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    • 专利摘要:
    An object of the present invention is to provide a component for a timepiece, a movement and a timepiece having excellent lubricating oil resistance performance. Another object is also to propose a component for a timepiece (235) comprising a sliding surface (115) having a surface tension of 10 to 35 mN / m. It is preferred that when a lubricating oil having a surface tension of 25 to 35 mN / m is applied to the sliding surface (115), the interfacial tension between the sliding surface (115) and the lubricating oil is 0. at 7 mN / m.
    公开号:CH714765A2
    申请号:CH00287/19
    申请日:2019-03-11
    公开日:2019-09-13
    发明作者:Nakamura Takahiko；Ebihara Natsuki
    申请人:Seiko Instr Inc；
    IPC主号:
    专利说明:

    CH 714 765 A2
    Description
    BACKGROUND OF THE INVENTION
    1. Field of the invention The present invention relates to a component for a timepiece, a movement and a timepiece.
    2. Description of the Prior Art [0002] A driving force is applied continuously or intermittently to a timepiece component used in a timepiece, such as an escapement mobile and a anchor. Therefore, in order to reduce friction due to sliding during rotation or the like, it is required to maintain a lubricating oil at a location where the timepiece component slides.
    Document JP-A-2001-288,452 (patent document 1) discloses a technology for forming an oleophobic repellant film which is located outside an area where the lubricating oil is maintained, in order to retain the lubricating oil. in this area.
    However, since the timepiece component is small, it is difficult to form the oleophobic repellant film only in a specific area, and it was not easy to use the technology described in patent document 1 .
    In Japanese patent No. 4545405 (patent document 2) is disclosed a technology for forming an oleophobic repellant film on the entire component for a timepiece to maintain the lubricating oil at a location lubrication.
    However, it was not possible to assert that the timepiece component described in patent document 2 has a sufficient retaining function for the lubricating oil. Therefore, there have been cases where abrasion of the component for a timepiece has occurred due to a lack of lubricating oil.
    In addition, in the case where the concentration of a treatment agent for the formation of the oleophobic repellant film is low, it may happen that a part has not been treated by the surface treatment. Consequently, there may occur cases where the lubricating oil allows the diffusion of moisture, and abrasion of the component for a timepiece then occurs due to the lack of lubricating oil which allows the moisture to 'appear more easily.
    SUMMARY OF THE INVENTION According to one aspect of the present application, it is sought to provide a component for a timepiece, a movement, and a timepiece having excellent performance in terms of lubricating oil behavior. .
    According to another aspect of the present application, it is sought to provide a component for a timepiece comprising a sliding surface having a surface tension of between 10 and 35 mN / m.
    In such a configuration, since the affinity with the lubricating oil increases, it is unlikely that the lubricating oil will flow outside of the sliding surface. Consequently, since a state is maintained in which there is lubricating oil on the sliding surface, it becomes possible to remove any deterioration of the timepiece component due to abrasion or the like, and operate it stably over a long period of time.
    It is preferable that, when the lubricating oil having a surface tension between 25 and 35 mN / m is applied to the sliding surface, an interfacial tension between the sliding surface and the lubricating oil is between 0 and 7 mN / m.
    In such a configuration, it is even less likely that the lubricating oil will flow outside of the sliding surface. As a result, it is possible to further improve the oil holding performance.
    According to another aspect of this patent application, there is provided a movement comprising such a component for a timepiece.
    In such a configuration, since the component is supplied for a timepiece, it becomes possible to achieve stable operation for a long period of time, and to improve reliability.
    According to another aspect of this patent application, there is provided a timepiece including the movement.
    In such a configuration, since the component for the timepiece is supplied, it becomes possible to achieve stable operation for the timepiece over a long period of time, and to improve its reliability.
    According to the present application, a high performance of oil resistance with respect to a lubricating oil is disclosed.
    CH 714 765 A2
    BRIEF DESCRIPTION OF THE DRAWINGS
    Fig. 1 is a plan view illustrating an aspect of a front side of a movement included in a component for a timepiece according to a first embodiment of the present invention.
    Fig. 2 is a plan view illustrating an aspect of an escapement mobile which is part of the component for a timepiece according to the first embodiment.
    Fig. 3 is a plan view illustrating an aspect of an anchor which is part of the component for a timepiece according to the first embodiment.
    Fig. 4 is a side view illustrating an aspect of a component for a timepiece according to a second embodiment of the present invention.
    Fig. 5 is a perspective view and a sectional view illustrating a part of a component for a timepiece according to a third embodiment of the present invention.
    Fig. 6 is a perspective view illustrating an aspect of a component for a timepiece according to another embodiment of the present invention.
    Fig. 7 is a perspective view illustrating an aspect of a component for a timepiece according to another embodiment of the present invention.
    DESCRIPTION OF THE EMBODIMENTS Embodiments for the present invention will be described with reference to the drawings.
    Furthermore, in the description which follows, the same reference numbers will be given to configurations performing the same or similar functions. In addition, there may be cases where redundant parts of the description for overlapping configurations will not be repeated.
    In addition, in each of the following drawings, in order to make the drawing more visible, it may happen that part of a component for a timepiece and a movement are omitted, and that the component for a d horology as well as the movement are illustrated in a simplified manner.
    [First embodiment] A movement and a timepiece comprising a component for a timepiece according to a first embodiment of the present invention will be described with reference to FIG. 1.
    In general, a mechanical body comprising a drive part of the timepiece is called the "movement". The state in which a dial and a hand are attached to the movement, put in a timepiece case to make a finished product, is called the "whole" of the timepiece.
    [0024] FIG. 1 is a plan view of the front side of the movement.
    As illustrated in FIG. 1, the mechanical timepiece 201 is configured with a movement 210 and a case (not shown) in which the movement 210 is housed.
    The movement 210 has a plate 211 which configures a plate. A dial (not illustrated) is arranged on the rear side of the plate 211. Furthermore, reference is made to the gear train incorporated at the front of the movement 210 as being the front train, and to the gear train incorporated at the 'rear of movement 210 as the rear cog.
    In the plate 211, a winding stem guide hole 211 a is produced, and a winding stem 212 is rotatably inserted in the winding stem guide hole 211a. The position of the winding stem 212 in the direction of the shaft is determined by a switching device comprising an adjustment lever 213, a rocker 214, a rocker spring 215, and a jumper of adjustment lever 216. In addition , a winding pinion 217 is rotatably mounted in the guide portion of the shaft of the winding stem 212.
    When the winding stem 212 is rotated in a state where the winding stem 212 is in a first winding stem position (level 0), the closest inward of the movement 210 along d 'A rotary direction of the shaft, the winding pinion 217 rotates through the rotation of a clutch wheel (not shown). In addition, as the winding pinion 217 rotates, a crown wheel 220 engaged with it also rotates. Furthermore, as the crown wheel 220 rotates, a röchet wheel 221 engaged therewith rotates. In addition, as the röchet 221 rotates, a main spring (energy source - not shown) housed in a movement barrel 222 is wound on itself.
    The front train of the movement 210 is formed by a second mobile (that is to say a wheel and a pinion) 225, a third mobile 226, and a fourth mobile 227 in addition to the barrel of the movement 222 described here. above, and realizes
    CH 714 765 A2 a function of transmitting a rotational force of the barrel of the movement 222. In addition, at the front of the movement 210 are disposed an exhaust mechanism 230 and a speed adjustment mechanism 231 for controlling the front wheel rotation.
