axis of a moving body, an axis of a toothed wheel, a toothed wheel, an anchor pallet, a mainspring, a bung of a barrel, a drum of a barrel, a lid of a barrel, a board of pendulum, a frame element, or a stem of winding. The invention also relates to a watch movement comprising the aforementioned component, a timepiece comprising such a movement, and the use of the lubricant defined above for the lubrication of a watch component. BRIEF DESCRIPTION OF THE DRAWINGS [0030] Other details of the invention will appear more clearly on reading the description which follows, made with reference to the appended drawings in which: Fig. 1 is a schematic view of a watch component provided with a lubricant layer according to the invention; Fig. 2-9 are representations of various molecules useful as lubricant additives; Fig. 10 and 11 show graphs illustrating the performance of certain reference lubricants and according to the invention; and Fig. 12 represents a graph illustrating the spreading of drops of lubricants according to the invention. Embodiments of the Invention The general principle on which the invention is based is, in a similar way to that of the documents WO 2012 085 134 and WO 2015 177 229, to functionalize the lubricant to anchor itself on the surface. all by itself instead of functionalizing the surface to better retain the lubricant. This principle is illustrated schematically in Figure 1, which shows a watch component 1 on which is deposited a lubricant 3 on a contact surface 5. This surface 5 is intended to come into dynamic contact with a corresponding surface of a other watchmaking component and thus to undergo friction. The component 1 may be, for example, a rocker shaft intended to come into contact with the stones of a shockproof bearing, an axis of a mobile which rubs against its bearing, an axis of a anchor, a toothed wheel whose teeth rub against complementary teeth of another toothed wheel, an anchor pallet which rubs against the teeth of an escape wheel, a mainspring, which rubs against itself and against the wall of the drum, against the bung as well as against the lid of a barrel, a winding stem, or any other component which undergoes friction such as for example a frame element which undergoes friction generated by a mobile which rubs on its area. Lubricant 3 comprises, as a base, a conventional grease or oil, such as for example a Synt-A-Lube ™ oil 9010, 9415, Sintescap 941 or similar marketed by The Swatch Group R & D Ltd.. Moebius Division. These lubricants are proprietary, and their compositions remain unchanged over time. Lubricants (oils or greases) from Drillwich, LRCB, among others, or proprietary lubricants developed within the watch brands can also be used. Alternatively, the base of the lubricant may be an ionic liquid such as a compound based on the cation 1-ethyl-3-methylimidazolium (EMIM), for example: EMIM: CI, EMIM dicyanamide. (C2H5) (CH3) C3H3N + 2 N (CN) 2, 1-butyl-3,5-dimethylpyridinium bromide, 1-Butyl-1-methylpyrrolidinium bis (oxalato) C13H2ONB08, or trihexyl (tetradecyl) phosphonium bis (oxalato) borate C36H68B08P. The lubricant 3 also comprises an amount of additive 7, of general structure: ## STR2 ## In this molecule, the group R comprises a lipophilic group or, more generally, a group which has a particular chemical affinity with one of the components of the lubricant to cling chemically (strong bonds) to fat or oil, or is ionic to exhibit the same effect (chemical affinity) when using an ionic liquid as a base for the lubricant. By cons, the group R1, called "head", is used to graft the molecule to the surface 5. By grafting on the surface, the additive 7 serves to retain the fat or oil on the molecule, and therefore on the surface. The R1 group may be hydrophobic or hydrophilic, and is rather lipophobic to prefer a grip on the surface instead of the base lubricant. Tests have shown that, surprisingly, silane groups, thiol groups, and phosphonic acid groups are particularly effective for this purpose. Furthermore, the group R may comprise a pentafluorophenol group, a silane group, a fluorocarbon group, a methyl group, or a hydroxyl group to be lipophilic. Alternatively, the R group may be an N-dimethyl-N-octadecylammonium group so as to be ionic and thus attract an ionic liquid as a base for the lubricant. More particularly, mention may be made of the following molecules which may serve as additive 7: • 11-Pentafluorophenoxyundecyltrimethoxysilane (FIG 2); • 1,10-bis (trimethoxysilyl) decane (Fig. 3); • 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoronadecanethiol (Fig. 4); • n-octadecylphosphonic acid (Figure 5); • 11-hydroxyundecylphosphonic acid (Fig. 6); • (12-phosphonododecyl) phosphonic acid (Figure 7); • N, N-Dimethyl-N-octadecyl ammonium (12-dodecylphosphonic acid) bromide or chloride (Fig. 8); • 12-Pentafluorophenoxydodecylphosphonic acid (Figure 9). Of course, other molecules are also possible, for example variants of the above-mentioned molecules whose length of the carbon chain between the R group and the R 1 group is between 1 and 22 carbon atoms in length. (hence