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    • 专利摘要:
    A lubricating composition for watches which contains a lubricant (A) and an anti-wear agent (B). The lubricant (A) contains at least one component selected from saturated aliphatic hydrocarbons (A-2) having a melting point of at least 45°C and a carbon number of 23 to 38 inclusive, and the anti- Wear (B) contains at least one component selected from a neutral phosphate ester and a neutral phosphite ester.
    公开号:CH715086B1
    申请号:CH01353/19
    申请日:2018-02-14
    公开日:2021-12-15
    发明作者:Akao Yuji
    申请人:Citizen Watch Co Ltd；
    IPC主号:
    专利说明:

    Technical area
    The present invention relates to the composition of a lubricant for watches, a treatment liquid for the lubrication of a watch, and a watch.
    State of the art
    [0002] A lubricating oil composition containing a lubricating component (A) containing a base oil (A1), an anti-wear agent (B) containing a neutral phosphate ester (B-1) or a neutral phosphite ester (B -2) having a specific structure, and an antioxidant (C), the total acid number of the composition not exceeding 0.8 mgKOH/g, is known from the prior art as a lubricating oil composition for watches (Reference 1).
    References
    [0003] Reference 1: International patent application No. 2014/115603
    Summary
    Technical problem
    [0004] When the composition of the lubricating oil for watches described in reference 1 is used in the sliding parts of a mechanical watch, an oil flow occurs. In addition, when the lubricating oil composition for watches described in Reference 1 is used in the clasp of a watch strap, oil leakage occurs.
    [0005] The object of the present invention is to provide a lubricating composition for watches which can suppress oil drippings even when it is used in the sliding parts of a mechanical watch or in the clasp of a watch strap.
    Solution to the technical problem
    [0006] A lubricating composition for watches according to the invention contains a lubricant (A) and an anti-wear agent (B), in which the lubricant (A) contains at least one component chosen from saturated aliphatic hydrocarbons (A-2 ) having a melting point of at least 45°C and a carbon number of between 23 and 38, and the antiwear agent (B) contains at least one component selected from a neutral phosphate ester and a neutral phosphite ester .
    Advantageous effects of the invention
    [0007] The lubricating composition for watches according to the present invention can suppress oil drippings even when it is used in the sliding parts of a mechanical watch or in the clasp of a watch band.
    Brief description of the drawings
    Figure 1 is a view illustrating a watch (mechanical watch) according to a first embodiment. FIG. 2 is a view illustrating a watch according to a second embodiment. FIG. 3 is a view illustrating the watch according to the second embodiment.
    detailed description
    [0009] Embodiments of the invention will be described in detail. The present invention is not limited by the contents of the embodiments described below. The constituent elements described below include elements which can be readily considered by a person skilled in the art and elements which are substantially identical. The configurations described below can also be combined if necessary. The configurations described below may also be omitted, substituted and modified in various ways within the scope which does not depart from the essence of the present invention.
    [0010] The lubricating composition for watches according to the embodiments contains a lubricant (A) and an anti-wear agent (B).
    The lubricating composition for watches according to a first embodiment
    The composition of the lubricant for watches according to the first embodiment will now be described. The lubricating composition for watches according to the first embodiment is also referred to as lubricating composition (I) in the present description. The lubricating composition for watches according to the first embodiment contains the lubricant (A) and the anti-wear agent (B). From the point of view of preparing a film formed from the harder lubricating composition (I), the lubricating composition (I) preferably does not contain a fluidity control agent (F) as described above. below.
    Lubricant (A)
    [0012] The lubricant (A) contains a paraffin wax (A-1) or contains at least one component chosen from saturated aliphatic hydrocarbons (A-2) having a melting point of at least 45° C. and a number carbon from 23 to 38 inclusive. Paraffin wax (A-1) and saturated aliphatic hydrocarbon (A-2) can be used alone or two or more types can be used in a mixture.
    [0013] The sliding parts of the escapement of a mechanical watch are subjected to high pressure and vibration. When a conventional watch lubricating oil composition is used to lubricate sliding parts, oil leakage may occur. After the sliding parts have undergone an oleophobic treatment in order to suppress oil seepage, the lubricating oil composition can be applied to the sliding parts. However, the layer of the lubricating oil composition applied (lubricant layer) is thicker when the oleophobic treatment is carried out. This can lead to an increase in sliding resistance, which reduces the performance of the mechanical watch. On the other hand, the lubricating composition for watches according to the first embodiment of the present invention contains the specific lubricant (A) and therefore can suppress oil leakage. It is not necessary to perform oleophobic treatment in advance, and the layer of the lubricating composition for watches applied (lubricating layer) according to the first embodiment is relatively thin. Thus, the increase in the sliding resistance can be suppressed and the performance of the mechanical watch can also be improved. In addition, since there is no need for oleophobic treatment, it is easy to lubricate the sliding parts of the exhaust. Further, since the lubricating composition for watches according to the first embodiment does not evaporate easily, the sliding parts can be lubricated for a long period of time. The escapement of a mechanical watch is described in detail below.
    The paraffin wax (A-1) preferably has a melting point between 45° C. and 80° C. inclusive and preferably between 50° C. and 75° C. inclusive. When the melting point is within these value ranges, oil seepage can be suppressed properly. Examples of paraffin wax (A-1) include unrefined paraffin wax (crude paraffin (slack wax), scale wax (scale wax) or the like) separated from a distilled oil by vacuum distillation, residual oil from vacuum distillation, heavy distilled oil or the like from petroleum with a method of dewaxing, and refined paraffin wax obtained by bleaching and refining unrefined paraffin wax.
    The saturated aliphatic hydrocarbon (A-2) has a melting point of at least 45°C. The saturated aliphatic hydrocarbon (A-2) preferably has a melting point not higher than 80°C. The saturated aliphatic hydrocarbon (A-2) has 23 to 38 carbon atoms inclusive, and is preferably a straight chain saturated aliphatic hydrocarbon, and is more preferably tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane or octatriacontane. Such a saturated aliphatic hydrocarbon (A-2) can suppress oil drippings well.
    Paraffin wax (A-1) is preferably used for its ease of handling.
    Anti-wear agent (B)
    The anti-wear agent (B) contains at least one component selected from a neutral phosphate ester and a neutral phosphite ester. The antiwear agent (B) preferably contains at least one component selected from a neutral phosphate ester (B-1) represented by the general formula (b-1) and a neutral phosphite ester (B-2) represented by the general formula (b-2). Neutral phosphate ester (e.g. neutral phosphate ester (B-1)) and neutral phosphite ester (e.g. neutral phosphite ester (B-2)) can be used alone or more than one can be used in combination. One or more types of neutral phosphate ester (eg, neutral phosphate ester (B-1)) and one or more types of neutral phosphite ester (eg, neutral phosphite ester (B-2)) may be mixed and used in a mixture.
    [0018] The sliding parts of the escapement of a mechanical watch are subjected to high pressure and vibration. When a conventional watch lubricating oil composition is used to lubricate the sliding parts, a deposit such as worn powder or rust may form, discoloring part of the sliding parts to a dark brown color. This result is probably due to the conventional composition of the lubricating oil produced to be suitable for a quartz watch, which has a low resistance to pressure. This result can also be attributed to the fact that the material of quartz watch is phosphor bronze or the like while the material of mechanical watch is ferrous material. On the other hand, the wear resistance and the properties under extreme pressure can be improved with the composition of the lubricant for watches according to the first embodiment because the antiwear agent (B) (in particular the neutral phosphate ester (B-1) or the neutral phosphite ester (B-2)) is combined with the lubricant (A). The formation of a deposit such as worn powder or rust is suppressed, and discoloration of sliding parts does not easily occur. Thus, proper lubrication over a long period of time is possible even in the escapement of a mechanical watch subject to high pressure and vibration.
    In formula (b-1), R<b11> to R<b14> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms. The aliphatic hydrocarbon groups of 10 to 16 carbon atoms can be straight chain, branched or cyclic aliphatic hydrocarbon groups, and can be saturated or unsaturated aliphatic hydrocarbon groups. Specific examples of aliphatic hydrocarbon groups of 10 to 16 carbon atoms preferably used include straight chain alkyl groups, such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a group pentadecyl, hexadecyl group (cetyl group).
    [0020] R<b15> to R<b18> each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms. Examples of straight and branched chain alkyl groups of 1 to 6 carbon atoms are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec-butyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, neopentyl group and isohexyl group.
    [0021] Because the neutral phosphate ester (B-1) has specific R<b15> to R<b18> components, wear resistance and extreme pressure properties are improved even when the watch lubricant composition is used in an escapement subjected to strong pressures and vibrations. This improvement is attributed to the fact that the film of the lubricating composition for watches applied to the sliding parts of the escapement is made resistant by the specific components R<b15> to R<b18>.
    [0022] In particular when R<b15> and R<b17> are each a straight chain alkyl group of 1 to 6 carbon atoms and preferably 1 to 3 carbon atoms, and R<b16> and R<b18 >are each a branched alkyl group of 3 to 6 carbon atoms and preferably 3 to 4 carbon atoms, the wear resistance and the extreme pressure properties are further improved.