    The second mobile 225 is perceived as a wheel meshing with the barrel of the movement 222. The third mobile 226 is perceived as a wheel meshing with the second mobile 225. The fourth mobile 227 is perceived as a wheel meshing with the third mobile 226.
    The speed adjustment mechanism 231 is a mechanism for adjusting the speed of the exhaust mechanism 230 and has a sprung balance 240.
    The exhaust mechanism 230 is a mechanism for controlling the rotation of the front wheel train described above, and comprises an exhaust mobile 235 meshing with the fourth mobile 227, and an anchor 236 which makes the mobile of exhaust 235 escapes and turns regularly. The escapement mechanism 230 is a component for a timepiece according to the first embodiment of the present invention.
    [0033] FIG. 2 is a plan view of the exhaust mobile 235 which configures the exhaust mechanism 230. FIG. 3 is a plan view of the anchor 236 which configures the exhaust mechanism 230.
    Mobile exhaust [0034] As illustrated in FIG. 2, the exhaust mobile 235 comprises an escape wheel 101 and a shaft 102 fixed coaxially to the escape wheel 101. Reference is made to a direction orthogonal to the axial line of the shaft 102 as being a radial direction. In fig. 2, the direction of rotation of the exhaust mobile 235 is indicated by the direction CW.
    The escape wheel 101 includes an annular serge 111, a hub 112 disposed inside the serge 111, and a plurality of spokes 113 mutually connecting the serge 111 to the hub 112. The hub 112 has a shape of disc, and the shaft 102 is fixed to its central part by fitting, driving or the like. Each of the spokes 113 extends radially from an outer circumferential edge of the hub 112 in the direction of an inner circumferential edge of the serge 111.
    On an outer circumferential surface of the serge 111, a plurality of special teeth 114 having a special hook shape protrude outward in the radial direction. Pallet stones 144a and 144b (see fig. 3) of the anchor 236 which will be described later mesh with ends of the plurality of teeth 114.
    The lateral surface of the end of the tooth 114 is positioned on the side of the exhaust mobile 235 the farthest in the direction of rotation CW, and has a stop surface 115a against which the pallet stones 144a and 144b come into abutment, a rear surface 115b positioned on the nearest side in the direction of rotation CW, and an impact surface 115c which is an end surface of the tip of the tooth 114.
    A corner formed between the stop surface 115a and the impact surface 115c functions as a locking corner 115d. A corner formed between the rear surface 115b and the impact surface 115c functions as an exit corner 115e.
    In tooth 114, an area extending from the stop surface 115a to the exit corner 115e via the locking corner 115d configures a sliding surface 115. The sliding surface is a surface which can enter contact with another timepiece component.
    The surface tension of the sliding surface 115 is from 10 to 35 mN / m, preferably from 11 to 35 mN / m, and even more preferably from 20 to 30 mN / m. When the surface tension of the sliding surface 115 is greater than or equal to the lower limit value, the affinity with the lubricating oil increases, and when the lubricating oil is applied to the sliding surface 115, a performance of higher resistance to lubricating oil. Therefore, it is unlikely that the lubricating oil will flow outside of the sliding surface 115. In this way, since a state in which lubricating oil is on the sliding surface 115 is maintained , it becomes possible to remove any deterioration of the exhaust mobile 235 due to abrasion or the like, and to operate the timepiece stably over a long period of time. When the surface tension of the sliding surface 115 is less than or equal to the upper limit value, it is unlikely that the lubricating oil will allow moisture to spread when the lubricating oil is applied to the sliding surface 115. Consequently, since it is unlikely that the lubricating oil will let moisture appear and that a state in which the lubricating oil remains on the sliding surface 115 is maintained, it becomes possible to remove any deterioration of the exhaust mobile 235 due to abrasion or the like, and to operate these components stably over a long period of time.
    In the meantime, when vibrations are applied to the timepiece component, the lubricating oil may be dispersed. In particular, at a part where an intermittent meshing is repeated, such as an escape mechanism comprising the escapement mobile and the anchor, or a calendar mechanism including a date indicator and a date jumper which will be described later, or the like, the dispersion of the lubricating oil tends to become spectacular.
    CH 714 765 A2 When the surface tension of the sliding surface 115 is between 11 and 35 mN / m, it is unlikely that the lubricating oil will be dispersed even when the vibration is applied to the exhaust mobile 235 Accordingly, since the lubricating oil remains more stable on the sliding surface 115, it is possible to more effectively suppress deterioration of the exhaust mobile 235 due to abrasion or the like.
    The surface tension of the sliding surface 115 is obtained by the method of graphical representation of Zisman. Specifically, first, a plurality of test liquids having different surface tensions are deposited on the sliding surface 115 and form droplets, and a contact angle (θ) between the droplet and the sliding surface 115 is measured to calculate cosO. Then, the surface tensions of each test liquid are plotted on the transverse axis and cosO is plotted on the longitudinal axis to prepare the Zisman curve, and the value of the surface tension is obtained when cos9 = 1 on the first segment straight line of approximation. A similar operation is carried out at five different locations on the sliding surface 115 to prepare the graphical representation curve of Zisman, the value of the surface tension when cos9 = 1 on the first rectilinear approximate segment, and the mean value is defined. as the surface tension of the sliding surface 115. In addition, the formation of droplets and the measurement of the contact angle (θ) are carried out at 25 ° C.
    The surface tension of the sliding surface 115 can take the same value or have different values at all the locations of the sliding surface 115 as long as the surface tension is within the range of values described above. above.
    As test liquid, pentane (16.0 mN / m), heptadecane (27.4 mN / m), iodocyclohexane (35.7 mN / m), ethylene glycol (48.4 mN / m) , formamide (58.1 mN / m), diiodomethane (66.2 mN / m), glycerin (63.4 mN / m), and distilled water (72.8 mN / m) are used.
    In addition, the numerical values in brackets are the surface tensions at 25 ° C.
    When the lubricating oil having a surface tension of 25 to 35 mN / m at 25 ° C is applied to the sliding surface 115, the interfacial tension between the sliding surface 115 and the lubricating oil is preferably included between 0 and 7 mN / m, more preferably between 0 and 5 mN / m, and even more preferably between 0.4 and 3 mN / m. A case where the interfacial tension between the sliding surface 115 and the lubricating oil is less than or equal to the upper limit means that the affinity with the lubricating oil is better, and that the lubricating oil exhibits better performance in terms of oil resistance. Therefore, it is more unlikely that the lubricating oil will flow out of the sliding surface 115. In addition, it is unlikely that the lubricating oil will allow moisture to spread, and also more unlikely to let it show through. Consequently, since a state where the lubricating oil remains on the sliding surface 115 is better maintained, it becomes possible to suppress any deterioration of the exhaust mobile 235 due to abrasion or the like, and to operate these components more stably over a long period of time. In particular, when the interfacial tension between the sliding surface 115 and the lubricating oil is between 0 and 5 mN / m, it is possible to suppress the dispersion of the lubricating oil even when vibrations are applied to the moving body. exhaust 235.
