Grease composition for timepieces and timepiece using same

Abstract

This grease composition for timepieces comprises: a base oil selected from paraffinic hydrocarbon oils, ester oils, and ether oils, or a base oil selected from vegetable oils and derivatives thereof; a thickener; a neutral phosphite ester represented by general formula (b1); and a pentavalent phosphate ester represented by general formula (b2). The pentavalent phosphate ester comprises two or more species, and the number of carbon atoms in the alkyl group represented by Rb21 in the two or more species of pentavalent phosphate esters differ from each other.

Description

Grease composition for watches and watches using the same

[0001] The present invention relates to a grease composition for a watch and a watch using the same.

[0002] Patent Document 1 describes a grease composition for watches containing lithium soap grease or urea grease and an anti-wear agent. Specific examples of the anti-wear agent include neutral phosphate esters such as trioleyl phosphate, neutral phosphite esters such as trioleyl phosphite, and calcium borate. The grease composition for watches is applied to the slip mechanism of a watch to form a lubricating film.

[0003] WO 2004 / 018594

[0004] However, the grease composition for a timepiece disclosed in Patent Document 1 leaves room for improvement in terms of torque when applied to the slip mechanism of a timepiece.

[0005] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a grease composition for watches that exhibits excellent lubricating properties when applied to the sliding parts of a watch.

[0006] The watch grease composition of the present invention comprises a base oil selected from paraffinic hydrocarbon oils, ester oils, and ether oils, or a base oil selected from vegetable oils and derivatives thereof, a thickener, a neutral phosphite ester represented by the following general formula (b1), and a pentavalent phosphate ester represented by the following general formula (b2), wherein two or more types of pentavalent phosphate esters are contained, and R in the two or more pentavalent phosphate esters is b21 The alkyl groups represented by the formula (I) have different numbers of carbon atoms.

[0007]

[0008] In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms; R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms; R b191 and R b192 ​each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R b191 and R b192 The total number of carbon atoms is 1 to 5.

[0009]

[0010] In formula (b2), R b21 represents an alkyl group having 4 to 22 carbon atoms, and n represents an integer of 1 or 2.

[0011] The grease composition for a watch of the present invention exhibits excellent lubricating properties when applied to the sliding parts of a watch.

[0012] Modes (embodiments) for carrying out the present invention will be described in detail. The present invention is not limited to the contents described in the following embodiments. Furthermore, the components described below include those that can be easily imagined by a person skilled in the art and those that are substantially the same. Furthermore, the configurations described below can be combined as appropriate. Furthermore, various omissions, substitutions, or modifications of the configurations can be made within the scope of the gist of the present invention.

[0013] <Watch Grease Composition According to Embodiment 1> The watch grease composition according to Embodiment 1 contains a base oil, a thickener, a neutral phosphite ester, and a pentavalent phosphate ester (a monophosphate or a diphosphate ester). Because a specific neutral phosphite ester and two or more specific pentavalent phosphate esters are used in combination, the watch grease composition according to Embodiment 1 exhibits excellent lubricating performance when applied to the sliding parts of a watch. Specifically, when applied to the slip mechanism of a watch, it is able to exert suitable torque.

[0014] [Base Oil] The base oil is selected from paraffinic hydrocarbon oils, ester oils, and ether oils. The paraffinic hydrocarbon oils, ester oils, and ether oils may be used alone or in combination of two or more. Paraffinic hydrocarbon oils are resistant to deterioration and are preferably used from the viewpoint of durability. Ester oils are preferably used from the viewpoint of low-temperature operability.

[0015] ​Examples of paraffinic hydrocarbon oils include α-olefin polymers having typically 30 or more carbon atoms, preferably 30 to 50. The number of carbon atoms in paraffinic hydrocarbon oils can be determined by measuring the number-average molecular weight by gel permeation chromatography (GPC) and calculating from the measured value. Examples of such α-olefin polymers include homopolymers of one monomer selected from ethylene and α-olefins having 3 to 18 carbon atoms, preferably α-olefins having 10 to 18 carbon atoms, and copolymers of at least two monomers selected from ethylene and α-olefins having 3 to 18 carbon atoms, preferably α-olefins having 10 to 18 carbon atoms. Specific examples include 1-decene trimer, 1-undecene trimer, 1-dodecene trimer, 1-tridecene trimer, 1-tetradecene trimer, and copolymers of 1-hexene and 1-pentene. The paraffinic hydrocarbon oil preferably has a kinematic viscosity at 100°C of 2 cSt or more and 100 cSt or less, and more preferably 4 cSt or more and 6 cSt or less.

[0016] Examples of ester oils include polyol ester oils. From the viewpoint of preventing corrosion of watch components, the polyol ester oil is preferably a polyol ester oil that does not have a hydroxyl group in the molecule. The polyol ester oils may be used alone or in combination of two or more.

[0017] Such polyol ester oils can be produced by reacting a polyol having at least two hydroxyl groups in one molecule with a monovalent acid or a salt thereof at a mixing molar ratio ((monovalent acid or its salt) / polyol) of 1 or more. In this case, the polyol ester oil obtained is a complete ester having no hydroxyl groups in the molecule.

[0018] Examples of the polyol include neopentyl glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0019] Examples of the monovalent acids include saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, and palmitic acid; unsaturated aliphatic monocarboxylic acids such as stearic acid, acrylic acid, crotonic acid, and oleic acid; and cyclic carboxylic acids such as benzoic acid, toluic acid, naphthoic acid, cinnamic acid, cyclohexanecarboxylic acid, nicotinic acid, isonicotinic acid, furan-2-carboxylic acid, pyrrole-N-carboxylic acid, monoethyl malonate, and ethyl hydrogen phthalate. Examples of the salts of the monovalent acids include chlorides of the monovalent acids.

[0020] Specific examples of polyol ester oils include neopentyl glycol-decanoic acid / octanoic acid mixed ester, trimethylolpropane-valeric acid / heptanoic acid mixed ester, trimethylolpropane-decanoic acid / octanoic acid mixed ester, trimethylolpropane nonanoate, and pentaerythritol-heptanoic acid / decanoic acid mixed ester.

[0021] The ether oil may have a hydroxyl group in the molecule, but from the viewpoint of preventing corrosion of watch parts, it is preferable that the ether oil does not have a hydroxyl group in the molecule, and an ether oil represented by the following formula (a1) is more preferable. The ether oil may be used alone or in combination of two or more types.

[0022]

[0023] In formula (a1), R a11 and R a13 R each independently represents an alkyl group having 1 to 18 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. a12 represents an alkylene group having 1 to 18 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. m is an integer of 1 to 5.

[0024] ​Specific examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Specific examples of monovalent aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, tolyl, xylyl, benzyl, phenethyl, 1-phenylethyl, and 1-methyl-1-phenylethyl groups.