    [0023] R<b191> and R<b192> each independently represent a hydrogen atom or a linear or branched alkyl group of 1 to 5 carbon atoms. Examples of straight and branched chain alkyl groups of 1 to 5 carbon atoms are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, sec-butyl, isobutyl group, t-butyl group, isopentyl group, t-pentyl group and neopentyl group.
    [0024] However, the total number of carbon atoms of R<b191> and R<b192> is 1 to 5. Thus, when R<b191> is, for example, a hydrogen atom, R<b192 >is a linear or branched alkyl group of 1 to 5 carbon atoms, when R<b191>is, for example, a methyl group, R<b192>is a linear or branched alkyl group of 1 to 4 carbon atoms and when R<b191>is, for example, an ethyl group, R<b192>is a linear or branched alkyl group of 2 to 3 carbon atoms. In particular, it is preferable that R<b191> is a hydrogen atom and that R<b192> is a straight or branched chain alkyl group of 1 to 5 carbon atoms, since a film originating from the lubricating composition for watches is further strengthened.
    In formula (b-2), R<b21> to R<b24> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms. Each of the aliphatic hydrocarbon groups of 10 to 16 carbon atoms can be a straight chain, branched or cyclic aliphatic hydrocarbon group, and can be a saturated or unsaturated aliphatic hydrocarbon group. Specific examples of aliphatic hydrocarbon groups of 10 to 16 carbon atoms preferably used include straight chain alkyl groups, such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a group pentadecyl, hexadecyl group (cetyl group).
    [0026] R<b25> to R<b28> each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms. Examples of straight or branched chain alkyl groups of 1 to 6 carbon atoms are methyl group, ethyl group, n-propyl group, n-butyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, sec-butyl group, isobutyl group, t-butyl group, isopentyl group, t-pentyl group, t-pentyl group, neopentyl group and ishexyl group.
    [0027] Because the neutral phosphite ester (B-2) has specific R<b25> to R<b28> components, wear resistance and extreme pressure properties are improved even when the lubricating composition for watches is used in an escapement subject to high pressure and vibration. This improvement is attributed to the fact that the film of the lubricating composition for watches applied to the sliding parts of the escapement is reinforced by the specific components from R<b25> to R<b28>.
    In particular when R<b25> and R<b27> are each a straight chain alkyl group of 1 to 6 carbon atoms and preferably 1 to 3 carbon atoms, and R<b26> and R<b28 >are each a branched alkyl group of 3 to 6 carbon atoms and preferably 3 to 4 carbon atoms, the wear resistance and extreme pressure properties are further improved.
    [0029] R<b291> and R<b292> each independently represent a hydrogen atom or a linear or branched alkyl group of 1 to 5 carbon atoms. Examples of straight and branched chain alkyl groups of 1 to 5 carbon atoms are methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, isopropyl group, sec-butyl, isobutyl group, t-butyl group, isopentyl group, t-pentyl group and neopentyl group.
    [0030] However, the total number of carbon atoms of R<b291> and R<b292> is 1 to 5. Therefore, when R<b291> is, for example, a hydrogen atom, R< b292> is a linear or branched alkyl group of 1 to 5 carbon atoms, when R<b291> is, for example, a methyl group, R<b292> is a linear or branched alkyl group of 1 to 4 carbon atoms and when R<b291> is for example an ethyl group, R<b292> is a linear or branched alkyl group of 2 to 3 carbon atoms. In particular, it is preferable that R<b291> is a hydrogen atom and that R<b292> is a linear or branched alkyl group of 1 to 5 carbon atoms, since a film of such a lubricating composition for watches is further strengthened.
    [0031] It is believed that the neutral phosphite ester (B-2) has greater structural stability when used in the lubricating composition for watches, and therefore the neutral phosphite ester (B-2) is used even more referencingly.
    [0032] A neutral phosphate ester other than the neutral phosphate ester (B-1) can also be used as the neutral phosphate ester, such as for example tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate, trimethylolpropane, triphenyl phosphate, tris(nonylphenyl) phosphate, triethyl phosphate, tris(tridecyl) phosphate and tetraphenyl dipropylene glycol diphosphate, tetraphenyl tetra(tridecyl)pentaerythritol tetraphosphate, tetra(tridecyl)-4,4' -isopropylidene-diphenyl phosphate, bis(tridecyl)pentaerythritol diphosphate, bis(nonylphenyl)pentaerythritol diphosphate, tristearyl phosphate, distearyl pentaerythritol diphosphate, tris(2,4-di-t-butylphenyl)-phosphate and a hydrogenated polymer of bisphenol A/pentaerythritol.
    [0033] A neutral phosphite ester other than the neutral phosphite ester (B-2) can also be used as the neutral phosphite ester, such as, for example, trioleyl phosphite, trioctyl phosphite, trioctyl phosphite, trimethylolpropane phosphite, triphenyl, tris(nonylphenyl) phosphite, triethyl phosphite, tridecyltriyl phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenyl phosphite, bis(tridecyl)pentaerythritol diphosphite , bis(nonylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite and a phosphite polymer of hydrogenated bisphenol A/pentaerythritol phosphite.
    [0034] The neutral phosphate ester (B-1) is better able to suppress the flow of oil in the sliding parts of a mechanical watch than the other neutral phosphate esters. The same applies to the neutral phosphite ester (B-2) which is also better able to suppress oil leaks in the sliding parts of a mechanical watch than the other neutral phosphite esters.
    Antioxidant (C)
    The lubricating composition for watches according to the first embodiment may additionally contain an antioxidant (C). If the lubricating composition for watches according to the first embodiment contains the antioxidant (C), deterioration can be suppressed for a long period of time. Examples of the antioxidant (C) include a phenol-based antioxidant and an amine-based antioxidant. One type of antioxidant (C) can be used alone or two or more types can be used in a mixture.
    [0036] Examples of phenol-based antioxidants include 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol and 4,4'-methylene-bis. (2,6-di-t-butylphenol).
    [0037] A diphenylamine derivative, that is to say a compound in which a hydrogen atom of the benzene ring of the diphenylamine is substituted by a linear or branched alkyl group of 1 to 10 carbon atoms, can be duly used as an amine antioxidant, because thereby the deterioration of the lubricating composition can be further suppressed. A specific example of such a compound which can be used more preferably is the diphenylamine derivative (C-1) represented by the general formula (c-1).
    In formula (c-1), R<c11> and R<c12> each independently represent a linear or branched alkyl group of 1 to 10 carbon atoms. Examples of straight and branched chain alkyl groups of 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, sec-butyl group, isobutyl group, t-butyl group, isopentyl group, t group -pentyl, a neopentyl group, an isohexyl group, a 2-ethylhexyl group, a 2,4,4-trimethylpentyl group and a 1,1,3,3-tetramethylbutyl group.
    p and q each independently represent an integer from 0 to 5, and preferably an integer from 0 to 3, but p and q do not represent 0 at the same time.
    The diphenylamine derivative (C-1) is obtained by reacting, for example, diphenylamine with a component to introduce a linear or branched alkyl group of 1 to 10 carbon atoms as a substituent (component having a double bond), such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 2-butene, 2-methylpropene, 3-methyl-1-butene, 2-methyl-1-butene, 4-methyl-1-pentene, 2-ethyl-1-hexene or 2,4,4-tricepentene).
    [0041] The hindered amine compound (C-2) represented by the general formula (c-2) can also be used as an amine antioxidant because the deterioration of the composition of the lubricant can thereby be further suppressed.
    In formula (c-2), R<c21> and R<c22> each independently represent an aliphatic hydrocarbon group of 1 to 10 carbon atoms. The aliphatic hydrocarbon group having 1 to 10 carbon atoms may be a straight chain, branched or cyclic aliphatic hydrocarbon group, and may be a saturated or unsaturated aliphatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon groups of 1 to 10 carbon atoms preferably used include straight and branched chain alkyl groups, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, sec-butyl group, isobutyl group, t-butyl group, isopentyl, t-pentyl group, neopentyl group, isohexyl group and 2-ethylhexyl group. Of these, straight and branched chain alkyl groups of 5 to 10 carbon atoms are more preferable from the viewpoint of enhanced durability.
    [0043] R<c23> represents a divalent aliphatic hydrocarbon group of 1 to 10 carbon atoms. Examples of divalent aliphatic hydrocarbon groups of 1 to 10 carbon atoms preferably used include straight and branched chain divalent alkylene groups, such as methylene group, 1,2-ethylene group, 1,3 -propylene, 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 1,7-heptylene group, 1,8-octylene group, 1,9-nonylene group , a 1,10-decylene group and a 3-methyl-1,5-pylene group. Among these examples, a divalent straight or branched chain alkylene group of 5 to 10 carbon atoms is more preferable from the viewpoint of enhanced durability.
    [0044] Particularly from the viewpoint of improving high temperature durability, the groups in which the total number of carbon atoms of R<c21>, R<c22> and R<c23> is 16 to 30 are most preferable among the above groups.