    The interfacial tension between the sliding surface 115 and the lubricating oil is obtained by the Young's equation. Specifically, firstly, the lubricating oil is deposited on the sliding surface 115 and forms droplets, and the contact angle (θ) between the droplet and the sliding surface 115 is measured to calculate the cosO. Separately, the surface tension (y s ) of the sliding surface 115 at the place where the lubricating oil was deposited is obtained by the method of graphical representation of Zisman described above. In addition, the surface tension (y L ) of the lubricating oil is obtained by a catalog value or a method of optical determination known as the hanging drop (“during drop”). Then, cosO, y s , and y L are substituted in the Young equation illustrated in the following equation (i) in order to obtain the interfacial tension (y L s) between the solid and the liquid. A similar operation is carried out at five different locations on the sliding surface 115 to obtain y L s, and its mean value is defined as the interfacial tension between the sliding surface 115 and the lubricating oil. In addition, the formation of droplets and the measurement of the contact angle (θ) are carried out at 25 ° C.
    Ys = 7LS + TL · COS0 ··· (i) [In equation (ί), γ 3 is the surface tension of the solid (sliding surface 115), Yls is the interfacial tension between the solid and the liquid (sliding surface 115 and lubricating oil), y L is the surface tension of the liquid (lubricating oil), and 0 is the contact angle between the solid (sliding surface 115) and the liquid [lubricating oil ]).
    The interfacial tension between the sliding surface 115 and the lubricating oil can consist of an identical value at all the places of the sliding surface 115, or take different values at all these places as long as the interfacial tension is found in the range of values described above.
    The lubricating oil is not particularly limited as long as the surface tension at 25 ° C. is within the range of values described above and as long as the lubricating oil is a lubricating oil to be used for a timepiece, but for example, aliphatic hydrocarbons, such as poly a-olefin (PAO) and polybutene; aromatic hydrocarbons, such as alkylbenzenes and alkylnaphthalenes; ester oils, such as esters
    CH 714 765 A2 of polyol and phosphate esters; ether oils, such as polyphenyl ethers; polyalkylene glycol oils; silicone oils; and fluorinated oils are used.
    In order to fix the surface tension of the sliding surface 115 or the interfacial tension between the sliding surface 115 and the lubricating oil in the ranges of value described above, for example, a place (a treated surface) having to be the sliding surface 115 can be treated using an oil maintenance treatment agent which will be described below before forming an oil maintenance film 116 therein.
    The surface tension of the exhaust mobile 235 at a part other than that corresponding to the sliding surface 115 is not particularly limited, and may be between 10 and 35 mN / m or may be outside this range of values. In addition, the interfacial tension between the surface of the exhaust mobile 235 at a part other than the sliding surface 115 (that is to say a non-sliding surface) and the lubricating oil having a surface tension between 25 and 35 mN / m at 25 ° C is not particularly limited, and may be between 0 and 7 mN / m or may even be outside this range of values. In other words, the oil retaining film 116 can be formed on a non-sliding surface of the exhaust mobile 235, or not be formed at all. In addition, a film having a surface tension lower than that of the sliding surface 115 can be formed on the non-sliding surface of the exhaust mobile 235, and a film having, for example (oleophobic repelling film) a tension surface of less than 10 mN / m, is used as such.
    Anchor As illustrated in FIG. 3, the anchor 236 includes an anchor body 142d and an anchor rod 142f which are formed in a T shape by three anchor beams 143. The anchor body 142d is configured to be rotatable around a anchor rod 142f which constitutes a tree. The two ends of the anchor rod 142f are rotatably mounted respectively between the plate 211 and an anchor bridge (not shown) of the movement 210 illustrated in FIG. 1. In addition, the range of rotation of the anchor 236 is limited by a limiting pin (not shown).
    Pallet stones (an internal pallet stone 144a and an external pallet stone 144b) are arranged at the ends of two anchor beams 143 of the three anchor beams 143, and a double plate (not illustrated) of the pendulum with hairspring 240 of movement 210 illustrated in fig. 1 and a detachable anchor part 145 (the stinger) are fixed to one end of the remaining anchor beam 143. The pallet stones (the internal pallet stone 144a and the external pallet stone 144b) are in ruby and have a prism shape, and adhere and are fixed to the anchor beam 143 by means of an adhesive or the like.
    The end of the outer pallet stone 144b has a stop surface 146a which is positioned on the nearest side in the direction of rotation CW of the escapement wheel 101 illustrated in fig. 2, and abuts against the stop surface 115a of the tooth 114, a rear surface 146b which is positioned on the side furthest in the direction of rotation CW, and an impact surface 146c which is a surface of end of external pallet stone 144b.
    A corner formed by the abutment surface 146a and the impact surface 146c functions as a locking corner 146d. A corner formed by the rear surface 146b and the impact surface 146c functions as an exit corner 146e.
    In the external pallet stone 144b, an area which extends from the stop surface 146a to the exit corner 146e via the locking corner 146d defines a sliding surface 146.
    In addition, since the configuration of the end of the internal pallet stone 144a among the pallet stones 144a and 144b is the same as the configuration of the end of the external pallet stone 144b, the description of this item will not be repeated.
    The surface tension of the sliding surface 146 is between 10 and 35 mN / m, preferably between 11 and 35 mN / m, and even more preferably between 20 and 30 mN / m. When the surface tension of the sliding surface 146 is equal to or greater than the lower limit value, the affinity with the lubricating oil increases, and when the lubricating oil is applied to the sliding surface 146, the lubricating oil demonstrates high holding performance. Therefore, it is unlikely that the lubricating oil will flow out of the sliding surface 146. As a result, since a condition where lubricating oil remains on the sliding surface 146 is maintained, it becomes possible to remove any deterioration of the anchor 236 due to abrasion or the like, and to operate it stably over a long period of time. When the surface tension of the sliding surface 146 is less than or equal to the upper limit value, it is unlikely that the lubricating oil will allow moisture to spread when the lubricating oil is applied to the slip 146. As a result, since the lubricating oil is unlikely to allow moisture to pass through and a state where lubricating oil remains on the sliding surface 146 is maintained, it becomes possible to remove any deterioration of the anchor 236 due to abrasion or the like, and to operate the anchor stably over a long period of time. In particular, when the surface tension of the sliding surface 146 is between 11 and 35 mN / m, it is unlikely that lubricating oil will be dispersed even when vibrations are applied to the anchor 236.
    The surface tension of the sliding surface 146 is obtained using the Zisman graphical determination method. Specifically, the surface tension is obtained in the same way as the surface tension of the sliding surface of the exhaust mobile.
    CH 714 765 A2 The surface tension of the sliding surface 146 can have an identical value at all the places of the sliding surface 146, or different values at all these places as long as the surface tension is in the range of values described above.
    When the lubricating oil having a surface tension between 25 and 35 mN / m at 25 ° C is applied to the sliding surface 146, an interfacial tension between the sliding surface 146 and the lubricating oil is comprised of preferably between 0 and 7 mN / m, more preferably between 0 and 5 mN / m, and even more preferably between 0.4 and 3 mN / m. A case where the interfacial tension between the sliding surface 146 and the lubricating oil is less than or equal to the upper limit value means that the affinity with the lubricating oil is even better, and the lubricating oil exhibits a higher oil holding performance. Therefore, it is more unlikely that the lubricating oil will flow out of the sliding surface 146. In addition, it is unlikely that the lubricating oil will allow moisture to spread, and that moisture is reflected on the sliding surface. Consequently, since a state where the lubricating oil remains on the sliding surface 146 is much better maintained, it becomes possible to suppress any deterioration of the anchor 236 due to abrasion or the like, and to operate it from more stable over a long period of time. In particular, when the interfacial tension between the sliding surface 146 and the lubricating oil is between 0 and 5 mN / m, it is possible to suppress any dispersion of the lubricating oil even when vibrations are applied to the anchor 236.