between n = 1 and n = 22), the nomenclature of the molecules being modified accordingly. Other variants of the silane, thiol, phosphonic acid, pentafluorophenol, fluorocarbon, methyl, hydroxyl or N-dimethyl-N-octadecylammonium groups are also possible. Furthermore, each of the groups R and R1 may optionally be branched to provide the molecule with other functions to the lubricant or to improve the anchoring of said molecule to the lubricant or to the surface 5. For example, the group R may start with one or more carbon atoms having a first branch to a lipophilic group (or ionic, if appropriate), and a second branch to a group having another functionality such as fluorescence for example. Still other branches are also possible. For this purpose, there may be mentioned a fluorescent group, a group that has an affinity for another component of the lubricant base, or any other desirable functionality. On the other hand, the group R 1 may be branched in the same way, for example also comprising a second optional functional group, serving for example to improve the adhesion to the surface 5, or to confer fluorescence or any other desirable property. . The important thing is that each R, R1 group comprises at least one group as mentioned above. The amount of additive 7 can vary between 0.01% and 5%, preferably between 0.01% and 2.5%, more preferably between 0.25% and 0.75% by weight of the lubricant 3. FIG. 10 represents a graph of a plurality of tests carried out which show that the additive 7 added to the base lubricant has advantages. In each of these tests, the pivoting movement of the kinematic chain from the barrel to the balance wheel were lubricated in a conventional manner with one of five lubricants. The lubricant "Reference" represents Moebius Sintescap 941 oil, and the axes of the mobiles are epilamized conventionally. The oscillation amplitude of the balance with movement in horizontal position was measured for ten months, which shows the effectiveness of lubricant 3: the better the lubricant (tribology and maintenance in place), the more the amplitude of the pendulum is high. A degradation of the lubricant is witnessed by a reduction of this amplitude over time, and the curve "Reference" represents the point of comparison. The other curves represent tests carried out with the axes of the non-epilamed mobiles, the pivots of which were lubricated with Moebius Sintescap 941 reference lubricant to which was added a particular additive 7. The "molecule A" to "molecule D" additives were chosen from the molecules illustrated in FIGS. 2 to 9, namely: • 11 -Pantafluorophenoxyundecyltrimethoxysilane (FIG. 2); • 1,10-Bis (trimetoxysilyl) decane (Fig. 3); • 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoronadecanethiol (Fig. 4); • n-octadecylphosphonic acid (Figure 5); • 11-hydroxyundecylphosphonic acid (Fig. 6); • (12-phosphonododecyl) phosphonic acid (Figure 7); • N, N-Dimethyl-N-octadecyl ammonium (12-dodecylphosphonic acid) bromide or chloride (Fig. 8); • 12-Pentafluorophenoxydodecylphosphonic acid (Figure 9). It is apparent that each of the additives tested improves the performance of the lubricant 3, and none of them affects its stability over time. On average, lubricants with additives improve the amplitude of the balance at a rate of between 10 ° and 20 ° amplitude, that is to say between about 4% and 8%, which is evidence of the improvement of the lubricant performance compared to the reference, even if an increase in amplitude is not necessarily sought in relation to the operation of the movement. FIG. 11 represents a second series of tests, in which two lubricants based on an ionic liquid have been compared with a reference identical to that of FIG. 10, that is to say a lubrication with the Moebius lubricant of reference on the epilamés pivots of the mobiles of the kinematic chain starting from the barrel with the pendulum. According to this series of tests, it is clear that the ionic liquid B can be considered promising lubricant. This ionic liquid is based on trihexyl (tetradecyl) phosphonium bis (oxalato) borate C36H68B08P and comprises N, N-dimethyl-N-octadecyl ammonium (12-dodecylphosphonic acid) chloride (FIG 8) as an additive. It is also shown an improvement over the reference lubricant, of the order of twenty degrees of amplitude, or about 7%. Observations on the spreading of the lubricant were also carried out, the results of which are reproduced in FIG. 12. This figure illustrates six drops of lubricants according to the invention which have been deposited on maraging steel plates (Durnico). previously cleaned in a conventional manner. The platelets were then vertically inclined for 24 hours. Each drop is based on the Moebius 941 lubricant mentioned above, with an addition of between 0.36% and 0.70% of a different additive 7 selected from those mentioned above. The evolution of the drops was observed using photographs taken by automatic triggering, and the diameters of the drops were then performed using a photo software. It is clear that five of the six tests (Reference + A-E molecules) show a