    One or more diphenylamine derivatives (C-1) and one or more hindered amine compounds (C-2) are preferably used in combination as amine antioxidants. In doing so, even when the lubricating composition for watches according to the first embodiment is used in the sliding parts of an escapement subjected to high pressures and vibrations, it suppresses the formation of a deposit such as worn powder and rust, and makes discoloration of sliding parts less likely and improves durability. It is assumed that these effects result from the production of active compounds due to high pressure and vibration during sliding, which are rendered harmless for a long period of time when the diphenylamine derivative (C-1) and the amine compound at steric hindrance (C-2) are combined.
    Metal Deactivator (D)
    The lubricating composition for watches according to the first embodiment may additionally contain a metal deactivator (D). When the lubricating composition contains the metal deactivator (D), metal corrosion is better suppressed. From the standpoint of metal corrosion suppression, the metal deactivator (D) is preferably benzotriazole or a derivative thereof. One type of metal deactivator (D) can be used alone or two or more types can be used in a mixture.
    Specific examples of benzotriazole derivatives include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(a,a-dimethylbenzyl )phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl-phenyl)-benzotriazole, and compounds having a structure represented by the following formula wherein R, R' and R" are each an alkyl group of 1 to 18 carbon atoms, such as 1-(N,N-bis(2-ethylhexyl)aminomethyl)benzotriazole.
    [0048] From the point of view of suppressing oil leaks in the sliding parts of a mechanical watch, the lubricating composition for watches according to the first embodiment preferably contains the anti-wear agent (B) in an amount from 1 to 200 parts by mass inclusive, preferably from 1 to 120 parts by mass inclusive, and even more preferably from 1 to 80 parts by mass inclusive per 100 parts by mass of the lubricant (A). Thanks to these content ranges, proper lubrication is possible for a long period of time.
    [0049] The amount of antioxidant (C) is preferably 0.01 to 1.2 parts by mass inclusive with respect to 100 parts by mass of the total amount of the lubricant (A) and the anti-wear agent (B). With this content range, durability can be further improved. The amount of the metal deactivator (D) is preferably 0.01 to 1.2 parts by mass inclusive with respect to 100 parts by mass of the total amount of the lubricant (A) and the anti-wear agent (B ). With this content range, corrosion can be further suppressed.
    The lubricating composition for watches according to the first embodiment is generally in the semi-solid state at ambient temperature. The expression ambient temperature designates the ambient temperature in an ordinary situation, that is from 15°C to 30°C inclusive and generally 25°C. The expression semi-solid designates a substance having the attributes of a liquid and a solid and which, at room temperature, is closer to a solid than to a liquid.
    The lubricating composition for watches according to the first embodiment can be obtained by mixing the components described above. The mixing can be carried out, for example, by heating the components at least to their melting temperature. Additionally, after a solvent such as a hydrocarbon solvent is added to the components to be mixed, the solvent can be evaporated. Evaporation can take place by applying hot air. Examples of solvent include, but are not limited to, hexane and nonane when paraffin wax (A-1) is used. When the saturated aliphatic hydrocarbon (A-2) is used, it is possible to choose, if appropriate, from hexane, toluene, THF, diethyl ether, chloroform, cyclohexane, heptane, methylcyclohexane, diethyl ether and methanol. In this way, the lubricating composition for watches according to the first embodiment can be prepared.
    Watch (mechanical watch) according to the first embodiment
    The lubricating composition for watches (lubricating composition (I)) is applied to the watch (mechanical watch) according to the first embodiment. Fig. 1 is a view for explaining the watch (mechanical watch) according to the first embodiment. As shown in Figure 1, the mechanical watch has an escapement 1 which contains an escapement wheel 2 and a paddle lever 3. The escapement wheel 2 is a gear which is positioned at the end of the gear train. gears and which rotates in response to the force of a spiral spring 4 which relaxes. The paddle lever 3 is connected to a pendulum 5 and advances the escape wheel 2 one tooth at a time by regular swinging produced by an alternating movement. During this advancement, the pallets 3a and 3b of the pallet lever 3 engage with and detach from the teeth of the escapement wheel 2. The sliding parts of the pallets 3a and 3b of the pallet lever 3 and the teeth of the wheel exhaust 2 are subjected to strong pressures and vibrations. The lubricating composition for watches is suitably used to lubricate these sliding parts.
    [0053] In particular, the lubricating composition for watches is applied to the parts that make up the sliding parts of the pallets 3a and 3b of the pallet lever 3 and the teeth of the escapement wheel 2. As the lubricating composition for watches is applied in a relatively thin layer as a lubricating layer without oil flow, an increase in slip resistance can be suppressed and the performance of the mechanical watch can be improved. In addition, since there is no need for oleophobic treatment, lubrication of the sliding parts of the escapement is easy. Further, since the lubricating composition for watches does not easily evaporate, the sliding parts remain lubricated for a long period of time.
    [0054] Examples of methods of applying the lubricating composition for watches include a method in which the lubricating composition for watches is heated and then applied in a soft state by a coating process on the parts that make up the sliding parts. Alternatively, the lubricating composition for watches can be used to prepare a treatment liquid for lubricating a watch and applied by a coating process to the parts that make up the sliding parts. The treatment liquid for lubricating a watch is described below.
    Treatment liquid for the lubrication of a watch
    The treatment liquid for the lubrication of a watch contains the lubricant (A), the anti-wear agent (B) and a solvent (E). The lubricant (A) and the anti-wear agent (B) are described above together with the composition of the lubricant for watches. The treatment liquid for the lubrication of a watch may also contain the antioxidant (C) and the metal deactivator (D). The antioxidant (C) and the metal deactivator (D) are described above as well as the lubricating composition for watches. These components are favorably contained in the treatment liquid for the lubrication of a watch in order to have the quantity ratios described above as well as the composition of the lubricant for watches.
    [0056] Suitable examples of solvent (E) include, but are not limited to, hexane and nonane when paraffin wax (A-1) is used. When the saturated aliphatic hydrocarbon (A-2) is used, it is possible to choose, if appropriate, from hexane, toluene, THF, diethyl ether, chloroform, cyclohexane, heptane, methylcyclohexane, diethyl ether and methanol. One type of solvent (E) can be used alone or two or more types can be used in a mixture. The solvent (E) is preferably added so that the total density of the lubricant (A) and the anti-wear agent (B) is 0.1 to 5 parts by mass inclusive. When these amounts are used, the lubricating composition for watches can be suitably applied to the sliding parts.
    More specifically, the treatment liquid for the lubrication of a watch is prepared by adding the lubricating composition for watches to the solvent (E) and stirring. Then, a small amount of the resulting treatment liquid for lubricating a watch is poured onto the sliding parts, and the solvent (E) evaporates. The lubricating composition for watches is thus applied to the sliding parts. In more detail, a layer containing a semi-solid watch lubricant composition is applied.
    [0058] When applying the lubricating composition for watches, the application must be on the pallet lever 3 on the side of the pallets 3a and 3b and/or on the gear side of the escape wheel. 2 among the parts that make up the sliding parts.
    The lubricating composition for watches according to the first embodiment can also be used on sliding parts subjected to strong pressures and vibrations in a mechanical watch, even on sliding parts other than those of the escapement described above. . When the lubricating composition for watches is so used, the effect described above is manifested. Specific examples of sliding parts subjected to high pressure and vibration include the sliding parts of the gear train, a lever and a spring for time correction.
    Lubricating composition for watches according to a second embodiment
    The composition of the lubricant for watches according to the second embodiment will now be described. The lubricating composition for watches according to the second embodiment is also referred to as lubricating composition (II) in this specification. The lubricating composition for watches according to the second embodiment contains a lubricant (A) and an anti-wear agent (B). The details, including the preferable value ranges, of the lubricant (A) and the antiwear agent (B) in the composition of the lubricant (II) are the same as in the composition of the lubricant (I). When the favorable value ranges are observed, the locking parts of the clasp can be lubricated for a long period of time. The lubricating composition (II) additionally contains the fluidity control agent (F).
    [0061] The clasp of a watch strap is subjected to high pressure when it is closed and opened. When a conventional watch lubricating oil composition is used on the clasp, oil dripping may occur. If the oil is wiped off, a stain may remain. On the other hand, the lubricating composition for watches according to the second embodiment contains the specific lubricant (A) and the fluidity control agent (F), which makes it possible to suppress the flow of oil and to form a film of the lubricating composition (II) with favorable hardness. In addition, since the lubricating composition for watches according to the second embodiment does not easily evaporate, the functions of the closing and unlocking clasp can be maintained for a long period of time. In addition, since the functions of the clasp are obtained with a small amount of the lubricating composition (II), the lubricating composition (II) is not easily recognizable as forming a stain.
    A conventionally known viscosity index improver can be used as the fluidity control agent (F). One type of flow control agent (F) may be used alone or two or more types may be used in a mixture. Examples of flow control agent (F) include polyacrylates, polymethacrylates, polyisobutylenes, polyalkylstyrenes, polyesters, α-olefin copolymers, isobutylene fumarate, styrene ester maleate, ester vinyl acetate fumarate, a polybutadiene/styrene copolymer, a polymethacrylate/vinylpyrrolidone copolymer and an ethylene/alkyl acrylate copolymer. Of these, polyisobutylene or α-olefin copolymer can be appropriately used and polyisobutylene being more suitable from the viewpoint of the film hardness of the lubricating composition (II).