    The interfacial tension between the sliding surface 146 and the lubricating oil is obtained using the Young's equation. Specifically, the interfacial tension is obtained in the same way as the interfacial tension between the sliding surface of the exhaust mobile and the lubricating oil.
    The interfacial tension between the sliding surface 146 and the lubricating oil can have a value identical to all the places of the sliding surface 146, or different in all these places as long as the interfacial tension is in the range of values described above.
    In order to fix the surface tension of the sliding surface 146 or the interfacial tension between the sliding surface 146 and the lubricating oil in the ranges of values described above, for example, a place (a treated surface) intended to be the sliding surface 146 can be treated using the oil holding treatment agent which will be described later, and an oil holding film 147 can be formed.
    The surface tension of the anchor 236 at a part other than the sliding surface 146 is not particularly limited, and may be between 10 and 35 mN / m, or may even be outside of this range of values. In addition, the interfacial tension between the surface (non-sliding surface) of the anchor 236 at a part other than the sliding surface 146 and the lubricating oil having a surface tension of between 25 and 35 mN / m at 25 ° C is not particularly limited; it can be between 0 and 7 mN / m or can be outside this range. In other words, the oil holding film 147 may be formed on a non-slip surface of the anchor 236, or the oil holding film 147 may not be formed at all. In addition, a film having a surface tension lower than that of the sliding surface 146 can be formed on the non-sliding surface of the anchor 236, and a film (oleophobic repellent film) having for example a surface tension of less 10 mN / m is used as such.
    Oil retaining film The oil retaining films 116 and 147 are made, for example, of a material having a greater surface energy than that of the material forming the treated surface.
    The oil holding films 116 and 147 contain, for example, a component - which will be referred to below as the "component (1)" - represented by the following general formula (1).
    In the general formula (1), Μ 1 is silicon, titanium, or zirconium, R is a hydrocarbon group, both Y 1 and Y 2 taken independently are a hydrocarbon group, a hydroxy group, or a functional group which generates the hydroxy group by hydrolysis or the like, and Z 1 is a polar group.
    Examples of hydrocarbon groups include an alkyl group and an aryl group. The hydrocarbon group is preferably an alkyl group. The alkyl group is represented by the formula C n H2n + i (n being an integer), “n” is preferably between 1 and 18, more preferably between 2 and 14, and even more preferably between 2 and 10, and particularly preferably from 3 to 6. When n is greater than or equal to the lower limit value
    CH 714 765 A2 described above, it is possible to improve the oil-holding properties. When n is less than or equal to the upper limit value described above, it is possible to avoid a deterioration in the quality of the oil-retaining film due to steric hindrance. In particular, when n is less than or equal to 10, it is possible to shorten the time required for the polymerization reaction.
    The "functional group which generates the hydroxy group by hydrolysis or the like" is, for example, an alkoxyl, an aminoxy group, a ketoxime group, an acetoxy group and the like, and one or more of these can be used . The alkoxyl is, for example, a methoxy group, an ethoxy group, a propoxy group and the like, and one or more of these can be used.
    The polar group is a functional group having a polarity. The polar group is, for example, a hydroxy group, a carboxy group, a sulfo group, an amino group, a phosphate group, a phosphino group, a silanol group, an epoxy group, an isocyanate group, a cyano group, a group vinyl, a thiol group and the like, and one or more of these can be used.
    In the compound (1), the functional group represented by Z 1 , Y 1 , and Y 2 can be in a configuration according to which a part of the elements which compose it is lost by adhesion. For example, the hydroxy group (-OH) which is Z 1 can be in an "-O-" configuration by adhesion - and the valence bond which results therefrom - with the surface treated by dehydration-condensation. The hydroxy group (-OH) which is Y 1 and Y 2 can be in a “-O-” configuration by bonding with the other Y 1 or Y 2 by dehydration-condensation. Similarly, the carboxy group (-COOH) can be in a “-COO-” type configuration by adhesion.
    The content of the compound (1) relative to the total mass of the oil retaining films 116 and 147 is, for example, greater than or equal to 50% of their mass.
    For example, the polar group of the compound (1) is linked to, or absorbed by a material (for example, an inorganic substance, such as a metal) which forms the surface treated by dehydration-condensation, hydrogen bonding or similar. Compound (1) can give high oil-holding performance to oil-holding films 116 and 147.
    As compound (1), for example, a compound represented by the following general formula (2) can be illustrated.
    OH
    I CH 3 (CH 2 ) 7 -S i-OH ··· (2)
    I
    OH The compound (1) can be obtained, for example, by hydrolysis of a compound represented by the following general formula (3).
    Y 1
    I,,
    R — Μ —X · (3)
    Y 2 In the general formula (3), Μ 1 is silicon, titanium, or zirconium, R is a hydrocarbon group, both Y 1 and Y 2 taken independently are a hydrocarbon group, a hydroxy group , or a functional group which generates the hydroxy group by hydrolysis or the like, and X 1 is a functional group which generates a hydroxy group by hydrolysis or the like.
    As the compound represented by the general formula (3), for example, octyltriethoxysilane (for example, triethoxy-n-octylsilane), triethoxyethylsilane, butyltrimethoxysilane or the like represented by the following general formula (4) can be used.
    CH 714 765 A2
    OCH 2 CH 3
    I CH 3 (CH 2 ) 7 -S i-OCH 2 CH 3 - (4)
    I
    OCH 2 CH 3 To form the oil maintenance films 116 and 147, for example, the oil maintenance treatment agent containing an oil maintenance agent containing the compound (1) and a solvent are used. One type of compound (1) can be used alone, or two or more types thereof can be used in combination.
    The oil maintenance agent preferably contains at least one acid and / or a base. The acid and base are not particularly limited as long as the acid and base accelerate the hydrolysis reaction, but the latter include acids such as acetic acid, hydrochloric acid, nitric acid, sulfuric acid; and bases, such as sodium hydroxide and potassium hydroxide. The combined amount of acid and base is, for example, from 1 to 20 moles based on 100 moles of the compound (1). An additive (for example, a curing catalyst, such as dibutyltin diaurate or the like) can be added to the oil preservative. The amount of additive added to the total mass of the oil preservative corresponds, for example, to a percentage between 0.001 and 5% of the mass.
    As a solvent, an alcohol, ketone or the like can be used. Alcohols include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol and the like. Ketones include acetone, ethyl methyl ketone or the like. In addition, the oil maintenance treatment agent may not contain a solvent.
    In order to form the oil retaining films 116 and 147, the treated surface is covered with the oil retaining treatment agent to form a coating film. By drying the coating film and removing the solvent, the oil retaining films 116 and 147 are obtained. The surfaces where the oil retaining films 116 and 147 have been applied constitute the sliding surfaces 115 and 146. The surface tension of the sliding surfaces 115 and 146 or the interfacial tension between the sliding surfaces 115 and 146 and the lubricating oil can be controlled, for example, by the type or content of the compound (1) in the holding films d oil 116 and 147 and the thickness of the oil retaining films 116 and 147.
    Examples of a coating method for the oil maintenance treatment agent include a soaking method, a spray coating method, a brush coating method, a curtain coating method, a spray coating method, or the like.
    In a case where the oil retaining films 116 and 147 contain the compound (1), the thickness of the oil retaining films 116 and 147 is preferably between 0.1 and 1 μm. When the thickness of the oil-holding films 116 and 147 is within the range described above, it is possible to easily demonstrate sufficient oil-holding performance, without this interfering with the functions of the exhaust mobile 235 and the anchor 236.