[0025] Specific examples of alkylene groups having 1 to 18 carbon atoms include methylene, ethylene, propylene, and butylene groups. Specific examples of divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenylene and 1,2-naphthylene groups.

[0026] [Thickener] Lithium soap or diurea compound is preferably used as the thickener. A watch grease composition obtained using lithium soap as the thickener has the advantage of being able to prevent deterioration of the slip mechanism and a decrease in torque even at low temperatures. Examples of lithium soap include lithium stearate soap and lithium 12-hydroxystearate soap, with lithium 12-hydroxystearate soap being preferably used. As the diurea compound, a diurea compound represented by the following formula (e1) is preferably used.

[0027]

[0028] In formula (e1), R e11 and R e13 each independently represents a hydrocarbon group having 1 to 10 carbon atoms; R e12 represents a hydrocarbon group having 6 to 15 carbon atoms.

[0029] R ｅ11 and R ｅ13 ​Specific examples of R include alkyl groups having 1 to 10 carbon atoms. Among these, butyl, pentyl, hexyl, and heptyl groups are preferred. ｅ12 Specific examples of the alkyl group include groups represented by the following formulae (e11) to (e13): Of these, groups represented by the following formulae (e11) and (e12) are preferred.

[0030]

[0031] [Neutral Phosphite Ester] The watch grease composition according to embodiment 1 contains a neutral phosphite ester represented by the following general formula (b1) as an anti-wear agent. The neutral phosphite ester may be used alone or in combination of two or more. The neutral phosphite ester has excellent wear resistance and extreme pressure resistance, and can improve the lubrication performance of the watch grease composition. That is, when a watch is operated using the grease composition on the sliding parts, the generation of deposits such as wear powder and rust is suppressed, and discoloration of the sliding parts is also less likely to occur. Furthermore, the grease composition can provide good lubrication even to sliding parts subjected to high pressure. In particular, when applied to the slip mechanism of a watch, it can exert favorable torque.

[0032]

[0033] In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0034] The aliphatic hydrocarbon group having 10 to 16 carbon atoms may be a linear, branched, or cyclic aliphatic hydrocarbon group, and may be a saturated or unsaturated aliphatic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group having 10 to 16 carbon atoms that can be suitably used include linear alkyl groups such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl (cetyl) groups.

[0035] R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0036] ​​Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an isopentyl group, a t-pentyl group, a neopentyl group, and an isohexyl group.

[0037] Neutral phosphite esters are R b15 ~R b18 The wear resistance and extreme pressure properties can be improved because R b15 ~R b18 This is thought to be because when the amine group has a specific substituent, the film of the watch grease composition applied to the sliding part becomes stronger.

[0038] In particular, R b15 and R b17 is a linear alkyl group having 1 to 6, preferably 1 to 3, carbon atoms, and R b16 and R b18 When is a branched alkyl group having 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms, the effect of improving the wear resistance and extreme pressure properties is further enhanced.

[0039] R b191 and R b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0040] Examples of the straight-chain or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an isopropyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an isopentyl group, a t-pentyl group, and a neopentyl group.

[0041] However, R b191 and R b192 The total number of carbon atoms in is 1 to 5. Therefore, for example, R b191 When is a hydrogen atom, R b192 is a linear or branched alkyl group having 1 to 5 carbon atoms, and R b191 When is a methyl group, R b192 is a linear or branched alkyl group having 1 to 4 carbon atoms, and Rb191 When is an ethyl group, R b192 is a straight or branched chain alkyl group having 2 to 3 carbon atoms.

[0042] The film of the watch grease composition becomes stronger, so R b191 is a hydrogen atom, and R b192 More preferably, is a straight or branched alkyl group having 1 to 5 carbon atoms.

[0043] [Pentavalent Phosphate Ester] The watch grease composition according to the first embodiment contains a pentavalent phosphate ester represented by the following general formula (b2) as an anti-wear aid.

[0044]

[0045] In formula (b2), R b21 represents alkyl having 4 to 22 carbon atoms, and n represents an integer of 1 or 2.

[0046] The watch grease composition according to the first embodiment contains two or more pentavalent phosphate esters, and R b21 The number of carbon atoms in the alkyl groups represented by the formula (I) is different. The watch grease composition according to the first embodiment contains two or more specific pentavalent phosphate esters in addition to the specific neutral phosphite ester, and therefore has excellent wear resistance and extreme pressure properties, further improving the lubricating performance of the watch grease composition. In particular, when applied to the slip mechanism of a watch, it is able to exert a suitable torque.

[0047] From the viewpoint of wear resistance and extreme pressure properties, in the above formula (b2), R b21 It is preferable that R represents an alkyl group having 12 to 18 carbon atoms. That is, the watch grease composition according to the first embodiment contains two or more pentavalent phosphate esters, and R in the two or more pentavalent phosphate esters b21 It is preferred that the alkyl groups represented by the following formula (I) have 12 to 18 carbon atoms and are different from each other.

[0048] More specifically, from the viewpoint of wear resistance and extreme pressure properties, the pentavalent phosphate ester in the grease composition for a watch according to the first embodiment is R​b21 is an alkyl group having 12 carbon atoms (C 12 H 25 -), pentavalent phosphate ester (B212), R b21 is an alkyl group having 13 carbon atoms (C 13 H 27 -), pentavalent phosphate ester (B213), R b21 is an alkyl group having 14 carbon atoms (C 14 H 29 -), pentavalent phosphate ester (B214), R b21 is an alkyl group having 15 carbon atoms (C 15 H 31 -), pentavalent phosphate ester (B215), R b21 is an alkyl group having 16 carbon atoms (C 16 H 33 -), pentavalent phosphate ester (B216), R b21 is an alkyl group having 17 carbon atoms (C 17 H 35 -), and pentavalent phosphate ester (B217), b21 is an alkyl group having 18 carbon atoms (C 18 H 37 It is preferable that the composition contains two or more pentavalent phosphate esters (B218) where n is 0 or 1. Furthermore, it is more preferable that the pentavalent phosphate esters include the pentavalent phosphate ester (B212), the pentavalent phosphate ester (B214), the pentavalent phosphate ester (B216), and the pentavalent phosphate ester (B218). Furthermore, it is more preferable that the pentavalent phosphate esters include the pentavalent phosphate ester (B213) and the pentavalent phosphate ester (B218). Note that the pentavalent phosphate ester (B212) may contain a mixture of a pentavalent phosphate ester where n is 1 and a pentavalent phosphate ester where n is 2 (along with a monophosphate ester and a diphosphate ester). The same applies to the pentavalent phosphate esters (B213) to (B218).