virtually non-existent spread of the drops, and that one of the tests (Reference + molecule F) show a very small spread. It is thus clear that each of the lubricants tested has the properties sought by the invention. As regards the basic materials for component 1, there may be mentioned: rhodium-plated nickel-plated brass, steel, stainless steel, maraging steel, copper-beryllium, synthetic ruby, silicon with or without surface SiO 2, diamond, nickel obtained by UV-LiGA, nickel-phosphorus obtained by UV-LiGA, and these (or other) materials provided with a layer of adamantine carbon (DLC), silicon oxide, alumina, silicon carbide or nitride, or any other material that can be used to produce watch components. Although the invention has been particularly shown and described with reference to a particular embodiment, other variants are possible without departing from the scope of the invention as defined in the claims. 1. watch component (1) comprising a contact surface (5) intended to be in dynamic contact with another watch component, at least a portion of said contact surface (5) on which is deposited a lubricant (3) comprising a base comprising at least one oil and / or one grease and / or one ionic liquid and at least one additive (7), characterized in that said additive (7) having the structure: R-WsR1 in which: R comprises a lipophilic group if said base comprises an oil and / or a fat, or is an ionic group if said base comprises an ionic liquid, R1 comprises a group chosen from phosphonic acids, silanes and thiols, and
权利要求:
Claims (14) [1] The "molecule A" to "molecule D" additives were chosen from the molecules illustrated in FIGS. 2 to 9, namely: • 11 -Pantafluorophenoxyundecyltrimethoxysilane (FIG. 2); • 1,10-Bis (trimetoxysilyl) decane (Fig. 3); • 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoronadecanethiol (Fig. 4); • n-octadecylphosphonic acid (Figure 5); • 11-hydroxyundecylphosphonic acid (Fig. 6); • (12-phosphonododecyl) phosphonic acid (Figure 7); • N, N-Dimethyl-N-octadecyl ammonium (12-dodecylphosphonic acid) bromide or chloride (Fig. 8); • 12-Pentafluorophenoxydodecylphosphonic acid (Figure 9). It is apparent that each of the additives tested improves the performance of the lubricant 3, and none of them affects its stability over time. On average, lubricants with additives improve the amplitude of the balance at a rate of between 10 ° and 20 ° amplitude, that is to say between about 4% and 8%, which is evidence of the improvement of the lubricant performance compared to the reference, even if an increase in amplitude is not necessarily sought in relation to the operation of the movement. FIG. 11 represents a second series of tests, in which two lubricants based on an ionic liquid have been compared with a reference identical to that of FIG. 10, that is to say a lubrication with the Moebius lubricant of reference on the epilamés pivots of the mobiles of the kinematic chain starting from the barrel with the pendulum. According to this series of tests, it is clear that the ionic liquid B can be considered promising lubricant. This ionic liquid is based on trihexyl (tetradecyl) phosphonium bis (oxalato) borate C36H68B08P and comprises N, N-dimethyl-N-octadecyl ammonium (12-dodecylphosphonic acid) chloride (FIG 8) as an additive. It is also shown an improvement over the reference lubricant, of the order of twenty degrees of amplitude, or about 7%. Observations on the spreading of the lubricant were also carried out, the results of which are reproduced in FIG. 12. This figure illustrates six drops of lubricants according to the invention which have been deposited on maraging steel plates (Durnico). previously cleaned in a conventional manner. The platelets were then vertically inclined for 24 hours. Each drop is based on the Moebius 941 lubricant mentioned above, with an addition of between 0.36% and 0.70% of a different additive 7 selected from those mentioned above. The evolution of the drops was observed using photographs taken by automatic triggering, and the diameters of the drops were then performed using a photo software. It is clear that five of the six tests (Reference + A-E molecules) show a virtually non-existent spread of the drops, and that one of the tests (Reference + molecule F) show a very small spread. It is thus clear that each of the lubricants tested has the properties sought by the invention. As regards the basic materials for component 1, there may be mentioned: rhodium-plated nickel-plated brass, steel, stainless steel, maraging steel, copper-beryllium, synthetic ruby, silicon with or without surface SiO 2, diamond, nickel obtained by UV-LiGA, nickel-phosphorus obtained by UV-LiGA, and these (or other) materials provided with a layer of adamantine carbon (DLC), silicon oxide, alumina, silicon carbide or nitride, or any other material that can be used to produce watch components. Although the invention has been particularly shown and described with reference to a particular embodiment, other variants are possible without departing from the scope of the invention as defined in the