    The oil holding films 116 and 147 are not limited to the above description, and for example, may contain fluorinated compounds.
    The fluorinated compound is not particularly limited as long as the surface surface tension (that is to say, sliding surfaces 115 and 146) when the oil retaining films 116 and 147 are produced and the interfacial tension between the sliding surfaces 115 and 146 and the lubricating oil are within the range described above. As a fluorinated compound, it is possible to use a commercially available product, for example, the product of the name "HFD-1098" manufactured by Harves Co., Ltd. and the product name "SFE-MS 01" manufactured by AGC Seimi Chemical Co. may be used.
    In the case where the oil retaining films 116 and 147 contain the fluorinated compound, the thickness of the oil retaining films 116 and 147 is preferably greater than or equal to 1 nm, and less than 100 nm . When the thickness of the oil-holding films 116 and 147 is within the range described above, it is possible to easily demonstrate sufficient oil-holding performance without interfering with the functions of the mobile 235 and the anchor 236.
    The surface tension of the sliding surfaces 115 and 146 or the interfacial tension between the sliding surface 115 and 146 and the lubricating oil can be controlled, for example, by the type or content of the fluorinated compound in the films of holding oil 116 and 147 and the thickness of the oil holding films 116 and 147.
    Since the exhaust mechanism 230 which constitutes the component for a timepiece for the present embodiment comprises the exhaust mobile 235 having a sliding surface 115 having a surface tension of between 10 and 35 mN / m, and the anchor 236 having a sliding surface 146 having a surface tension of between 10 and 35 mN / m, the sliding surfaces 115 and 146 show great affinity with the lubricating oil, and d '' high oil holding performance for lubricating oil. Therefore, it is little
    CH 714 765 A2 likely that the lubricating oil does not flow out of the sliding surfaces 115 and 146. Consequently, since a state is maintained where the lubricating oil remains at the location where the sliding occurs, it becomes possible to suppress any deterioration of the exhaust mechanism 230 due to abrasion or the like, and to operate the mechanism stably over a long period of time. In particular, when the surface tension of the sliding surfaces 115 and 146 is between 11 and 35 mN / m, it is unlikely that the lubricating oil will be dispersed from the location where the sliding occurs, even when vibrations are applied to the exhaust mechanism 230.
    [Second embodiment] A component for a timepiece according to a second embodiment of the present invention will be described with reference to FIG. 4.
    FIG. 4 is a side view illustrating a wheel 60 which constitutes the component for a timepiece according to the second embodiment for the present invention.
    As illustrated in FIG. 4, the wheel 60 comprises a shaft 51 and a wheel part 52 fixed to the shaft 51.
    A first end 53 (first part corresponding to a post) and a second end 54 (second part corresponding to a second post) of the shaft 51 are rotatably supported by a bearing (not shown). It is possible that the outer circumferential surfaces of the first end 53 and the second end 54 slide against the inner circumferential surface of the bearing. It is possible that the external circumferential surface of an intermediate part 55 (intermediate part in the longitudinal direction) of the shaft 51 slides against the internal circumferential surface of a carriageway (barrel of a pinion - not illustrated). In other words, the outer circumferential surfaces of the first end 53, of the second end 54, and the intermediate part 55 of the shaft 51 constitute the sliding surfaces of the wheel 60.
    The surface tension of the outer circumferential surface (sliding surface) of the first end 53, of the second end 54, and the intermediate part 55 of the shaft 51 is between 10 and 35 mN / m, preferably between 11 and 35 mN / m, and even more preferably between 20 and 30 mN / m. When the surface tension of the sliding surface of the wheel 60 is greater than or equal to the lower limit value, the affinity with the lubricating oil increases, and when the lubricating oil is applied to the sliding surface of the wheel 60 , a high performance of oil resistance with respect to the lubricating oil is achieved. Therefore, it is unlikely that the lubricating oil will flow out of the sliding surface of the wheel 60. Thus, since a state where lubricating oil remains on the sliding surface of the wheel 60 is maintained, it becomes possible to suppress any deterioration of the wheel 60 due to abrasion or the like, and to operate the wheel stably over a long period of time. When the surface tension of the sliding surface of the wheel 60 is less than or equal to the upper limit value, it is unlikely that the lubricating oil will allow moisture to spread when the lubricating oil is applied to the sliding surface of the wheel 60. Consequently, since it is unlikely that the lubricating oil will reveal moisture and only a state where lubricating oil remains on the sliding surface of the wheel 60 is maintained, it becomes possible to suppress any deterioration of the wheel 60 due to abrasion or the like, and to operate it stably over a long period of time. In particular, when the surface tension of the sliding surface of the wheel 60 is between 11 and 35 mN / m, it is unlikely that lubricating oil will be dispersed even when vibrations are applied to the wheel 60.
    The surface tension of the sliding surface of the wheel 60 is obtained using the Zisman graphical determination method. Specifically, the surface tension is obtained in the same way as the surface tension of the sliding surface of the exhaust mobile, described in the context of the first embodiment. The surface tension of the sliding surface of the wheel 60 can have a constant value at all places on the sliding surface, or different at these different places as long as the surface tension is within the described range. above.
    When the lubricating oil having a surface tension of between 25 and 35 mN / m at 25 ° C is applied to the sliding surface of the wheel 60, the interfacial tension between the sliding surface and the lubricating oil is preferably between 0 and 7 mN / m, more preferably between 0 and 5 mN / m, and even more preferably between 0.4 and 3 mN / m. A case where the interfacial tension between the sliding surface of the wheel 60 and the lubricating oil is less than or equal to the upper limit value means that the affinity with the lubricating oil is excellent, and the lubricating oil will demonstrate '' higher oil-holding performance. Consequently, it is more unlikely that the lubricating oil will flow out of the sliding surface of the wheel 60. In addition, it is unlikely that the lubricating oil will allow moisture to spread, and even more improbable that it lets the latter show through. Consequently, since a state where lubricating oil remains on the sliding surface of the wheel 60 is much better maintained, it becomes possible to remove any deterioration of the wheel 60 due to abrasion or the like, to make it operate more stable over a long period of time. In particular, when the interfacial tension between the sliding surface of the wheel 60 and the lubricating oil is between 0 and 5 mN / m, it is possible to suppress any dispersion of the lubricating oil even when vibrations are applied to wheel 60.
    CH 714 765 A2 [0100] The interfacial tension between the sliding surface of the wheel 60 and the lubricating oil is obtained by the Young's equation. Specifically, the interfacial tension is obtained in the same way as the interfacial tension between the sliding surface of the exhaust mobile and the lubricating oil, described in the context of the first embodiment.
    The interfacial tension between the sliding surface of the wheel 60 and the lubricating oil can take a constant value at all locations on the sliding surface, or different values at these locations as long as the surface tension stays in the range of values described above.
    In order to fix the surface tension of the sliding surface of the wheel 60 and the interfacial tension between the sliding surface of the wheel 60 and the lubricating oil in the range of values described above, for example, the oil retaining film 61 can be respectively formed at a location (treated surface) intended to constitute a sliding surface.
    The material or the like of the oil retaining film 61 may be the same as the oil retaining film according to the first embodiment.