[0049] From the viewpoint of wear resistance and extreme pressure properties, when two pentavalent phosphate esters are used, it is preferable that one pentavalent phosphate ester is contained in an amount of 10% by mass to 90% by mass and the other pentavalent phosphate ester is contained in an amount of 90% by mass to 10% by mass, where the total of the two pentavalent phosphate esters is taken as 100% by mass. Also, from the viewpoint of wear resistance and extreme pressure properties, when three or more pentavalent phosphate esters are used, it is preferable that one pentavalent phosphate ester is contained in an amount of 10% by mass to 90% by mass and the other pentavalent phosphate esters are contained in a total amount of 90% by mass to 10% by mass, where the total of the three or more pentavalent phosphate esters is taken as 100% by mass.

[0050] [Viscosity Index Improver] The watch grease composition according to embodiment 1 preferably further contains a viscosity index improver. The viscosity index improver may be used alone, or two or more may be used in combination. The inclusion of a viscosity index improver can further improve the lubricating performance of the watch grease composition. In particular, when applied to the slip mechanism of a watch, more suitable torque can be exerted. This is thought to be because the inclusion of a viscosity index improver makes the film of the watch grease composition applied to the sliding part stronger. Furthermore, conventional watch grease compositions sometimes contain fluorine-based resins such as polytetrafluoroethylene to improve lubricating performance. However, the use of a viscosity index improver in the watch grease composition according to embodiment 1 allows it to exhibit lubricating performance equivalent to or better than conventional watch grease compositions without the addition of a fluorine-based resin, which is also preferable from an environmental perspective.

[0051] Viscosity index improvers include olefin polymers, olefin oligomers, polyacrylates, polymethacrylates, polyalkylstyrenes, polyesters, isobutylene fumarate, styrene maleate esters, vinyl acetate fumarate esters.

[0052] Examples of the olefin oligomer include an olefin homo-oligomer of one type selected from olefins having 2 to 20 carbon atoms, and an olefin co-oligomer of two or more types selected from olefins having 2 to 20 carbon atoms, with a co-oligomer of ethylene and an α-olefin being preferred. Furthermore, the olefin oligomer preferably has a kinematic viscosity at 100°C of 600 cSt or more and 2000 cSt or less. Among these, polypropylene, polyisobutylene, ethylene-propylene co-oligomer, and ethylene-isobutylene co-oligomer are preferred because they are resistant to deterioration and have excellent durability, with an ethylene-propylene co-oligomer being more preferred.

[0053] As polyacrylate and polymethacrylate, polymers of acrylic acid and methacrylic acid, and polymers of alkyl esters having 1 to 10 carbon atoms can be used. Of these, polymethacrylate obtained by polymerizing methyl methacrylate is preferred. The viscosity index improver may contain mineral oil in addition to polyacrylate and polymethacrylate.

[0054] [Antioxidant] The watch grease composition according to the first embodiment preferably further contains, as an antioxidant, a diphenylamine derivative represented by the following general formula (c1), a hindered amine compound represented by the following general formula (c2), or a 2,6-di-t-butylphenol derivative represented by the following general formula (c3). In other words, the watch grease composition according to the first embodiment preferably further contains, as an antioxidant, an antioxidant selected from the group consisting of a diphenylamine derivative represented by the following general formula (c1), a hindered amine compound represented by the following general formula (c2), and a 2,6-di-t-butylphenol derivative represented by the following general formula (c3). The inclusion of such an antioxidant extends the life of the watch grease composition. In other words, it is possible to lubricate sliding parts over a long period of time. In particular, it is possible to maintain a suitable slip torque when applied to the slip mechanism of a watch. As the antioxidant, only a diphenylamine derivative, only a hindered amine compound, or only a 2,6-di-t-butylphenol derivative may be used. Two or three compounds selected from diphenylamine derivatives, hindered amine compounds, and 2,6-di-t-butylphenol derivatives may be used in combination. For example, a diphenylamine derivative and a hindered amine compound may be used in combination. Furthermore, the combination of a hindered amine compound and a 6-di-t-butylphenol derivative enables the lubrication of sliding parts for a longer period of time. In particular, when applied to the slip mechanism of a watch, it is possible to maintain a suitable slip torque. Furthermore, even when a watch grease composition is used on sliding parts that are subjected to high pressure during sliding, the generation of deposits such as wear powder and rust is further suppressed, thereby improving durability. This is thought to be because even if active species are generated in sliding parts that are subjected to high pressure during sliding, they can be neutralized for a long period of time. Furthermore, diphenylamine derivatives may be used alone or in combination of two or more. Hindered amine compounds may be used alone or in combination of two or more. Furthermore, 2,6-di-t-butylphenol derivatives may be used alone or in combination of two or more.

[0055] ​

[0056] In formula (c1), R c11 and R c12 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms.

[0057] Examples of the straight-chain or branched alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an isopropyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an isopentyl group, a t-pentyl group, a neopentyl group, an isohexyl group, a 2-ethylhexyl group, a 2,4,4-trimethylpentyl group, and a 1,1,3,3-tetramethylbutyl group.

[0058] p and q each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, provided that p and q do not simultaneously represent 0.

[0059] Diphenylamine derivatives can be obtained, for example, by reacting diphenylamine with a compound for introducing a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent (a compound 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-trimethylpentene).

[0060]

[0061] In formula (c2), R c21 and R c22 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0062] 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.

[0063] ​Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms that can be suitably used include linear or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl, isopropyl, sec-butyl, isobutyl, t-butyl, isopentyl, t-pentyl, neopentyl, isohexyl, and 2-ethylhexyl. Of these, linear or branched alkyl groups having 5 to 10 carbon atoms are more preferred from the viewpoint of improving durability.

[0064] R c23 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0065] Suitable divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms include divalent linear or branched alkylene groups such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, and 3-methyl-1,5-pentylene. Of these, divalent linear or branched alkylene groups having 5 to 10 carbon atoms are more preferred from the viewpoint of improving durability.

[0066] In particular, from the viewpoint of improving durability, among the above, R c21 , R c22 and R c23 It is more preferable that the sum of the numbers of carbon atoms of the groups be 16 to 30.

[0067]

[0068] In formula (c3), R c31 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

[0069] ​Examples of the linear or branched alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, heptyl, isoheptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl. The above alkyl groups improve the compatibility of the 2,6-di-t-butylphenol derivative.

[0070] [Metal Deactivator] The watch grease composition according to embodiment 1 preferably further contains a metal deactivator. The inclusion of a metal deactivator can prevent corrosion. In particular, when the watch grease composition according to embodiment 1 is used in a watch made up of watch parts containing copper, it is preferable to contain a metal deactivator from the perspective of corrosion prevention. The metal deactivators may be used alone or in combination of two or more. Benzotriazole or a derivative thereof is preferred as the metal deactivator.

[0071] Specific examples of the benzotriazole derivative include compounds represented by the following formula (d1) such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, and 1-(N,N-bis(2-ethylhexyl)aminomethyl)benzotriazole, and compounds represented by the following formula (d2).