    [0063] Specific examples of polyacrylates are a polymer of acrylic acid and a polymer of an alkyl ester of a C1 to C10 acrylic acid. Examples of polymethacrylates are a polymer of methacrylic acid and a polymer of an alkyl ester of a C1 to C10 methacrylic acid. Of these, a polymethacrylate in which methyl methacrylate is polymerized is preferable.
    The polyisobutylene is preferably a homopolymer. The polyisobutylene preferably has a number-average molecular mass (Mn) of 3000 to 80000 inclusive, and more preferably, from the point of view of the lubricating properties, of 3000 to 50000 inclusive. The number average molecular mass (Mn) is the mass average molecular mass equivalent to polystyrene found with the technique of gel permeation chromatography (GPC) (reference standard: polystyrene).
    [0065] Specific examples of polyalkylstyrenes include polymers of monoalkylstyrenes having components of 1 to 18 carbon atoms, such as poly-α-methylstyrene, poly-β-methylstyrene, poly-α-ethylstyrene and poly -β-ethylstyrene.
    [0066] Specific examples of polyesters include polyesters obtained from polyhydric alcohols having 1 to 10 carbon atoms, such as ethylene glycol, propylene glycol, neopentyl glycol and dipentaerythritol, and polybasic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid and phthalic acid.
    Among the specific examples of α-olefin copolymers, mention may be made of an ethylene-α-olefin copolymer. For example, a copolymer of ethylene (15 to 80% by mole) and an α-olefin (20 to 85% by mole) of 3 to 20 carbon atoms such as propylene, 1-butene and 1- decene, which can be a random copolymer or a block copolymer. The α-olefin copolymer preferably has a weight-average molecular weight (Mw) of 2000 to 9000 inclusive, and more preferably of 3000 to 8000 inclusive. The weight-average molecular mass (Mw) is the weight-average molecular mass equivalent to the polystyrene obtained with the technique of gel permeation chromatography (GPC) (reference standard: polystyrene).
    The lubricating composition (II) may also contain the antioxidant (C) or the metal deactivator (D). The details, including the ranges of preferable values, of the antioxidant (C) and the deactivator (D) in the composition of the lubricant (II) are the same as in the composition of the lubricant (I). When the favorable value ranges are observed, the locking parts of the clasp can be lubricated for a long period of time.
    [0069] When the total amount of the lubricant (A), the anti-wear agent (B) and the fluidity control agent (F) is 100 parts by mass in the lubricating composition for watches according to the second embodiment, it is preferable that the total amount of the lubricant (A) and the fluidity control agent (F) be 10 to 80 parts by mass inclusive, and the amount of the anti-wear agent (B ) is 20 to 90 parts by mass inclusive, and it is preferable that the total amount of the lubricant (A) and the fluidity control agent (F) be 25 to 35 parts by mass inclusive and the amount of the anti-wear agent (B) is 65 to 75 parts by weight inclusive. When these amounts are used, oil outflows can be suppressed and a film of the lubricating composition (II) which has a favorable hardness can be formed. Thanks to this, the locking parts of the clasp can be lubricated for a long period of time.
    [0070] When the total amount of the lubricant (A) and the fluidity control agent (F) is 100 parts by mass in the composition of the lubricant for watches according to the second embodiment, it is preferable that the amount of the lubricant (A) is 10 to 90 parts by mass inclusive and the amount of the fluidity control agent (F) is 10 to 90 parts by mass inclusive. When these amounts are used, oil outflows can be suppressed and a film of the lubricating composition (II) which has a favorable hardness can be formed. Thanks to this, the locking parts of the clasp can be lubricated for a long period of time.
    [0071] The amount of antioxidant (C) is preferably from 0.01 to 1.2 parts by mass inclusive with respect to 100 parts by mass of the total quantity of the lubricant (A), the anti-wear agent (B) and anti-wear agent (F). This amount improves durability. The amount of the metal deactivator (D) is preferably 0.01 to 1.2 mass parts inclusive with respect to 100 mass parts of the total quantity of the lubricant (A), the anti-wear agent (B ) and anti-wear agent (F). This amount further suppresses corrosion.
    The lubricating composition for watches according to the second embodiment is generally in the creamy state at room temperature.
    The lubricating composition for watches according to the second embodiment can be obtained by mixing the components described above. Mixing can be done, for example, by heating the components. In case of heating, it is better to return to room temperature and mix again in order to knead. In this way, the lubricating composition for watches according to the second embodiment can be prepared.
    Watch according to the second embodiment
    The lubricating composition for watches (lubricating composition (II)) is applied to a watch according to the second embodiment. For example, the lubricating composition for watches is applied to the locking parts of a clasp of a watch strap. Clasp locking parts are under high pressure when closed and opened. The lubricating composition for watches is suitably used to lubricate the locking parts. Specifically, the lubricating composition for watches is applied to the locking parts. The lubricating composition for watches can be applied in a relatively thin lubricating layer with favorable hardness and without oil dripping. In addition, since the lubricating composition for watches does not easily evaporate, the functions of the clasp of closing and opening can be maintained for a long period of time. Further, since the functions of the clasp are obtained already with a small amount of the lubricating composition (II), the lubricating composition (II) is not easily recognizable as forming a stain.
    The watch according to the second embodiment preferably contains a watch strap whose locking parts of a clasp are subjected to a particularly high pressure. The effect of the lubricating composition (II) can best be demonstrated when the lubricating composition (II) is used in the locking parts of a clasp which are subjected to particularly high pressure. An example of a watch with such locking parts will be described in detail.
    Figures 2 and 3 are views to explain the watch according to the second embodiment. As shown in Figure 2, the watch strap has a clasp structure 10. The clasp structure 10 is provided with a clasp body 24 to which is attached a band member 26 so that the clasp body 24 can slide along the band element 26 in the longitudinal direction. The clasp body 24 is equipped with a sliding frame 28 of substantially U-shaped cross-section and consists of a bottom plate 30 and side walls 32 mounted on both sides of the bottom plate 30 in the width direction. . The clasp body 24 is provided with a pressing plate 34. A support projection 36 formed at both ends of the pressing plate 34 in the width direction fits into a long hole 38 formed in the side walls 32 of the sliding frame 28 so as to have a slight play. The support projection 36 is thus guided in the long hole 38 and fixed so that the pressing plate 34 can move vertically. The pressing plate 34 is slightly in contact with the upper surface of the band element 26, so that the sliding frame 28 can slide along the band element 26 in the longitudinal direction. The distal end of the pressing plate 34 is curved slightly upwards, so that the band member 26 can be easily inserted between the pressing plate 34 and the lower plate 30 of the sliding frame 28. A connecting plate 16 is connected to the end of another strip element 12 with a pin 14 so as to be able to rotate. An inner connecting plate 20 is connected to the other end of the outer connecting plate 16 by a pin 18 so as to be rotatable relative to the outer connecting plate 16. The other end of the inner connecting plate 20 is connected to the closure body 24 by a pin 22. A locking plate 42 is connected to the end of the outer connection plate 16 via a pin 40 so as to be rotatable relative to the connecting plate. outer connection 16. The latch plate 42 engages a latch hook 44 protruding from the latch plate 42 with a pin 46 with the outer connection plate 16 and the inner connection plate 20 in the collapsed state. The diameter of the strap is thus reduced so that the watch can be attached to the arm. Specifically, inner connecting plate 20, outer connecting plate 16, and locking plate 42 constitute a folding piece that folds over closure body 24. A locking frame 58 is attached to pin 46. The frame latch 58 is made of a pair of side plates 60 and a top plate 62, and an inwardly projecting latch projection 64 is formed on the pair of side plates 60. When the latch projection 64 is engaged with the locking holes 66 of the side walls 32 of the sliding frame 28 of the closure body 24, the folding part locked to the closure body 24 is reliably fixed with respect to the closure body 24.
    The locking hook 44 and the pin 46 are subjected to particularly high pressure during locking and unlocking. When the lubricating composition (II) is applied to the locking parts subjected to particularly high pressure, the effect of the lubricating composition (II) can be better demonstrated.
    As illustrated in Figure 3, a clasp structure 10 of the watch strap has a structure fundamentally identical to the clasp structure 10 illustrated in Figure 2. For the same elements, the same reference signs are used and a detailed description is omitted. In the clasp structure 10 of Fig. 3, an outer connecting plate 16 and an inner connecting plate 20, which are folding parts, are omitted, and another band member 12 is configured so as to be separable from each other. a clasp body 24 and a band element 26. A locking plate 78 is rotatably connected to the end of the other band element 12 and a hook 80 protrudes from the back of the locking plate. 78. A hook 96 protrudes from the end of the other band member 12. A locking pin 98 for locking the hook 80 and a locking pin 100 for locking the hook 96 are each provided on the side walls 32 d a sliding frame 28 of the closure body 24. With this configuration, the hook 96 at the end of the other band member 12 locks onto the locking pin 100 when the locking plate 78 locks onto the body. loop 24. Set Next, the hook 80 on the rear side of the locking plate 78 engages the locking pin 98.