    The surface tension of the shaft 51 at a part other than that of the sliding surface is not particularly limited; it can be between 10 and 35 mN / m or can be outside the range. In addition, the interfacial tension between the external circumferential surface (non-sliding surface) of the shaft 51 at a part other than the sliding surface and the lubricating oil having a surface tension of between 25 and 35 mN / m at 25 ° C is not particularly limited; it can be between 0 and 7 mN / m or can be outside the range. In other words, at the level of the non-slip surface of the shaft 51, the oil retaining film 61 may or may not be formed. Furthermore, on the non-sliding surface of the shaft 51, a film having a surface tension lower than that of the sliding surface of the wheel 60 can be formed, and for such a film, for example, a film ( oleophobic repellent film) having a surface tension of less than 10 mN / m can be used.
    Since the sliding surface having a surface tension of between 10 and 35 mN / m is located on the wheel 60 which constitutes the component for a timepiece according to the embodiment presently described, the sliding surface shows proof '' a great affinity with lubricating oil and a high performance of oil behavior with respect to lubricating oil. Therefore, it is unlikely that the lubricating oil will flow out of the sliding surface of the wheel 60. Consequently, since a state where the lubricating oil remains is maintained at the location where a Instead of slipping, it becomes possible to suppress any deterioration of the wheel 60 due to abrasion or the like, and to make it operate stably over a long period of time. In particular, when the surface tension of the sliding surface of the wheel 60 is between 11 and 35 mN / m, it is unlikely that lubricating oil will flow outside the location where the sliding has place, or is dispersed even when vibrations are applied to the wheel 60.
    In addition, in the movement and the timepiece provided with the component for the timepiece according to the first embodiment described above, such as the movement barrel 222, the second mobile 225, the third mobile 226 , and the fourth mobile 227 illustrated in FIG. 1, the wheel 60 according to the second embodiment can be used.
    [Third embodiment] [0107] A component for a timepiece according to a third embodiment of the present invention will be described with reference to FIG. 5.
    [0108] FIG. 5 is a perspective view and a sectional view illustrating a hole stone 75, also often called a "pad", which constitutes the component for a timepiece according to the third embodiment of the present invention.
    As illustrated in FIG. 5, the hole stone 75 has a circular shape, for example, in a plan view. Hole stone 75 is provided with a through hole 74. Hole stone 75 consists, for example, of a ruby, synthetic ruby or the like.
    The through hole 74 is arranged so as to pass through the hole stone 75 right through in the thickness direction. The through hole 74 is formed, for example, in the center of the hole stone 75 in a plan view. The through hole 74 has a circular shape, for example, in a plan view. In the through hole 74, for example, a tenon portion of the shaft body is inserted. As a shaft body, it is possible to use, by way of example, the same structure as that of the shaft 51 of the wheel 60 illustrated in FIG. 4.
    An internal circumferential surface 74a of the through hole 74 of the hole stone 75 then constitutes the sliding surface of the hole stone 75.
    The surface tension of the internal circumferential surface (sliding surface) 74a of the through hole 74 of the hole stone 75 is between 10 and 35 mN / m, preferably between 11 and 35 mN / m, and so even more preferred between 20 and 30 mN / m. When the surface tension of the sliding surface of the hole stone 75 is greater than or equal to the lower limit value, the affinity with the lubricating oil increases, and when lubricating oil is applied to the sliding surface of the 75 hole stone, this shows a high performance of oil resistance. Therefore, it is unlikely that the lubricating oil will flow out of the sliding surface of the stone.
    CH 714 765 A2 with hole 75. Consequently, since a state is maintained where lubricating oil remains on the sliding surface of the stone with hole 75, it becomes possible to remove any deterioration of the stone with hole 75 due to abrasion or the like, and to guarantee stable operation for this part over a long period of time. When the surface tension of the sliding surface of the hole stone 75 is less than or equal to the upper limit value, it is unlikely that the lubricating oil will allow moisture to spread when the lubricating oil is applied to the sliding surface of the hole stone 75. Consequently, since it is unlikely that the lubricating oil will let moisture through and that a state is maintained where the lubricating oil remains on the surface sliding the hole stone 75, it becomes possible to remove any deterioration of the hole stone 75 due to abrasion or the like, and to operate this component stably over a long period of time. In particular, when the surface tension of the sliding surface of the hole stone 75 is between 11 and 35 mN / m, it is unlikely that lubricating oil will disperse even when vibrations are applied to the stone with hole 75.
    The surface tension of the sliding surface of the hole stone 75 is obtained using the Zisman graphical determination method. Specifically, the surface tension is obtained in the same way as the surface tension of the sliding surface of the exhaust mobile, described in the context of the first embodiment.
    The surface tension of the sliding surface of the hole stone 75 may have a constant value at all locations on the sliding surface, or different values at these locations as long as the surface tension is within the range of values described above.
    When the lubricating oil having a surface tension of between 25 and 35 mN / m at 25 ° C is applied to the sliding surface of the hole stone 75, the interfacial tension between the sliding surface and the oil lubricant is preferably between 0 and 7 mN / m, more preferably between 0 and 5 mN / m, and even more preferably between 0.4 and 3 mN / m. A case where the interfacial tension between the sliding surface of the hole stone 75 and the lubricating oil is less than or equal to the upper limit value means that the better the affinity with the lubricating oil, the higher the performance holding oil for lubricating oil. Therefore, it is more unlikely that the lubricating oil will flow out of the sliding surface of the hole stone 75. In addition, it is unlikely that the lubricating oil will allow moisture to spread, and unlikely to see moisture. Consequently, since a state where the lubricating oil remains on the sliding surface of the hole stone 75 is better maintained, it becomes possible to suppress any deterioration of the hole stone 75 due to abrasion or the like, and to operate this component stably over a long period of time. In particular, when the interfacial tension between the sliding surface of the hole stone 75 and the lubricating oil is between 0 and 5 mN / m, it is possible to suppress the dispersion of the lubricating oil even when vibrations are applied to hole stone 75.
    The interfacial tension between the sliding surface of the hole stone 75 and the lubricating oil is obtained using the Young's equation. Specifically, the interfacial tension is obtained in the same way as the interfacial tension between the sliding surface of the exhaust mobile and the lubricating oil, described in the context of the first embodiment.
    The interfacial tension between the sliding surface of the hole stone 75 and the lubricating oil may have an identical value at all locations on the sliding surface, or different values at these locations as long as the interfacial tension remains within the range of values described above.
    In order to fix the surface tension of the sliding surface of the hole stone 75 or the interfacial tension between the sliding surface of the hole stone 75 and the lubricating oil in the range of values described above, for example, oil retaining films 71 can be respectively formed at locations (constituting a treated surface) intended to be a sliding surface.
    The material or the like of the oil retaining film 71 may be the same as the oil retaining film according to the first embodiment.
    The surface tension of the hole stone 75 at a part (first surface 75a and second surface 75b) other than the sliding surface is not particularly limited; it can be between 10 and 35 mN / m, or can be outside this range. In addition, the interfacial tension between the first surface 75a and the second surface 75b and the lubricating oil having a surface tension of between 25 and 35 mN / m at 25 ° C is not particularly limited; it can be between 0 and 7 mN / m or can be outside this range. In other words, on the first surface 75a and the second surface 75b, the oil retaining film 71 may or may not be formed. Furthermore, on the first surface 75a and the second surface 75b, a film having a surface tension lower than that of the sliding surface of the hole stone 75 can be formed, and for such a film, for example, one can use films (oleophobic repellent films) 72 and 73 having a surface tension of less than 10 mN / m, as illustrated in FIG. 5.