[0072]

[0073]

[0074] In formula (d1), R d11 , R d12 and R d13 each independently represents an alkyl group having 1 to 18 carbon atoms. d21 represents an alkyl group having 1 to 18 carbon atoms.

[0075] ​​The watch grease composition according to the first embodiment may contain other components as needed, as long as the effects of the present invention are not impaired. For example, other components may include a colorant.

[0076] In the watch grease composition according to embodiment 1, from the viewpoints of wear resistance and extreme pressure properties, the neutral phosphite ester is preferably contained in an amount of 0.1% by mass to 20% by mass inclusive per 100% by mass of the watch grease composition. Furthermore, from the viewpoints of wear resistance and extreme pressure properties, the pentavalent phosphate ester is preferably contained in a total amount of 0.1% by mass to 20% by mass inclusive per 100% by mass of the watch grease composition. Furthermore, when a viscosity index improver is used, from the viewpoint of lubrication performance, the viscosity index improver is preferably contained in an amount of 0.1% by mass to 50% by mass inclusive, and more preferably in an amount of 0.1% by mass to 20% by mass inclusive, per 100% by mass of the watch grease composition. When a diphenylamine derivative is used alone as the antioxidant, from the viewpoint of extending the life of the watch grease composition, the diphenylamine derivative is preferably contained in an amount of 0.01% by mass to 3% by mass inclusive per 100% by mass of the watch grease composition. When a hindered amine compound is used alone as the antioxidant, from the viewpoint of extending the life of the watch grease composition, the hindered amine compound is preferably contained in an amount of 0.01% by mass or more and 3% by mass or less, based on 100% by mass of the watch grease composition. When a diphenylamine derivative and a hindered amine compound are used in combination as the antioxidant, from the viewpoint of extending the life of the watch grease composition, the diphenylamine derivative and the hindered amine compound are preferably used in an amount of 0.01% by mass or more and 1.5% by mass or less, based on 100% by mass of the watch grease composition. Furthermore, when a 2,6-di-t-butylphenol derivative is used as the antioxidant, from the viewpoint of extending the life of the watch grease composition, the 2,6-di-t-butylphenol derivative is preferably contained in an amount of 0.01% by mass or more and 3% by mass or less, based on 100% by mass of the watch grease composition. When a hindered amine compound and a 2,6-di-t-butylphenol derivative are used in combination as an antioxidant, from the viewpoint of extending the life of the watch grease composition, the hindered amine compound and the 2,6-di-t-butylphenol derivative are preferably used in an amount of 0.01% by mass or more and 1.5% by mass or less, based on 100% by mass of the watch grease composition.When two or three compounds selected from diphenylamine derivatives, hindered amine compounds, and 2,6-di-t-butylphenol derivatives are used in combination, it is preferable to use each compound in an amount of 0.01% by mass or more and 1.5% by mass or less, based on 100% by mass of the watch grease composition, from the viewpoint of extending the life of the watch grease composition. When a metal deactivator is used, it is preferable to include the metal deactivator in an amount of 0.01% by mass or more and 3% by mass or less, based on 100% by mass of the watch grease composition, from the viewpoint of corrosion prevention. When a colorant is used, it is preferable to use the colorant in an amount of more than 0% by mass and 0.1% by mass or less, based on 100% by mass of the watch grease composition. It should be noted that in the watch grease composition according to embodiment 1, the remainder is typically a base oil and a thickener (the base grease, described below).

[0077] The watch grease composition according to embodiment 1 may be solid or semi-solid, and may be in a paste or liquid form. The state of the watch grease composition can be adjusted by changing the blending amounts of base oil and thickener. In the case of a solid or semi-solid form, the thickener is contained in an amount of, for example, 8.5 parts by mass or more and 25.0 parts by mass or less per 100 parts by mass of base oil. In the case of a paste form, the thickener is contained in an amount of, for example, more than 2.7 parts by mass and less than 8.5 parts by mass, preferably 3.0 parts by mass or more and 8.0 parts by mass or less per 100 parts by mass of base oil. In the case of a liquid form, the thickener is contained in an amount of, for example, 0.25 parts by mass or more and 2.7 parts by mass or less per 100 parts by mass of base oil.

[0078] When the watch grease composition according to embodiment 1 is solid or semi-solid, the worked penetration measured in accordance with JIS K 2220 7 is preferably 20 or more and 45 or less. When the watch grease composition according to embodiment 1 is in a paste state, the worked penetration measured in accordance with JIS K 2220 7 is preferably 400 or more and 450 or less. When the watch grease composition according to embodiment 1 is in a liquid state, the viscosity at 25°C is preferably 1000 mPa·s or more and 3000 mPa·s or less. The viscosity can be measured at 25°C using an E-type viscometer. In this specification, the term "watch grease composition" refers not only to solid or semi-solid compositions (solid watch lubricating compositions, semi-solid watch lubricating compositions), but also to paste and liquid compositions (paste watch lubricating compositions, liquid watch lubricating compositions).

[0079] When the watch grease composition according to embodiment 1 is used in the slip mechanism of a watch, the rate of decrease in slip torque (torque decrease rate) after 15 years of accelerated testing at room temperature (e.g., 25°C) can be made 10% or less. In this specification, torque decrease rate refers to the rate of change in slip torque after 15 years of accelerated testing for setting the watch, relative to the slip torque at the start of the slip mechanism operation test. In particular, when lithium soap is used as a thickener, the torque decrease rate can be made 10% or less even at low temperatures (e.g., -50°C).

[0080] When the watch grease composition according to embodiment 1 is kept at 90°C for 1000 hours, the rate of change in weight of the watch grease composition before and after keeping (evaporation rate) is, for example, 7% by weight or less, preferably 3% by weight or less, more preferably 0.7% by weight or less, and particularly preferably 0.3% by weight or less. When the evaporation rate is within the above range, watches using the watch grease composition according to embodiment 1 have excellent operational stability.

[0081] Furthermore, when the watch grease composition according to embodiment 1 contains a metal deactivator, it is preferable that when copper corrosion resistance is evaluated by a copper corrosion test (test time: 2 hours, test temperature: 100°C) in accordance with JIS K 2513:2000, the copper corrosion standard evaluation value (discoloration number) is 1 or less. This evaluation value prevents corrosion of watch components. Therefore, when used in the slip mechanism of a watch, a watch using the watch grease composition according to embodiment 1 has excellent operational stability. Furthermore, when the watch grease composition according to embodiment 1 contains the above-mentioned components in the preferred amounts, the evaluation values ​​of the torque reduction rate, evaporation rate, and copper corrosion resistance can usually be adjusted to fall within the above-mentioned ranges.