    The hook 80 and the locking pin 98 are subjected to particularly high pressure during locking and unlocking. When the lubricating composition (II) is applied to locking parts subjected to particularly high pressure, the effect of the lubricating composition (II) is appropriately manifested.
    [0080] Examples of methods of applying the watch lubricating composition include a method in which the watch lubricating composition is applied by coating the locking parts with a cleanroom cotton swab and the excess composition is wiped off. . By this, an application layer containing the lubricating composition for watches in a creamy state is formed.
    The lubricating composition for watches according to the second embodiment can also be used on sliding parts subjected to high pressures and vibrations in a mechanical watch. For example, the sliding parts of the escapement, a gear train, a lever and the sliding parts of a spring for time correction. The effect described above is demonstrated even with such examples.
    In light of the above description, the present invention relates to the following.
    [0083] [1] Lubricating composition for watches containing a lubricant (A) and an anti-wear agent (B), the lubricating composition for watches is characterized in that the lubricant (A) contains at least one saturated aliphatic hydrocarbon (A -2) having a melting point of at least 45°C and a carbon number of 23 to 38 inclusive and the antiwear agent (B) contains at least one type selected from a neutral phosphate ester and a phosphite ester neutral.
    [0084] [2] The lubricating composition for watches according to [1] is characterized in that the anti-wear agent (B) contains at least one type selected from a neutral phosphate ester (B-1) represented by the general formula (b-1) and a neutral phosphite ester (B-2) represented by the general formula (b-2). (In formula (b-1), R<b11> to R<b14> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms, R<b15> to R<b18> each independently represent a linear alkyl group or branched with 1 to 6 carbon atoms, R<b191> and R<b192> each independently represents a hydrogen atom or a linear or branched alkyl group with 1 to 5 carbon atoms and the total number of carbon atoms of R<b191>and R<b192>is 1 to 5.) (In formula (b-2), R<b21> to R<b24> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms, R <b25>to R<b28>each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms, R<b291>and R<b292>each independently represent a hydrogen atom or a linear or branched alkyl group of 1 to 5 carbon atoms and the total number of carbon atoms of R<b291> and R<b292> is 1 to 5.)
    [0085] Thanks to the lubricating composition for watches, oil leaks can be suppressed even when the lubricating composition for watches is used in the sliding parts of a mechanical watch or the clasp of a watch strap.
    The lubricating composition for watches is characterized in that it preferably further contains an antioxidant (C), the antioxidant (C) containing at least one type selected from a diphenylamine derivative (C-1) represented by the general formula (c-1) and a hindered amine compound (C-2) represented by the general formula (c-2). (In formula (c-1), R<c11> and R<c12> each independently represent a linear or branched alkyl group of 1 to 10 carbon atoms, and p and q each independently represent an integer of 0 to 5, provided that p and q do not represent 0 at the same time). (In formula (c-2), R<c21> and R<c22> each independently represents an aliphatic hydrocarbon group of 1 to 10 carbon atoms, and R<c23> represents a divalent aliphatic hydrocarbon group of 1 to 10 carbon atoms. of carbon.)
    [0087] When such an antioxidant (C) is used, the deterioration can be restrained for a long period of time.
    The lubricating composition for watches is characterized in that it preferably additionally contains a metal deactivator (D).
    [0089] When the metal deactivator (D) is used, the corrosion of the metal is better suppressed.
    The lubricating composition for watches is characterized in that the paraffin wax (A-1) preferably has a melting point of 45°C to 80°C inclusive.
    [0091] When paraffin wax (A-1) is used, oil drips are better suppressed.
    The lubricating composition for watches is characterized in that the saturated aliphatic hydrocarbon (A-2) is preferably chosen from tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane , tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane, heptatriacontane or octatriacontane.
    [0093] When saturated aliphatic hydrocarbon (A-2) is used, oil drips are better suppressed.
    [0094] Treatment liquid for the lubrication of a watch containing a lubricant (A), an anti-wear agent (B) and a solvent (E), characterized in that the lubricant (A) contains at least one type chosen from a paraffin wax (A-1) and a saturated aliphatic hydrocarbon (A-2) having a melting point of at least 45°C and a carbon number of 23 to 38 inclusive and the antiwear agent ( B) contains at least one type selected from a neutral phosphate ester and a neutral phosphite ester.
    The treatment liquid for lubricating a watch is characterized in that the antiwear agent (B) preferably contains at least one type selected from a neutral phosphate ester (B-1) represented by the general formula (b-1) and a neutral phosphite ester (B-2) represented by the general formula (b-2). (In formula (b-1), R<b11> to R<b14> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms, R<b15> to R<b18> each independently represent a linear alkyl group or branched with 1 to 6 carbon atoms, R<b191> and R<b192> each independently represents a hydrogen atom or a linear or branched alkyl group with 1 to 5 carbon atoms and the total number of carbon atoms of R<b191>and R<b192>is 1 to 5.) (In formula (b-2), R<b21> to R<b24> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms, R <b25>to R<b28>each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms, R<b291>and R<b292>each independently represent a hydrogen atom or a linear or branched alkyl group of 1 to 5 carbon atoms and the total number of carbon atoms of R<b291> and R<b292> is 1 to 5.)
    [0096] When the treatment liquid for watches is used, the lubricating composition for watches is suitably applied to the sliding parts of a mechanical watch.
    A watch is characterized in that it is applied to the lubricating composition for watches according to the invention.
    [0098] The watch (eg mechanical watch) performs better and is lubricated for a long time.
    The lubricant composition for is characterized in that it preferably contains anti-wear agent (B) in an amount of 1 to 200 parts by mass inclusive with respect to 100 parts by mass of the lubricant (A).
    [0100] When these amounts are used, adequate lubrication is ensured for a long time even if the lubricating composition for watches is used in sliding parts subjected to high pressure and vibration in a mechanical watch.
    [0101] [11] The lubricating composition for watches is characterized in that it preferably also contains a fluidity control agent (F), and in that when the total quantity of the lubricant (A), of the agent antiwear (B) and fluidity control agent (F) is 100 parts by mass, the total amount of lubricant (A) and fluidity control agent (F) is 10 to 80 parts by mass. mass included, the amount of the anti-wear agent (B) is 20 to 90 parts by mass inclusive.
    [0102] When using these amounts, proper lubrication of the locking parts of a clasp is possible for a long period of time.
    The lubricating composition for watches according to [11] is characterized in that the fluidity control agent (F) is a polyacrylate, a polymethacrylate, a polyisobutylene, a polyalkylstyrene, a polyester or an α-olefin copolymer.
    [0104] When such a fluidity control agent (F) is used, proper lubrication of the locking parts of a clasp is possible for a long period of time.
    Examples
    Example 1-1
    [0105] 100 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1) and 80 parts by mass of 4,4'-butylidene bis(3-methyl- 6-t-Butylphenyl ditridecyl phosphite as a neutral phosphite ester (B-2) was added to hexane and mixed, then the hexane was vaporized to obtain the composition of watch lubricant (lubricant composition (I)).
    [0106] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of hexane as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 1-2
    [0107] In addition to the use of 5 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl-ditridecyl phosphite instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same manner as in Example 1-1 The lubricating composition for watches was used to obtain the treatment liquid for the lubrication of a watch in the same manner as in Example 1 -1.
    Example 1-3
    In addition to the use of 120 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl-ditridecyl phosphite instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same manner as in Example 1-1 The lubricating composition for watches was used to obtain the treatment liquid for the lubrication of a watch in the same manner as in Example 1 -1.
    Example 1-4
    [0109] In addition to the use of 200 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl-ditridecyl phosphite instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same manner as in Example 1-1 The lubricating composition for watches was used to obtain the treatment liquid for the lubrication of a watch in the same manner as in Example 1 -1.
    Example 1-5
    In addition to the use of 40 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl-ditridecyl phosphite instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same manner as in Example 1-1 The lubricating composition for watches was used to obtain the treatment liquid for the lubrication of a watch in the same manner as in Example 1 -1.
    Example 1-6
    [0111] 100 parts by mass of paraffin wax 130°F (melting point: 55°C), 80 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl ditridecyl phosphite as ester neutral phosphite (B-2), 0.9 parts by mass of diphenylamine derivative (product name: Irganox L57, manufactured by Ciba Specialty Chemicals) and 0.9 parts by mass of bis(2,2,6,6,6-tetramethyl -1-(octyloxy)piperidin-4-yl) of decanedioic acid as the hindered amine compound (C-2) were added to hexane and mixed, then the hexane was evaporated to obtain the lubricating composition for watches (lubricating composition (I)) The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 1-1.
    Example 1-7
    [0112] 100 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 80 parts by mass of 4,4'-butylidene bis(3-methyl- 6-t-butylphenyl ditridecyl phosphite as the neutral phosphite ester (B-2), and 0.09 parts by mass of benzotriazole as the metal deactivator (D) were added to hexane, then the hexane was vaporized to obtaining a lubricating composition for watches (lubricating composition (I)) The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 1-1.
    Example 1-8
    Besides using paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 1-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 1-1.