    Since the sliding surface having a surface tension of between 10 and 35 mN / m is located on the hole stone 75 which constitutes the component for a timepiece of the embodiment, the sliding surface exhibits great affinity with lubricating oil and high oil holding performance for lubricating oil. Therefore, it is unlikely that the lubricating oil will flow out of the sliding surface of the hole stone 75. Consequently, since a condition where the lubricating oil remains at the location where the slip occurs
    CH 714 765 A2 is maintained, it becomes possible to remove any deterioration of the hole stone 75 due to abrasion or the like, and to operate this component stably over a long period of time. In particular, when the surface tension of the sliding surface of the hole stone 75 is between 11 and 35 mN / m, it is unlikely that the lubricating oil will flow out of the location where the sliding has place, or be dispersed even when shocks are applied to the hole 75 stone.
    [Other embodiments] The component for a timepiece according to the present invention is not limited to the description above, but could for example be a date indicator 80 as illustrated in FIG. 6, or a date jumper 90 as illustrated in fig. 7.
    In the date indicator 80 illustrated in FIG. 6, at a date indication tooth 81, an engagement surface 81a with which an engagement claw of the date jumper engages constitutes the sliding surface.
    The date jumper 90 illustrated in FIG. 7 is a component for correcting the position of the date indicator in the direction of rotation, and is provided with an elastically deformable date jumper spring 92, one end 91 of which is in the form of a point constitutes a free end. At the end 91 of the date jumper spring 92 is formed an engagement claw 93, which can be combined with the date indication tooth of the date indicator. In the date jumper 90, the surface of the engagement claw 93 constitutes a sliding surface.
    The surface tension of the engagement surface (sliding surface) 81a of the date indicator 80 and the surface (sliding surface) of the engagement claw 93 of the date jumper 90 is between 10 and 35 mN / m, preferably between 11 and 35 mN / m, and even more preferably between 20 and 30 mN / m.
    The surface tension of the sliding surface of the date indicator 80 and the date jumper 90 is obtained using the Zisman graph determination method. Specifically, the surface tension is obtained in the same way as the surface tension of the sliding surface of the exhaust mobile, described in the context of the first embodiment.
    The surface tension of the sliding surface of the date indicator 80 and the date jumper 90 can have a constant value at all places on the sliding surface, or different at all places, as long that the surface tension remains within the range of values described above.
    When the lubricating oil having a surface tension between 25 and 35 mN / m at 25 ° C is applied to the sliding surface of the date indicator 80 and the date jumper 90, an interfacial tension between the sliding surface and the lubricating oil is preferably between 0 and 7 mN / m, more preferably 0 to 5 mN / m, and even more preferably 0.4 to 3 mN / m.
    The interfacial tension between the sliding surface of the date indicator 80 and the date jumper 90 and the lubricating oil is obtained by the Young equation. Specifically, the interfacial tension is obtained in the same way as the interfacial tension between the sliding surface of the exhaust mobile and the lubricating oil, described in the context of the first embodiment.
    The interfacial tension between the sliding surface of the date indicator 80 and the date jumper 90 and the lubricating oil can have an identical value at all the locations of the sliding surface, or take values different, as long as the interfacial tension remains in the range of values described above.
    In order to fix the surface tension of the sliding surface of the date indicator 80 and the date jumper 90 or the interfacial tension between the sliding surface of the date indicator 80 and the date jumper 90 and the lubricating oil in the range described above, for example, oil holding films can be respectively formed at a location (constituting a treated surface) intended to be a sliding surface.
    The material or the like of the oil retaining film may be the same as the oil retaining film according to the first embodiment.
    The surface tension of the date indicator 80 and the date jumper 90 at a part other than the sliding surface is not particularly limited, and can be between 10 and 35 mN / m or may be outside this range of values. In addition, the interfacial tension between the surface (non-sliding surface) of the date indicator 80 and the date jumper 90 at a part other than the sliding surface and the lubricating oil having a surface tension. 25 to 35 mN / m at 25 ° C is not particularly limited; it can be between 0 and 7 mN / m or can be outside this range. In other words, on the non-slip surface of the date indicator 80 and the date jumper 90, the oil holding film may or may not be formed. In addition, on the non-slip surface of the date indicator 80 and the date jumper 90, a film having a surface tension lower than that of the sliding surface of the date indicator 80 and the date jumper 90 can be formed, and for such a film, one can use, for example, a film (oleophobic repellent film) having a surface tension of less than 10 mN / m.
    CH 714 765 A2 [Examples] [0134] Hereinafter, the present invention will be specifically described with reference to examples, without however being limited to the present invention.
    [Example 1] The oil maintenance treatment agent was prepared by mixing triethoxyethylsilane (a compound in which Μ 1 is silicon, R is ethyl, and Y 1 , Y 2 , and X 1 are ethoxy groups in general formula (3)), water, and acetic acid in a molar ratio such that the triethoxyethylsilane: water: acetic acid ratio is equal to 10: 15: 1, and stirring the mixture at 80 ° C for 1 hour.
    A test sample was obtained, in which the oil retaining film was formed on a board by coating the board (carbon nickel-plated steel) with the treatment oil retaining agent obtained in such a way. that the thickness after drying reaches approximately 0.5 μm, and by drying the covered board at 150 ° C for one hour. The area of the oil retaining film is defined as the sliding area.
    The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured as follows. The results are illustrated in Table 1.
    In addition, the sliding surface was evaluated in the following manner. The results are illustrated in the table
    1.
    Measurement of surface tension [0139] The surface tension of the sliding surface was obtained using the Zisman graphical determination method.
    First, a plurality of test liquids having different surface tensions was deposited on the sliding surface and formed droplets, and the contact angle (θ) between the droplet and the sliding surface was measured to calculate cos6. Then, the surface tensions of each test liquid were plotted on the transverse axis and cos9 was plotted on the longitudinal axis to prepare the graphical representation of Zisman, and the value of the surface tension is obtained when cosO = 1 on the first rectilinear approximation segment. A similar operation is carried out at five different places on the sliding surface 115 to prepare the graph of Zisman representation, the value of the surface tension when cosO = 1 on the first rectilinear approximate segment, and the mean value is defined as the surface tension of the sliding surface 115. In addition, the formation of droplets and the measurement of the contact angle (θ) are carried out at 25 ° C.
    As the test liquid, pentane, heptadecane, iodocyclohexane, ethylene glycol, formamide, diiodomethane, glycerin, and distilled water were used.
    Interfacial tension measurement [0142] The interfacial tension between the sliding surface and the lubricating oil was obtained by the Young equation.
    First, the lubricating oil was deposited on the sliding surface and formed droplets, and the contact angle (θ) between the droplet and the sliding surface was measured to calculate cosO. Separately, the surface tension (γ 3 ) of the sliding surface where the lubricating oil was deposited was obtained by the method for determining the Zisman graph described above. In addition, the surface tension (y L ) of the lubricating oil was obtained by a catalog value or via a method of optical determination known as the hanging drop ("during drop"). Then, cosO, y s , and y L were substituted in the Young equation illustrated in the following equation (i) in order to obtain the interfacial tension (y ls ) between the solid and the liquid. A similar operation was carried out at five different locations on the sliding surface in order to obtain y ls , and its mean value was defined as the interfacial tension between the sliding surface and the lubricating oil. In addition, the droplet formation and the measurement of the contact angle (θ) were carried out at 25 ° C.
    Ys = YLS + TL COS0 ·· (ï) [0144] As lubricating oil, ΓΑ0-3 was used (manufactured by Citizen Watch Co., Ltd., product name "AO-3", surface tension at 25 ° C: 30.5 mN / m) or MA (manufactured by Moebius, product name "SYNT-A-LUBE", surface tension at 25 ° C: 32.7 mN / m).