[0082] The watch grease composition according to the first embodiment can be produced by a known method. Typically, a base grease containing a base oil and a thickener is first prepared. For example, the base grease contains 80% to 90% by mass of the base oil and 10% to 20% by mass of the thickener, based on 100% by mass of the base grease.

[0083] Next, to this base grease, further base oil is added as necessary and mixed so that the final watch grease composition is in the desired state, either solid or semi-solid, paste-like or liquid, to obtain the grease. Specifically, if a solid, semi-solid, or paste-like state is to be obtained, it is preferable to add base oil as necessary so that the worked penetration falls within the above-mentioned range. Furthermore, if a liquid state is to be obtained, it is preferable to add base oil so that the viscosity at 25°C falls within the above-mentioned range. This usually allows the blending amounts of base oil and thickener in the final watch grease composition to fall within the above-mentioned ranges.

[0084] In this way, a base oil is further added to the base grease to obtain a grease, and then an anti-wear agent and the like are added and mixed to produce a grease composition for a watch.

[0085] Since the watch grease composition according to embodiment 1 is produced as described above, it can also be referred to as a watch grease composition containing lithium soap grease and a neutral phosphite ester, a pentavalent phosphate ester, or the like, or a watch grease composition containing urea grease and a neutral phosphite ester, a pentavalent phosphate ester, or the like. Here, lithium soap grease refers to a grease in which a base oil is further added to a base grease as needed, and the thickener is a lithium soap. Furthermore, urea grease refers to a grease in which a base oil is further added to a base grease as needed, and the thickener is a diurea compound.

[0086] <Watch Grease Composition According to Embodiment 2> The watch grease composition according to embodiment 2 is the same as the watch grease composition according to embodiment 1, and the effects obtained are also the same, except that a base oil selected from vegetable oils and their derivatives is used as the base oil. As such, everything other than the base oil is the same, and therefore a description thereof will be omitted.

[0087] The base oil is selected from vegetable oils and their derivatives. The vegetable oils may be used alone or in combination. The vegetable oil derivatives may be used alone or in combination. Furthermore, vegetable oils and their derivatives may be used in combination. Vegetable oils are a type of fatty oil, specifically, ester compounds of fatty acids and glycerin, and are liquid at room temperature. The fatty acid residues (acyl groups) contained in vegetable oils typically have 6 to 22 carbon atoms. Due to the distribution of fatty acid residue lengths, vegetable oils easily dissolve components added to watch grease compositions. This also broadens the range of components that can be added to watch grease compositions. Furthermore, vegetable oils themselves have excellent lubricity. This is thought to be due to the distribution of hydrocarbon group lengths in their derivatives. Vegetable oils also have the advantage of being biodegradable and highly compatible with a decarbonized society.

[0088] The vegetable oil is not particularly limited, and examples thereof include rapeseed oil, soybean oil, corn oil, rice bran oil, sesame oil, olive oil, cottonseed oil, palm oil, sunflower oil, safflower oil, perilla oil, linseed oil, coconut oil, etc. The vegetable oil preferably has a kinematic viscosity at 40°C (JIS K 2283) of 1 cSt or more and 150 cSt or less.

[0089] Examples of vegetable oil derivatives include transesterified oils (A1) obtained by transesterifying vegetable oils, diester or monoester oils (A2) obtained by hydrolyzing vegetable oils, fatty acids (A3) obtained by hydrolyzing vegetable oils, saturated fatty acids (A4) obtained by hydrogenating unsaturated fatty acids contained in the fatty acids (A3), hydrocarbons (A5) obtained by reducing the fatty acids (A3), saturated hydrocarbons (A6) obtained by hydrogenating unsaturated hydrocarbons contained in the hydrocarbons (A5), and polymers (A7) obtained by polymerizing unsaturated fatty acids contained in the fatty acids (A3) and / or unsaturated hydrocarbons contained in the hydrocarbons (A5). Similar to vegetable oils, derivatives have a distribution of hydrocarbon group lengths, which facilitates the dissolution of components added to watch grease compositions. This also broadens the range of components that can be added to watch grease compositions. Furthermore, derivatives themselves have excellent lubricity. This is believed to be due to the distribution of hydrocarbon group lengths within the derivatives. When derivatives have side chains within their skeletons, the side chains are also believed to contribute to improved lubricity. Furthermore, the derivatives are usually biodegradable and have the advantage of being highly compatible with a decarbonized society. The derivatives preferably have a kinematic viscosity at 40°C (JIS K 2283) of 1 cSt or more and 150 cSt or less.

[0090] Specifically, the derivative is preferably an interesterified oil (A1) represented by the following formula (a2), having a molecular weight of 88 to 1500 and a kinematic viscosity at 40°C (JIS K 2283) of 1 to 150 cSt. Also preferably used is a polymer (A7) of the above unsaturated fatty acid and / or unsaturated hydrocarbon having 6 to 22 carbon atoms, having a molecular weight of 88 to 1500 and a kinematic viscosity at 40°C (JIS K 2283) of 1 to 150 cSt. The use of such a derivative further broadens the range of components to be added to the watch grease composition. Furthermore, among the polymers (A7), polymers obtained by polymerizing unsaturated hydrocarbons contained in the hydrocarbons (A5) are resistant to deterioration and are therefore preferably used from the standpoint of durability. More specifically, an alkene oligomer having 12 to 18 carbon atoms (having 24 to 84 carbon atoms in one oligomer molecule) is preferably used.

[0091]

[0092] In the above formula (a2), R a21 represents a saturated or unsaturated hydrocarbon group having 5 to 21 carbon atoms.

[0093] The derivative preparation step can be carried out by a known method. Specific examples of the derivative preparation step include a step of transesterifying a vegetable oil to obtain a transesterified oil (A1) as a derivative, a step of hydrolyzing a vegetable oil to obtain a diester oil or monoester oil (A2) as a derivative, a step of hydrolyzing a vegetable oil to obtain a fatty acid (A3) as a derivative, a step of hydrogenating an unsaturated fatty acid contained in the fatty acid (A3) to obtain a saturated fatty acid (A4) as a derivative, a step of reducing the fatty acid (A3) to obtain a hydrocarbon (A5) as a derivative, a step of hydrogenating an unsaturated hydrocarbon contained in the hydrocarbon (A5) to obtain a saturated hydrocarbon (A6) as a derivative, and a step of polymerizing the unsaturated fatty acid contained in the fatty acid (A3) and / or the unsaturated hydrocarbon contained in the hydrocarbon (A5) to obtain a polymer (A7) as a derivative.

[0094] ​The step of obtaining interesterified oil (A1) allows the preparation of interesterified oil (A1) in which the acyl groups in the vegetable oil have been converted to the desired acyl groups. Furthermore, the step of obtaining diester or monoester oil (A2) allows the preparation of diester or monoester oil (A2) having the desired acyl groups by hydrolyzing a portion of the acyl groups in the vegetable oil. The step of obtaining fatty acid (A3) uses, for example, an enzyme lipase. This allows the preparation of fatty acid (A3) having acyl groups in the vegetable oil. The step of obtaining saturated fatty acid (A4) and the step of obtaining saturated hydrocarbon (A6) use, for example, a nickel catalyst. This allows the unsaturated bonds in the fatty acid (A3) and the hydrocarbon (A5) to be saturated.