    Example 1-9
    [0114] Besides using paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 1-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 1-1.
    Example 1-10
    [0115] 100 parts by mass of tetracosane (melting point: 50° to 53° C.) in the form of a saturated aliphatic hydrocarbon (A-2) and 80 parts by mass of 4,4'-butylidene bis(3-methyl -6-t-Butylphenyl ditridecyl phosphite as a neutral phosphite ester (B-2) was added to toluene and mixed, then the toluene was evaporated to obtain the lubricating composition for watches (lubricating composition (I)).
    [0116] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of toluene as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 1-11
    Besides the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition for watches (lubricating composition (I)) was obtained in the same way as in the example 1-10. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 1-10.
    Example 1-12
    [0118] 100 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1) and 80 parts by mass of 4,4'-butylidene bis(3-methyl- 6-t-Butylphenyl ditridecyl phosphite as the neutral phosphite ester (B-2) were mixed while heating to obtain the lubricating composition for watches (lubricating composition (I)).
    Example 2-1
    [0119] 100 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1) and 80 parts by mass of 4,4'-butylidene bis(3-methyl- 6-t-butylphenyl ditridecyl phosphate) as a neutral phosphate ester (B-1) was added to hexane and mixed, then the hexane was evaporated to obtain the composition of watch lubricant (lubricant composition (I)).
    [0120] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of hexane as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 2-2
    [0121] In addition to the use of 5 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl ditridecyl phosphate) instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same way as in Example 2-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-1.
    Example 2-3
    [0122] In addition to the use of 120 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl ditridecyl phosphate) instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same way as in Example 2-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-1.
    Example 2-4
    [0123] In addition to the use of 200 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl ditridecyl phosphate) instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same way as in Example 2-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-1.
    Example 2-5
    [0124] In addition to the use of 40 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenyl ditridecyl phosphate) instead of 80 parts by mass, the lubricating composition for watches (lubricating composition ( I)) was obtained in the same way as in Example 2-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-1.
    Example 2-6
    [0125] Besides using paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 2-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-1.
    Example 2-7
    [0126] Besides using paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 2-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-1.
    Example 2-8
    [0127] 100 parts by mass of tetracosane (melting point: 50°C to 53°C) as saturated aliphatic hydrocarbon (A-2) and 80 parts by mass of 4,4'-butylidene bis(3-methyl-6 -t-butylphenyl ditridecyl phosphate) as a neutral phosphate ester (B-1) are added to toluene and mixed, then the toluene is evaporated to obtain the lubricating composition for watches (lubricating composition (I)).
    [0128] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of toluene as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 2-9
    [0129] In addition to the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition for watches (lubricating composition (I)) was obtained in the same way as in the example 2-8. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 2-8.
    Example 3-1
    [0130] 100 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1) and 80 parts by mass of trioleyl phosphite as neutral phosphite ester (B-2) were added to hexane and mixed, then the hexane was evaporated to obtain the composition of watch lubricant (lubricant composition (I)).
    [0131] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of hexane as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 3-2
    [0132] Besides using paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 3-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 3-1.
    Example 3-3
    [0133] Besides using paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 3-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 3-1.
    Example 3-4
    100 parts by mass of tetracosan (melting point: 50°C to 53°C) as saturated aliphatic hydrocarbon (A-2) and 80 parts by mass of trioleyl phosphite as neutral phosphite ester (B-2) have were added to toluene and mixed, then the toluene was evaporated to obtain the lubricating composition for watches (lubricating composition (I)).
    [0135] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of toluene as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 3-5
    Besides the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition for watches (lubricating composition (I)) was obtained in the same way as in the example 3-4. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 3-4.
    Example 4-1
    [0137] 100 parts by mass of paraffin wax 130F (melting point: 55C) as paraffin wax (A-1) and 80 parts by mass of tricresyl phosphate as neutral phosphate ester (B-1) were added to hexane and mixed, then the hexane was evaporated to obtain the lubricating composition for watches [lubricating composition (1)].
    [0138] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of hexane as the solvent (E) and mixed to obtain the treatment liquid for watch lubrication.
    Example 4-2
    [0139] Besides using paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 4-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 4-1.
    Example 4-3
    [0140] Besides using paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition for watches (lubricating composition (I)) was obtained from the same way as in Example 4-1. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 4-1.
    Example 4-4
    [0141] 100 parts by mass of tetracosane (melting point: 50°C to 53°C) as saturated aliphatic hydrocarbon (A-2) and 80 parts by mass of tricresyl phosphate as neutral phosphate ester (B-1) have were added to toluene and mixed, then the toluene was evaporated to obtain the lubricating composition for watches (lubricating composition (I)).
    [0142] 0.9 parts by mass of the lubricating composition was added to 99.1 parts by mass of toluene as the solvent (E) and mixed to obtain the treatment liquid for the lubrication of a watch.
    Example 4-5
    [0143] In addition to the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition for watches (lubricating composition (I)) was obtained in the same way as in the Example 4-4. The lubricating composition for watches was used to obtain the treatment liquid for lubricating a watch in the same manner as in Example 4-4.
    Comparative Examples
    [0144] A lubricating oil composition for watches (product name: 9415, manufactured by Mavis) was prepared as a comparative example.
    Evaluation method and results
    The treatment liquid for the lubrication of a watch obtained in Example 1-1 was applied to the pallets 3a and 3b of the pallet lever 3 in the escapement 1 represented in FIG. 1 and the solvent ( E) was evaporated. A mechanical watch having escapement 1 was manufactured with these parts and operated for two months respectively three months. A mechanical watch operated in the same way for two months respectively three months with the treatment liquids for the lubrication of a watch obtained in Examples 1-2 to 1-11, 2-1 to 2-9, 3-1 at 3-5, and 4-1 at 4-5.
    [0146] The lubricating composition for watches (lubricating composition (I)) obtained in Example 1-12 was applied to the pallets 3a and 3b of the pallet lever 3 of the escapement 1 illustrated in FIG. mechanism having escapement 1 was manufactured with these parts and operated for two months respectively three months.
    [0147] After carrying out an oleophobic treatment on the pallets 3a and 3b of the pallet lever 3 in the escapement 1 shown in Figure 1, the lubricating oil composition for watches of the comparative example was applied to the pallets 3a and 3b of the pallet lever 3. A mechanical watch having the escapement 1 was manufactured with these parts and operated for two months respectively three months.
    After two months respectively three months of operation of the mechanical watch, the time indication was checked to see if there was an advance or a delay. The results of the evaluation performed according to the following criteria are shown in Table 1-4. A: No advance or delay was observed in the time indication of the watch. B: A small delay was observed in the time indication of the watch. C: A significant advance or a significant delay has been observed in the time indication of the watch.
    No significant advance or delay was observed in the indication of the time of mechanical watches using the lubricating compositions for watches (lubricating composition (I)) obtained according to the examples after two months and after three months. It is believed that there was no change in slip resistance and there was no significant advance or significant delay in timekeeping because the flows of oil have been eliminated following the use of the lubricating compositions for watches (lubricating composition (I)) obtained according to the examples.
    [0150] In the mechanical watch using the composition of the lubricating oil for watches of the comparative example, there was a great advance in the time indication after two months respectively after three months. It is believed that the slip resistance has increased and there have been no great advances over time because the oil leaks have occurred as a result of using the watch lubricating oil composition of the watch. comparative example.
    [0151] The treatment liquid for the lubrication of a watch obtained according to Example 1-1 was applied to the pallets 3a and 3b of the pallet lever 3 represented in FIG. 1 and the solvent (E) was evaporated . The escapement wheel 2 was immersed in the treatment liquid for the lubrication of a watch obtained according to Example 1-1, then the solvent (E) was evaporated. A mechanical watch with escapement 1 was made with these parts and ran for two months and three months. After two months and three months of operation of the mechanical watch, the time indication was checked to see if there was any advance or delay. The same evaluation results as those obtained when applying the treatment liquid for the lubrication of a watch to the pallets 3a and 3b of the pallet lever 3 were obtained („A“ after two months and after three months ). The same evaluation results were obtained for the treatment liquid for the lubrication of a watch obtained according to Examples 1-2 to 1-11, 2-1 to 2-9, 3-1 to 3-5, and 4-1 to 4-5. In more detail, the same evaluation results as those obtained when applying the treatment liquid for lubricating a watch to the paddles 3a and 3b of the paddle lever 3 were obtained in each case.
    Example 5-1
    [0152] 15 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass of an ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, product name: LUCANT HC2000, weight average molecular weight (Mw): 7000) as fluidic agent (F), and 70 parts by mass of 4,4'-butylidene bis(3-methyl-6-t-butylphenylbutyl -ditylridecylphosphite as a phosphite neutral ester (B-2) were mixed while heating, After bringing the mixture to room temperature, further kneading was carried out to obtain the lubricating composition (II).
    Example 5-2
    Besides the use of 27 parts by mass of 130°F paraffin wax and 3 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (lubricating composition (II)) was obtained in the same way than in Example 5-1.