    Evaluation [0145] In a state where the sliding surface of the test sample is horizontal, the lubricating oil was deposited on the sliding surface. Then, the condition of the lubricating oil was visually checked and evaluated according to the following evaluation criteria when the test sample was gradually lifted so that the sliding surface was perpendicular to the horizon.
    CH 714 765 A2 [0146] O: The lubricating oil does not drip even when the test sample is standing vertically, and the lubricating oil is kept on the sliding surface even when the test sample vibrates.
    Δ: The lubricating oil does not drip even when the test sample is standing vertically, but the lubricating oil slides down when the test sample vibrates.
    X: The lubricating oil easily lets moisture spread when the lubricating oil is deposited on the sliding surface, or the lubricating oil easily slides down when the test sample is placed vertically.
    [Example 2] The oil maintenance treatment agent was prepared by mixing triethoxy-n-octylsilane (a compound expressed in general formula (4)), water, and acetic acid in a molar ratio such as the triethoxy-noctylsilane ratio: water: acetic acid is equal to 10: 15: 1, and stirring the mixture at 80 ° C for 8 hours.
    A test sample was obtained in which the oil retaining film was formed on a board by covering the board (carbon nickel-plated steel) with the treatment oil retaining agent obtained so that the thickness after drying reaches approximately 0.5 μm, and by drying the covered board at 150 ° C for hours. The area of the oil retaining film is defined as the sliding area.
    The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured in a similar manner as in Example 1. In addition, the sliding surface was evaluated by similar to that used for Example 1. The results are illustrated in Table 1.
    [Example 3] The oil maintenance treatment agent was prepared by mixing butyltrimethoxysilane (a compound in which Μ 1 is silicon, R is a butyl group, and Y 1 , Y 2 , and X 1 are methoxy groups in the general formula (3)), water, and acetic acid in a molar ratio such that the butyltrimethoxysilane: water: acetic acid ratio is equal to 10: 15: 1, and stirring the mixture at 80 ° C for 1 hour.
    A test sample was obtained in which the oil retaining film was formed on a board by covering the board (carbon nickel-plated steel) with the treatment oil retaining agent obtained so that the thickness after drying reaches approximately 0.5 μm, and by drying the covered board at 150 ° C for 1 hour. The area of the oil retaining film is defined as the sliding area.
    The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured in a similar manner to that used for example 1. In addition, the sliding surface was evaluated similarly to that used for Example 1. The results are illustrated in Table 1.
    [Example 4] A test sample was obtained in which the oleophobic repellent film was formed on a board by covering the board (carbon nickel-plated steel) with the fluorine-based treatment agent (manufactured by Harves Co., Ltd., product name: "HFD-1098") so that the thickness after drying reaches approximately 30 nm, and by drying the covered board at 100 ° C for 30 minutes. The surface of the oleophobic repellent film is defined as the sliding surface.
    The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured in a similar manner to that used for example 1. In addition, the sliding surface was evaluated similarly to that used for Example 1. The results are illustrated in Table 1.
    [Example 5] [0157] A test sample was obtained in which the oleophobic repellent film was formed on a board by covering the board (carbon nickel-plated steel) with a fluorine-based treatment agent (manufactured by AGC Seimi Chemical Co., Ltd., product name: "SFE-MS01", a solution diluted with 600 times SFE solvent) so that the thickness after drying reaches approximately 5 nm, and by drying the covered board for 30 minutes at 100 ° C. The surface of the lubricating repellant film is defined as the sliding surface.
    The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured in a similar manner to that used for example 1. In addition, the sliding surface was evaluated similarly to Example 1. The results are illustrated in Table 1.
    [Comparative Example 1] The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured in a similar manner to that used for Example 1, while the surface of the board (steel
    CH 714 765 A2 carbon nickel-plated) is the sliding surface. In addition, the sliding surface was evaluated in a similar manner to Example 1. The results are illustrated in Table 1.
    [Comparative Example 2] [0160] A test sample was obtained, in which the lubricating repellant film was formed on a board by vacuum deposition of polytetrafluoroethylene relative to the board (carbon nickel-plated steel), so that the thickness after deposition reaches approximately 5 nm. The surface of the oleophobic repellent film is defined as the sliding surface.
    The surface tension of the sliding surface and the interfacial tension between the sliding surface and the lubricating oil were measured in a similar manner to that used for example 1. In addition, the sliding surface was evaluated similarly to Example 1. The results are illustrated in Table 1.
    Table 1 [0162]
    Surface tension of the sliding surface [mN / m] Lubricating oil Interfacial tension between the sliding surface and the lubricating oil [mN / m] Evaluation Example 1 29.3 AO-3 2.9 0 Example 2 25.5 AO-3 1.7 0 Example 3 24.1 AO-3 0.4 0 Example 4 10.8 AO-3 6.9 Δ Example 5 10.4 AO-3 6.8 Δ Comparative example 1 40.0 AO-3 10.2 X MY 8.8 X Comparative example 2 8.0 AO-3 33.0 X
    As can be seen from table 1, in each example, the lubricating oil did not drip even when the test sample was placed vertically, and the holding performance of the lubricating oil was excellent. In particular, in the cases of Examples 1 to 3, it was unlikely that the lubricating oil would be dispersed even when vibrations were applied to the test sample, and the lubricating oil was better in terms of holding performance of the l lubricating oil.
    权利要求:
    Claims (3)
    [1]
    On the contrary, in the case of Comparative Example 1, in which the surface tension of the sliding surface exceeds 35 mN / m, the lubricating oil was capable of allowing moisture to propagate when the oil lubricant has been deposited on the sliding surface. In addition, when the test sample is positioned vertically, the lubricating oil easily slid down.
    [0165] In the case of Comparative Example 2, in which the surface tension of the sliding surface was less than 10 mN / m, the lubricating oil easily slipped when the test sample was positioned vertically.
    claims
    1. Component for a timepiece (201), comprising:
    a sliding surface (115) having a surface tension of 10 to 35 mN / m.
    [2]
    2. Timepiece component (201) according to claim 1, in which, when a lubricating oil having a surface tension of 25 to 35 mN / m is applied to the sliding surface (115), the interfacial tension between the sliding surface (115) and the lubricating oil is 0 to 7 mN / m.
    [3]
    3. Movement (210) comprising:
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    同族专利:
    公开号 | 公开日
    JP2019158469A|2019-09-19|
    US20190278228A1|2019-09-12|
    CN110244541A|2019-09-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    SG121787A1|2002-08-16|2006-05-26|Citizen Watch Co Ltd|Oil retention treatment agent, oil retention treatment method using the same, and watch having been oil retention treated by the oil retention treatment method|
    CN1294224C|2002-10-10|2007-01-10|清美化学股份有限公司|Oil-barrier composition|
    CN1957047A|2004-05-25|2007-05-02|清美化学股份有限公司|Barrier composition against lubricating oil and use thereof|
    JP2011102780A|2009-11-11|2011-05-26|Seiko Instruments Inc|Component for timepiece and timepiece|
    JP2014074585A|2012-10-02|2014-04-24|Seiko Instruments Inc|Timepiece component and manufacturing method of the same|
    JP6963971B2|2017-02-10|2021-11-10|セイコーインスツル株式会社|Machine parts, mechanical modules, movements and watches|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP2018043194A|JP7026538B2|2018-03-09|Watch parts, movements and watches|
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