[0095] In the process for obtaining hydrocarbon (A5), for example, hydrocarbon (A5) can be obtained from fatty acid (A3) via alcohol. Specifically, alcohol can be obtained from fatty acid (A3) by chemical reduction using lithium aluminum hydride (LiAlH4) or direct hydrogenation of higher fatty acid ester. The alcohol can then be converted to a leaving group such as a halide or sulfonate ester, followed by reduction with a metal hydride source (e.g., LiAlH4, LiHBEt3, Bu3SnH + radical initiator) to obtain hydrocarbon (A5). Methods for reductively removing halogen include catalytic hydrogenation and Birch reduction. For halogenation, PX3, PX5, SOCl2, (COCl)2, etc. are used. Furthermore, the Appel reaction can be used under neutral conditions. For sulfonate esterification, MsCl-Et3N or TsCl-Py(-DMAP) systems can also be used. In the case of primary alcohols, a method of reducing the alkyl iodide generated in the system using NaBHCN-(PhO)P-CHI may be used. Furthermore, Barton-McCombie deoxygenation or Marco-Lamb deoxygenation may be performed, or a photoredox catalyst may be used.

[0096] In the step of obtaining the polymer (A7), the unsaturated fatty acid contained in the fatty acid (A3) and / or the unsaturated hydrocarbon contained in the hydrocarbon (A5) are polymerized to prepare the desired polymer. The above-described steps of obtaining a derivative may be appropriately combined to prepare a derivative having a desired structure. Furthermore, the above-described steps of obtaining a derivative may be combined with a step of carrying out a hydroisomerization reaction to prepare a derivative.

[0097] More specifically, as the derivative, a hydroisomerization product (CAS No.: 2241366-04-9) of a hydrogenation reaction product of an addition reaction product of an alkene (C=16, 18, linear or branched) (limited to those having one double bond and located at position 1)) and oligomerization products of 1-tetradecene and 1-dodecene, hydrogenated, C24-84 fraction (C24-84 fraction of the hydrogenated oligomer of 1-tetradecene and 1-dodecene, CAS No.: 883233-93-0) are preferably used. Examples of such hydroisomerization reaction products include SynNova (registered trademark) 4 and SynNova 9 (trade names, manufactured by Novvi LLC). Derivatives that can be used include Novvi EL26, NovaSolv 160, PureNova 2609, PureNova 2304, and PureNova 1351 (trade names, manufactured by Novvi LLC). Derivatives that can be used include branched paraffinic hydrocarbon components obtained by the methods described in Japanese Patent Nos. 5,281,409 and 5,325,777 using vegetable oils.

[0098] <Timepiece According to the Embodiments> In the timepiece according to the embodiments, the above-mentioned timepiece grease composition (the timepiece grease composition according to Embodiment 1 or Embodiment 2) is adhered to the sliding parts. This allows the sliding parts to be suitably lubricated. An example of the sliding part is the sliding part of the center wheel and pinion having a slip mechanism. The timepiece exhibits stable operation over a long period of time, suppressing wear and friction of the slip mechanism components. The sliding part may also be a gear train unit comprising a group of gears for driving the hour, minute, and second hands, or a sliding part such as a lever. In particular, when the timepiece grease composition is in a paste or liquid form, it tends to remain where it is adhered, making it suitable for use in the above-mentioned sliding parts. Furthermore, materials for the timepiece components that make up the timepiece include brass containing copper and zinc, nickel, iron, and engineering plastic materials such as polyoxymethylene (POM), polycarbonate (PC), and polyphenylene ether (PPE). Regardless of the material of the timepiece components, the sliding parts of the timepiece according to the embodiments are suitably lubricated because the above-mentioned timepiece grease composition is used. Furthermore, even in watches with complex structures that are subjected to high loads, the sliding parts are suitably lubricated because the above-mentioned watch grease composition is used. As mentioned above, in the case of watches that are composed of watch parts that contain copper, it is preferable to add a metal deactivator to the above-mentioned watch grease composition from the viewpoint of corrosion prevention.

[0099] The timepiece according to the embodiment is obtained by applying the above-described timepiece grease composition to the sliding parts.

[0100] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. [Examples] [Components Used in the Preparation of Watch Grease Compositions] <Base Oil> Base oil (1): A paraffinic hydrocarbon oil, specifically a 1-decene trimer, was used. This 1-decene trimer had a kinematic viscosity at 100°C in the range of 2 cSt to 100 cSt and contained 30 carbon atoms. Base oil (2): An ester oil, specifically a polyol ester oil, was used. This polyol ester oil was a neopentyl glycol-caprylic / capric acid mixed ester. Base oil (3): An ether oil, specifically an alkyl-substituted diphenyl ether (manufactured by Matsumura Oil Research Institute, Inc., product name: Moresco Hi-Lube LB32), was used. Base oil (4): A vegetable oil, specifically a coconut oil (kinematic viscosity at 40°C (JIS K 2283) 27.55 cSt, manufactured by Kaneda Co., Ltd.). Base oil (5): A vegetable oil derivative, specifically a hydroisomerization product of a hydrogenation product of an addition reaction product of an alkene (C=16, 18, linear and branched) (limited to those having one double bond and located at position 1)) (CAS number: 2241366-04-9) (trade name: SynNova 4, manufactured by Novvi LLC, kinematic viscosity at 40°C (JIS K 2283) 19 cSt) was used. Base oil (6): A vegetable oil derivative, specifically, oligomerization products of 1-tetradecene and 1-dodecene, hydrogenated, C24-84 fraction (CAS number: 883233-93-0) was used.