    Example 5-3
    Besides the use of 21 parts by mass of 130°F paraffin wax and 9 parts by mass of ethylene-α-olefin copolymer, the lubricating composition [(lubricating composition (II)) was obtained from the same way as in Example 5-1.
    Example 5-4
    Besides the use of 9 parts by mass of 130°F paraffin wax and 21 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (lubricating composition (II)) was obtained in the same way than in Example 5-1.
    Example 5-5
    Besides the use of 3 parts by mass of 130°F paraffin wax and 27 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (lubricating composition (II)) was obtained in the same way than in Example 5-1.
    Example 5-6
    Besides the use of paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the Example 5-1.
    Example 5-7
    Besides the use of paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the Example 5-1.
    Example 5-8
    Besides the use of tetracosane (melting point: 50° C. to 53° C.) instead of 130° F. paraffin, the lubricating composition (II) was obtained in the same way as in example 5-1.
    Example 5-9
    Besides the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition (II) was obtained in the same way as in Example 5-1.
    Example 5-10
    [0161] In addition to using an ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, product name: LUCANT HC600, weight-average molecular mass (Mw): 4700) instead of the ethylene-α-olefin copolymer ( manufactured by Mitsui Chemicals, product name: LUCANT HC2000, weight average molecular mass (Mw): 7000), the lubricating composition (II) is obtained according to the same method as in Example 5-1.
    Example 6-1
    [0162] 15 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass of an ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, product name: LUCANT HC2000, weight average molecular weight (Mw): 7000) as a fluidity control agent (F), and 70 parts by mass of 4,4'-butylidene bis(3-methyl-6- t-butylphenyl ditridecyl phosphate) as the neutral phosphate ester (B-1) were mixed while heating. After having brought the mixture back to room temperature, a new mixing was carried out to obtain the lubricating composition (II).
    Example 6-2
    [0163] In addition to the use of 27 mass parts of. paraffin wax 130° F. and 3 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in example 6-1.
    Example 6-3
    Besides the use of 21 parts by mass of 130°F paraffin wax and 9 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 6-1.
    Example 6-4
    Besides the use of 9 parts by mass of 130°F paraffin wax and 21 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 6-1.
    Example 6-5
    Besides the use of 3 parts by mass of 130°F paraffin wax and 27 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 6-1.
    Example 6-6
    Besides the use of paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the Example 6-1.
    Example 6-7
    [0168] Besides the use of paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the Example 6-1.
    Example 6-8
    Besides tetracosane (melting point: 50° C. to 53° C.) instead of 130° F. paraffin, the lubricating composition (II) was obtained in the same way as in Example 6-1.
    Example 6-9
    Besides the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition (II) was obtained in the same way as in Example 6-1.
    Example 6-10
    [0171] In addition to using an ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, product name: LUCANT HC600, weight-average molecular mass (Mw): 4700) instead of the ethylene-α-olefin copolymer ( manufactured by Mitsui Chemicals, product name: LUCANT HC2000, weight average molecular weight (Mw): 7000), the lubricating composition (II) is obtained in the same way as in Example 6-1.
    Example 7-1
    [0172] 15 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, name of product: Tetrax Grade 3T, number average molecular weight (Mn): 49000) as fluidity control agent (F), and 70 parts by mass of 4,4'-butylidene bis(3-methyl-6-t- butylphenyl ditridecyl phosphite as the neutral phosphite ester (B-2) were mixed while heating, After bringing the mixture to room temperature, further kneading was carried out to obtain the lubricating composition (II).
    Example 7-2
    Besides the use of 27 parts by mass of 130°F paraffin wax and 3 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 7-1.
    Example 7-3
    Besides the use of 21 parts by mass of 130°F paraffin wax and 9 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 7-1.
    Example 7-4
    Besides using 9 parts by mass of 130°F paraffin wax and 21 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 7-1.
    Example 7-5
    Besides the use of 3 parts by mass of 130°F paraffin wax and 27 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 7-1.
    Example 7-6
    Besides the use of paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the Example 7-1.
    Example 7-7
    Besides the use of paraffin wax 150°F (melting point: 66°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the Example 7-1.
    Example 7-8
    Besides the use of tetracosane (melting point: 50° C. to 53° C.) instead of 130° F. paraffin, the lubricating composition (II) was obtained in the same way as in example 7-1.
    Example 7-9
    Besides the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition (II) was obtained in the same way as in example 7-1.
    Example 7-10
    [0181] Besides using polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 4T, number average molecular weight (Mn): 59000) instead of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 3T, number average molecular weight (Mn): 49000), the lubricating composition (II) is obtained in the same way as in Example 7-1.
    Example 7-11
    [0182] Besides using polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 5T, number average molecular weight (Mn): 69000) instead of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 3T, number average molecular weight (Mn): 49000), the lubricating composition (II) is obtained in the same way as in Example 7-1.
    Example 7-12
    [0183] Besides using polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 6T, number average molecular weight (Mn): 80000) instead of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 3T, number average molecular weight (Mn): 49000), the lubricating composition (II) is obtained as in Example 7-1.
    Example 8-1
    [0184] 15 parts by mass paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, name of product: Tetrax Grade 3T, number average molecular weight (Mn): 49000) as fluidity control agent (F), and 70 parts by mass of 4,4'-butylidene bis(3-methyl-6-t- butylphenyl ditridecyl phosphate) as the neutral phosphate ester (B-1) were mixed while heating. After having brought the mixture back to room temperature, a new mixing was carried out to obtain the lubricating composition (II).
    Example 8-2
    Besides the use of 27 parts by mass of 130°F paraffin wax and 3 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 8-1.
    Example 8-3
    Besides the use of 21 parts by mass of 130°F paraffin wax and 9 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 8-1.
    Example 8-4
    Besides the use of 9 parts by mass of 130°F paraffin wax and 21 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 8-1.
    Example 8-5
    Besides the use of 3 parts by mass of 130°F paraffin wax and 27 parts by mass of ethylene-α-olefin copolymer, the lubricating composition (II) was obtained in the same way as in the example 8-1.
    Example 8-6
    Besides the use of paraffin wax 120°F (melting point: 50°C) instead of paraffin wax 130°F, the lubricating composition (II) was obtained in the same way as in the example 8-1.
    Example 8-7
    [0190] In addition to the use of 150°F paraffin wax (melting point: 66°C) instead of 130°F paraffin wax, the lubricating composition (II) was obtained in the same way as in the example 8-1.
    Example 8-8
    Besides tetracosane (melting point: 50° C. to 53° C.) instead of 130° F. paraffin, the lubricating composition (II) was obtained in the same way as in Example 8-1.
    Example 8-9
    Besides the use of dotriacontane (melting point: 69° C. to 72° C.) instead of tetracosane, the lubricating composition (II) was obtained in the same way as in Example 8-1.
    Example 8-10
    [0193] Besides using polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 4T, number average molecular weight (Mn): 59000) instead of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 3T, number average molecular weight (Mn): 49000), the lubricating composition (II) is obtained as in Example 8-1.
    Example 8-11
    [0194] Besides using polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 5T, number average molecular weight (Mn): 69000) instead of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 3T, number average molecular weight (Mn): 49000), the lubricating composition (II) is obtained in the same way as in Example 8-1.
    Example 8-12
    [0195] Besides using polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 6T, number average molecular weight (Mn): 80000) instead of polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, product name: Tetrax Grade 3T, number average molecular weight (Mn): 49000), the lubricating composition (II) is obtained in the same way as in Example 8-1.
    Example 9-1
    [0196] 15 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass of an ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, product name: LUCANT HC2000, weight average molecular weight (Mw): 7000) as a flow control agent (F) and 70 parts by mass of trioleyl phosphite as a neutral phosphate ester (B-2) were mixed while heating. After bringing the mixture back to ambient temperature, the mixing was continued to obtain the lubricating composition (II).
    Example 9-2
    [0197] 15 parts by mass of paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass of an ethylene-α-olefin copolymer (manufactured by Mitsui Chemicals, product name: LUCANT HC2000, weight average molecular weight (Mw): 7000) as a flow control agent (F) and 70 parts by mass while heating. After bringing the mixture back to room temperature, the kneading was continued to obtain the lubricating composition (II).
    Example 10-1
    [0198] 15 parts by mass paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, name of product: Tetrax Grade 3T, number average molecular weight (Mn): 49,000) as flow control agent (F) and 70 parts by weight of trioleyl phosphite, neutral phosphite ester (B-2) were mixed while heating. After bringing the mixture back to room temperature, the kneading was continued to obtain the lubricating composition (II).
    Example 10-2
    [0199] 15 parts by mass paraffin wax 130°F (melting point: 55°C) as paraffin wax (A-1), 15 parts by mass polyisobutylene (manufactured by JXTG Nippon Oil & Energy Corporation, name of the product: Tetrax Grade 3T, number average molecular weight (Mn): 49000) as a flow control agent (F) and 70 parts by mass of tricresyl phosphate as a neutral phosphate ester (B-1) were mixed while heating. After bringing the mixture back to ambient temperature, the mixing was continued to obtain the lubricating composition (II).