claims. claims A watch component (1) comprising a contact surface (5) intended to be in dynamic contact with another watch component, at least a portion of said contact surface (5) on which a lubricant (3) comprising a base comprising at least one oil and / or one grease and / or one ionic liquid and at least one additive (7), characterized in that said additive (7) having the structure: R-WsR1 in which: R comprises a lipophilic group if said base comprises an oil and / or a fat, or is an ionic group if said base comprises an ionic liquid, R1 comprises a group chosen from phosphonic acids, silanes and thiols, and n is a positive integer . [2] 2. Watchmaking component (1) according to the preceding claim, wherein the group R comprises a group chosen from: • a pentafluorophenol group • a silane group • a fluorocarbon group • a methyl group • a hydroxyl group • a N-dimethyl group N-octadecylammonium [3] 3. watch component (1) according to one of the preceding claims, wherein said additive is selected from: • 11 -Pentafluorophenoxyundecyltrimethoxysilane; • 1,10-Bis (trimethoxysilyl) decane; • 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadecafluoronadecanethiol; • n-octadecylphosphonic acid; • 11-hydroxyundecylphosphonic acid; • (12-phosphonododecyl) phosphonic acid; 12-dodecylphosphonic acid chloride or bromide N, N-Dimethyl-N-octadecylammonium; "12-pentafluorophenoxydodecylphosphonic acid. [4] 4. watch component (1) according to one of the preceding claims, wherein n is in the range between 1 and 22 [5] 5. Horological component (1) according to one of the preceding claims, wherein the proportion of said additive in said lubricant is between 0.1% and 5%, preferably between 0.01% and 2.5%, more preferably between 0.25% and 0.75%. , by weight. [6] 6. Watch component (1) according to one of the preceding claims, wherein said clock component is selected from: • a balance shaft; o an axis of a mobile; • an axis of an anchor; • a gear wheel; • an anchor pallet; • a mainspring; • a bung of a barrel; • a drum of a barrel; • a lid of a barrel; • a balance board; • an anchor; • a winding stem; • a frame element. [7] 7. Watchmaking movement comprising a component (1) according to one of the preceding claims. [8] 8. Timepiece comprising a movement according to claim 7. [9] 9. Use of a lubricant (3) for lubricating a watch component (1), said lubricant (3) comprising at least one base comprising an oil and / or a grease and / or an ionic liquid and a additive (7) having the structure: R-HsR1 in which: R comprises a lipophilic group in the case where said base comprises an oil and / or a fat, or is an ionic group in the case where said base comprises an ionic liquid, R1 comprises a group selected from phosphonic acids, silanes and thiols, and n is a positive integer. [10] Use according to claim 9, wherein the R group is selected from: a pentafluorophenol group • a silane group • a fluorocarbon group • a methyl group • a hydroxyl group • an N-dimethyl-N-octadecyl ammonium group [11] 11. Use according to one of claims 9 and 10, wherein said additive is selected from: • 11-Pentafluorophenoxyundecyltrimethoxysilane; • 1,10-bis (trimethoxysilyl) decane; • 12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19,19-heptadécafluoronadécanethiole; • n-octadecylphosphonic acid; • 11-hydroxyundecylphosphonic acid; • (12-phosphonododecyl) phosphonic acid; • N, N-dimethyl-N-octadecyl ammonium (12-dodecylphosphonic acid) chloride or bromide; • 12-pentafluorophenoxydodecylphosphonic acid. [12] 12. Use according to one of claims 9 to 11, wherein n is in the range between 1 and 22. [13] 13. Use according to one of claims 9 to 12, wherein the proportion of said additive (7) in said lubricant (3) is between 0.1% and 5%, preferably between 0.01% and 2.5%, more preferably between 0.25 % and 0.75%, by weight. [14] 14. Use according to one of claims 9 to 13, wherein said clock component (1) is selected from: • a balance shaft; • an axis of a mobile; • an axis of an anchor; • a gear wheel; • an anchor pallet; • a mainspring; • a bung of a barrel; • a drum of a barrel; • a lid of a barrel; • a balance board; • a plateau pin; • an anchor; • a winding stem; • a frame element.
类似技术:
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同族专利:
公开号 | 公开日 CH713671B1|2021-02-15|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 WO2021005564A1|2019-07-10|2021-01-14|Patek Philippe Sa Geneve|Watch assembly having at least two contacting elements|
法律状态:
2020-10-30| AZW| Rejection (application)| 2020-11-13| AEN| Modification of the scope of the patent|Free format text: :LA DEMANDE DE BREVET A ETE REACTIVEE SELON LA DEMANDE DE POURSUITE DE LA PROCEDURE DU 28.10.2020. | 2021-01-29| PCOW| Change of address of patent owner(s)|Free format text: NEW ADDRESS: LEON BREITLING-STRASSE 2, 2540 GRENCHEN (CH) |
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申请号 | 申请日 | 专利标题 CH00458/17A|CH713671B1|2017-04-05|2017-04-05|Lubricated watch component.|CH00458/17A| CH713671B1|2017-04-05|2017-04-05|Lubricated watch component.| 相关专利
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