[0101] <Greases> Grease (1-1): A base grease (1-1) containing base oil (1) (85% by mass) and lithium 12-hydroxystearate soap (15% by mass) was prepared. Next, base oil (1) was further added to the base grease and mixed to obtain a lithium soap grease. The base grease was used in an amount of 10 parts by mass per 90 parts by mass of base oil (1). All of the watch grease compositions using grease (1-1), described below, had a viscosity of 1500 mPa·s at 25°C and were liquid. Grease (1-2): A base grease (1-2) containing base oil (1) (85% by mass) and lithium 12-hydroxystearate soap (15% by mass) was prepared. Next, base oil (1) was further added to the base grease and mixed to obtain a lithium soap grease. The base grease was used in an amount of 20 parts by mass per 80 parts by mass of base oil (1). All watch grease compositions using grease (1-2) described below had a worked penetration of 440 as measured in accordance with JIS K 2220 7 and were in a paste state. Grease (1-3): A base grease (1-3) containing base oil (1) (85% by mass) and lithium 12-hydroxystearate soap (15% by mass) was prepared. Next, base oil (1) was further added to the base grease and mixed to obtain a lithium soap grease. The amount of base grease used was 165 parts by mass per 30 parts by mass of base oil (1). All watch grease compositions using grease (1-3) described below had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7 and were in a semi-solid state. Grease (1-4): A base grease (1-4) containing base oil (1) (85% by mass) and diurea compound (U) (15% by mass) represented by the following formula was prepared. Next, base oil (1) was further added to the above base grease and mixed to obtain a urea grease. Here, the amount of the above base grease was 10 parts by mass per 90 parts by mass of base oil (1) added. Note that all of the watch grease compositions using grease (1-4) described below had a viscosity of 1500 mPa s at 25°C and were liquid.

[0102]

[0103] Grease (1-5): A base grease containing base oil (1) (85% by mass) and diurea compound (U) (15% by mass) was prepared. Next, base oil (1) was further added to the base grease and mixed to obtain a urea grease. The base grease was used in an amount of 20 parts by mass per 80 parts by mass of base oil (1). All of the watch grease compositions using grease (1-5) described below had a worked penetration of 440 as measured in accordance with JIS K 2220-7 and were paste-like. Grease (1-6): A base grease containing base oil (1) (85% by mass) and diurea compound (U) (15% by mass) was prepared. Next, base oil (1) was further added to the base grease and mixed to obtain a urea grease. The base grease was used in an amount of 165 parts by mass per 30 parts by mass of base oil (1). The watch grease compositions using grease (1-6) described below all had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7, and were semi-solid.

[0104] Greases (2-1) to (2-6): Greases (2-1) to (2-6) were obtained in the same manner as for greases (1-1) to (1-6), except that base oil (2) was used instead of base oil (1). The watch grease compositions using grease (2-1) and grease (2-4), described below, both had a viscosity of 1500 mPa·s at 25°C and were liquid. The watch grease compositions using grease (2-2) and grease (2-5), described below, both had a worked penetration of 440 as measured in accordance with JIS K 2220 7 and were paste-like. The watch grease compositions using grease (2-3) and grease (2-6), described below, both had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7 and were semi-solid.

[0105] ​Greases (3-1) to (3-6): Greases (3-1) to (3-6) were obtained in the same manner as for greases (1-1) to (1-6), except that base oil (3) was used instead of base oil (1). The watch grease compositions using grease (3-1) and grease (3-4), described below, both had a viscosity of 1500 mPa·s at 25°C and were liquid. The watch grease compositions using grease (3-2) and grease (3-5), described below, both had a worked penetration of 440 as measured in accordance with JIS K 2220 7 and were paste-like. The watch grease compositions using grease (3-3) and grease (3-6), described below, both had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7 and were semi-solid.

[0106] Greases (4-1) to (4-6): Greases (4-1) to (4-6) were obtained in the same manner as for greases (1-1) to (1-6), except that base oil (4) was used instead of base oil (1). The watch grease compositions using grease (4-1) and grease (4-4), described below, both had a viscosity of 1500 mPa·s at 25°C and were liquid. The watch grease compositions using grease (4-2) and grease (4-5), described below, both had a worked penetration of 440 as measured in accordance with JIS K 2220 7 and were paste-like. The watch grease compositions using grease (4-3) and grease (4-6), described below, both had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7 and were semi-solid.

[0107] Greases (5-1) to (5-6): Greases (5-1) to (5-6) were obtained in the same manner as for greases (1-1) to (1-6), except that base oil (5) was used instead of base oil (1). The watch grease compositions using grease (5-1) and grease (5-4), described below, both had a viscosity of 1500 mPa·s at 25°C and were liquid. The watch grease compositions using grease (5-2) and grease (5-5), described below, both had a worked penetration of 440 as measured in accordance with JIS K 2220 7 and were paste-like. The watch grease compositions using grease (5-3) and grease (5-6), described below, both had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7 and were semi-solid.

[0108] Greases (6-1) to (6-6): Greases (6-1) to (6-6) were obtained in the same manner as for greases (1-1) to (1-6), except that base oil (6) was used instead of base oil (1). The watch grease compositions using grease (6-1) and grease (6-4), described below, both had a viscosity of 1500 mPa·s at 25°C and were liquid. The watch grease compositions using grease (6-2) and grease (6-5), described below, both had a worked penetration of 440 as measured in accordance with JIS K 2220 7 and were paste-like. The watch grease compositions using grease (6-3) and grease (6-6), described below, both had a worked penetration of 27.9 as measured in accordance with JIS K 2220 7 and were semi-solid.

[0109] <Neutral phosphite> Neutral phosphite (1): 4,4′-butylidenebis(3-methyl-6-t-butylphenylditridecyl phosphite) (in the above formula (b1), R b11 ~R b14 = tridecyl group, R b15 , R b17 = methyl group, R b16 , R b18 = t-butyl group, R b191 = hydrogen atom, R b192 = n-propyl group) Neutral phosphite esters (2) to (7): In the above formula (b1), Rb11 ~R b14 , R b15 , R b17 , R b16 , R b18 , R b191 , R b192 However, neutral phosphites (2) to (7) shown in Table 1-1 were used.

[0110]

[0111] <Pentavalent phosphate ester> Pentavalent phosphate ester mixture (1): R in the above formula (b2) b21 is an alkyl group having 12 carbon atoms (C 12 H 25 -), a pentavalent phosphate ester (B212) in which R in the above formula (b2) b21 is an alkyl group having 14 carbon atoms (C 14 H 29 -), a pentavalent phosphate ester (B214) in which R in the above formula (b2) b21 is an alkyl group having 16 carbon atoms (C 16 H 33 -), and a pentavalent phosphate ester (B216) in which R b21 is an alkyl group having 18 carbon atoms (C 18 H 37 A mixture of pentavalent phosphate esters (B212) and (B218) was used. This mixture contained 70% by mass of pentavalent phosphate ester (B212), 10% by mass of pentavalent phosphate ester (B214), 10% by mass of pentavalent phosphate ester (B216), and 10% by mass of pentavalent phosphate ester (B218), where the total amount of the four pentavalent phosphate esters was taken as 100% by mass. Pentavalent phosphate ester mixture (2): R in the above formula (b2) b21 is an alkyl group having 13 carbon atoms (C 13 H 27 -), and a pentavalent phosphate ester (B213) in which R b21 is an alkyl group having 18 carbon atoms (C 18 H 37 ​A mixture of the pentavalent phosphate ester (B213) and the pentavalent phosphate ester (B218) was used. This mixture contained 40% by mass of the pentavalent phosphate ester (B213) and 60% by mass of the pentavalent phosphate ester (B218), where the total amount of the two pentavalent phosphate esters was taken as 100% by mass.