    Evaluation method and results
    [0200] The lubricating composition (II) prepared was used to treat the locking parts of the clasp shown in Figure 2. The locking parts of the clasp as manufactured and without modifications were used and did not work before the treatment. In other words, the lock parts couldn't lock or unlock. More specifically, the lubricating composition (II) obtained in Example 5-1 was applied to pin 46 with a cleanroom cotton swab. Next, a locking and unlocking operation of the locking piece was repeated, subjecting the pin 46 to pressure, and the composition was applied to the surface of the pin 46 and to the locking hook 44. Then, the excess applied composition was wiped off. Thus, the locking hook 44 and the surface of the pin 46 have been treated. Thanks to this treatment, the locking parts have become functional. The treatment of the locking hook 44 and the surface of the pin 46 was carried out in the same way using the lubricating compositions (II) obtained in Examples 5-2 to 5-10, 6-1 to 6-10, 7-1 to 7-12, 8-1 to 8-12, 9-1, 9-2, 10-1, and 10-2.
    [0201] Thanks to this treatment, the locking parts have become functional. No stains appeared on the lock parts after the treatment.
    [0202] A locking operation and an unlocking operation of a locking piece (test of repetition of locking/unlocking operations) were repeated 1000 times on a clasp with the composition applied. The lubricating properties of the locking parts were investigated after repeating the locking/unlocking operation to see if the locking/unlocking operations could proceed smoothly. Also, it was examined whether a stain appeared on the locking parts. The results were evaluated using the criteria below. The results of the evaluation are presented in Tables 5-9.
    Lubricating properties
    [0203] A: The locking/unlocking operations went smoothly.B: Locking/unlocking operations were slightly stiff and could not be performed without problems.
    Coloring
    [0204] A: No stain appeared.B: A stain has appeared.
    Table 9
    [0205] Lubricating properties B B B B Coloring A A A A
    List of reference signs
    [0206] 1 escapement 2 escapement wheels 3 paddle lever 3a, 3b paddles 4 spiral spring 5 balance wheel 10 clasp structure 12 other band members 24 clasp body 26 band member 44 locking hook 46 pin 80 hook 98 safety pin
    权利要求:
    Claims (12)
    [1]
    1. Lubricating composition for watches, the lubricating composition comprising:a lubricant A; andan antiwear agent B, whereinlubricant A contains at least one component selected from saturated aliphatic hydrocarbons having a melting point of at least 45°C and a carbon number of 23 to 38 inclusive, andwherein anti-wear agent B contains at least one component selected from a neutral phosphate ester and a neutral phosphite ester.
    [2]
    2. The lubricating composition for watches according to claim 1, wherein the anti-wear agent B contains at least one component selected from a neutral phosphate ester B-1 represented by the general formula (b-1) and a neutral phosphite ester B -2 represented by the general formula (b-2), in the formula (b-1), R<b11> to R<b14> each independently represent an aliphatic hydrocarbon group having 10 to 16 carbon atoms, R<b15> to R<b18> each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms, R<b191> and R<b192> each independently represent a hydrogen atom or a linear or branched alkyl group of 1 to 5 carbon atoms, and the total number of carbon atoms of R<b191> and R<b192> is 1 to 5, and, in the formula (b-2), R<b21> to R<b24> represent each independently an aliphatic hydrocarbon group of 10 to 16 carbon atoms, R<b25> to R<b28> each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms, R<b291> and R<b292> each independently represents a hydrogen atom or a linear or branched alkyl group of 1 to 5 carbon atoms, and the total number of carbon atoms of R<b291> and R<b292> is 1 to 5:
    [3]
    3. Lubricating composition for watches according to claim 1 or 2, further comprising:an antioxidant C, whereinthe antioxidant C contains at least one component selected from a diphenylamine derivative C-1 represented by the general formula (c-1) and a sterically hindered amine compound C-2 represented by the general formula (c-2), in the formula (c-1), R<c11> and R<c12> each independently represent a straight or branched chain alkyl group having 1 to 10 carbon atoms, and p and q each independently represent an integer of 0 to 5 provided that p and q do not represent 0 at the same time, and, in formula (c-2), R<c21> and R<c22> each independently represent an aliphatic hydrocarbon group of 1 to 10 carbon atoms and R <c23> represents a divalent aliphatic hydrocarbon group of 1 to 10 carbon atoms:
    [4]
    4. A lubricating composition for watches according to any one of claims 1 to 3, further comprising a metal deactivator D.
    [5]
    5. A lubricating composition for watches according to any one of claims 1 to 4, in which the paraffin wax has a melting point of 45°C to 80°C inclusive.
    [6]
    6. Lubricating composition for watches according to any one of claims 1 to 5, wherein the saturated aliphatic hydrocarbon is tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratatriacontane, pentatriacontane, heptatriacontane or octatriacontane.
    [7]
    7. A lubricating composition for watches according to any one of claims 1 to 6, wherein the anti-wear agent B is contained in an amount of 1 to 200 parts by mass inclusive with respect to 100 parts by mass of the lubricant A.
    [8]
    8. Lubricating composition for watches according to any one of claims 1 to 6, further comprising a fluidity control agent F), wherein when the total amount of lubricant A, anti-wear agent B and fluidity control agent F is 100 parts by mass, the total amount of the lubricant (A) and the fluidity control agent F contained is 10 to 80 parts by mass inclusive, and the amount of the agent anti-wear B) contained is 20 to 90 parts by mass included.
    [9]
    9. Lubricating composition for watches according to claim 8, in which the fluidity control agent F) is a polyacrylate, a polymethacrylate, a polyisobutylene, a polyalkylstyrene, a polyester or an α-olefin copolymer.
    [10]
    10. Treatment liquid for lubricating a watch, the treatment liquid comprising:a lubricant A;an anti-wear agent B; anda solvent E, in whichthe lubricant (A) contains contains at least one component selected from saturated aliphatic hydrocarbons having a melting point of at least 45°C and a carbon number of 23 to 38 inclusive, and in whichanti-wear agent B contains at least one component selected from a neutral phosphate ester and a neutral phosphite ester.
    [11]
    The treatment liquid for the lubrication of a watch according to claim 10, wherein the anti-wear agent B contains at least one component selected from a neutral phosphate ester B-1 represented by the general formula (b-1). and a neutral phosphite ester B-2 represented by the general formula (b-2), in the formula (b-1), R<b11> to R<b14> each independently represent an aliphatic hydrocarbon group having 10 to 16 carbon atoms. carbon, R<b15> to R<b18> each independently represent a linear or branched alkyl group of 1 to 6 carbon atoms, R<b191> and R<b192> each independently represent a hydrogen atom or a linear alkyl group or branched with 1 to 5 carbon atoms, and the total number of carbon atoms of R<b191> and R<b192> is 1 to 5, and, in formula (b-2), R<b21> to R<b24> each independently represent an aliphatic hydrocarbon group of 10 to 16 carbon atoms, R<b25> to R<b28> each independently represent a linear alkyl group or branched with 1 to 6 carbon atoms, R<b291> and R<b292> each independently represent a hydrogen atom or a linear or branched alkyl group with 1 to 5 carbon atoms, and the total number of atoms of carbon of R<b291> and R<b292> is 1 to 5:
    [12]
    12. A watch which has been treated with the lubricating composition for watches according to any one of claims 1 to 6.
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    CN110494538A|2019-11-22|
    WO2018173555A1|2018-09-27|
    引用文献:
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    DE60120596T2|2000-02-09|2007-06-06|Citizen Watch Co., Ltd., Nishitokyo|Use of a lubricating oil composition in a watch and watch with this composition|
    JP2001303088A|2000-04-18|2001-10-31|Citizen Watch Co Ltd|Adherent oil and method for producing watch using the same|
    JPWO2004018594A1|2002-08-21|2005-12-08|シチズン時計株式会社|Grease composition for precision equipment and watch using the same|
    JP5215747B2|2008-06-18|2013-06-19|シチズン時計株式会社|Lubricating composition for watch band and watch band using the same|
    WO2010074242A1|2008-12-26|2010-07-01|シチズン電子株式会社|Lubrication kit and small electronic device utilizing the lubrication kit|
    FR2990433A1|2012-05-10|2013-11-15|Surfactis Technologies|CATANIONIC SURFACE RECOVERY COMPOSITIONS THROUGH PHOSPHONIC MOLECULES AND AMINES|
    EP2949739B1|2013-01-22|2017-06-28|Citizen Watch Co., Ltd.|Clock lubricating-oil composition and clock|
    US9777242B2|2013-01-22|2017-10-03|Citizen Watch Co., Ltd.|Lubricating oil composition for timepiece and timepiece|JP2020083935A|2018-11-16|2020-06-04|シチズン時計株式会社|Lubricating composition for timepiece band, method for manufacturing timepiece band, and timepiece band|
    CN111117745A|2019-12-30|2020-05-08|兰州道合石化有限公司|Lubricating oil composition suitable for medical abrasive drilling handle|
    法律状态:
    2021-11-15| PL| Patent ceased|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2017059799|2017-03-24|
    PCT/JP2018/005095|WO2018173555A1|2017-03-24|2018-02-14|Lubricant composition for watch, treatment solution for watch lubrication, and watch|
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