[0112] <Viscosity index improvers> Viscosity index improver (1): A cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., trade name LUCANT (registered trademark) HC-600) was used. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Viscosity index improver (2): A cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., trade name LUCANT HC-2000) was used. This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C. Viscosity index improver (3): A viscosity index improver containing polymethacrylate and mineral oil as main components (manufactured by Sanyo Chemical Industries, Ltd., trade name Aclub 806T) was used.

[0113] <Antioxidants> Diphenylamine derivative (1): Irganox (registered trademark) L57, manufactured by Ciba Specialty Chemicals Co., Ltd. Diphenylamine derivatives (2) to (5): In the above formula (c1), R c11 ~R c12 Diphenylamine derivatives (2) to (5) in which p and q are groups shown in Table 1-2 were used.

[0114]

[0115] Hindered amine compound (1): bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (in the above formula (c2), R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group) Hindered amine compounds (2) to (7): In the above formula (c2), R c21 , R c22 , R c23 The hindered amine compounds (2) to (7) having the groups shown in Table 1-3 were used.

[0116] ​​

[0117] 2,6-di-t-butylphenol derivative (1): octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (CAS 125643-61-0, trade name: Irganox (registered trademark) L135, manufactured by BASF Japan Ltd.)

[0118] <Metal Deactivator> Metal Deactivator (1): Benzotriazole

[0119] Example 1-1-1 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (1) were added to grease (1-1) to obtain a watch grease composition (1-1-1). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0120] Examples 1-1-2 to 1-1-7 Watch grease compositions (1-1-2) to (1-1-7) were prepared in the same manner as in Example 1-1-1, except that neutral phosphite esters (2) to (7) were used instead of the neutral phosphite ester (1).

[0121] Example 1-1-8 A watch grease composition (1-1-8) was prepared in the same manner as in Example 1-1-1, except that the neutral phosphite ester (1) was contained in an amount of 0.1 mass % and the mixture of pentavalent phosphate esters (1) was contained in an amount of 0.1 mass %.

[0122] Example 1-1-9 A watch grease composition (1-1-9) was prepared in the same manner as in Example 1-1-1, except that the neutral phosphite ester (1) was contained in an amount of 20 mass % and the mixture of pentavalent phosphate esters (1) was contained in an amount of 20 mass %.

[0123] Examples 1-1-10 to 1-1-14 Watch grease compositions (1-1-10) to (1-1-14) were prepared in the same manner as in Example 1-1-1, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0124] Example 1-1-15 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (2) were added to grease (1-1) to obtain a watch grease composition (1-1-15). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (2) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0125] Examples 1-1-16 to 1-1-21 Watch grease compositions (1-1-16) to (1-1-21) were prepared in the same manner as in Example 1-1-15, except that neutral phosphite esters (2) to (7) were used instead of neutral phosphite ester (1).

[0126] Example 1-1-22 A watch grease composition (1-1-22) was prepared in the same manner as in Example 1-1-15, except that the neutral phosphite ester (1) was contained in an amount of 0.1 mass % and the mixture of pentavalent phosphate esters (2) was contained in an amount of 0.1 mass %.

[0127] Example 1-1-23 A watch grease composition (1-1-23) was prepared in the same manner as in Example 1-1-15, except that the neutral phosphite ester (1) was contained in an amount of 20 mass % and the mixture of pentavalent phosphate esters (2) was contained in an amount of 20 mass %.

[0128] Examples 1-1-24 to 1-1-28 Watch grease compositions (1-1-24) to (1-1-28) were prepared in the same manner as in Example 1-1-15, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0129] Example 1-2-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), and a viscosity index improver (1) were added to a grease (1-1) to obtain a watch grease composition (1-2-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), and the viscosity index improver (1) were contained in amounts of 5% by mass, 10% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0130] Examples 1-2-2 to 1-2-3 Watch grease compositions (1-2-2) to (1-2-3) were prepared in the same manner as in Example 1-2-1, except that viscosity index improvers (2) to (3) were used instead of viscosity index improver (1).

[0131] Example 1-2-4 A watch grease composition (1-2-4) was prepared in the same manner as in Example 1-2-1, except that the neutral phosphite ester (1) was contained in an amount of 0.1 mass %, the mixture of pentavalent phosphate esters (1) was contained in an amount of 0.1 mass %, and the viscosity index improver (1) was contained in an amount of 0.1 mass %.

[0132] Example 1-2-5 A watch grease composition (1-2-5) was prepared in the same manner as in Example 1-2-1, except that the neutral phosphite ester (1) was contained in an amount of 20 mass %, the mixture of pentavalent phosphate esters (1) was contained in an amount of 20 mass %, and the viscosity index improver (1) was contained in an amount of 50 mass %.

[0133] Examples 1-2-6 to 1-2-10 Grease compositions for watches (1-2-6) to (1-2-10) were prepared in the same manner as in Example 1-2-1, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0134] Example 1-2-11 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), and a viscosity index improver (1) were added to grease (1-1) to obtain a watch grease composition (1-2-11). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (2), and the viscosity index improver (1) were contained in amounts of 5% by mass, 10% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0135] Examples 1-2-12 to 1-2-13 Watch grease compositions (1-2-12) to (1-2-13) were prepared in the same manner as in Example 1-2-11, except that viscosity index improvers (2) to (3) were used instead of viscosity index improver (1).

[0136] Example 1-2-14 A watch grease composition (1-2-14) was prepared in the same manner as in Example 1-2-11, except that the neutral phosphite ester (1) was contained in an amount of 0.1 mass %, the mixture of pentavalent phosphate esters (2) was contained in an amount of 0.1 mass %, and the viscosity index improver (1) was contained in an amount of 0.1 mass %.

[0137] Example 1-2-15 A watch grease composition (1-2-15) was prepared in the same manner as in Example 1-2-11, except that the neutral phosphite ester (1) was contained in an amount of 20 mass%, the mixture of pentavalent phosphate esters (2) was contained in an amount of 20 mass%, and the viscosity index improver (1) was contained in an amount of 50 mass%.

[0138] Examples 1-2-16 to 1-2-20 Grease compositions for watches (1-2-16) to (1-2-20) were prepared in the same manner as in Example 1-2-11, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0139] Example 1-3-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), and a diphenylamine derivative (1) were added to a grease (1-1) to obtain a watch grease composition (1-3-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), and the diphenylamine derivative (1) were contained in amounts of 5% by mass, 10% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0140] Examples 1-3-2 to 1-3-5 Watch grease compositions (1-3-2) to (1-3-5) were prepared in the same manner as in Example 1-3-1, except that diphenylamine derivatives (2) to (5) were used instead of diphenylamine derivative (1).

[0141] Example 1-3-6 A watch grease composition (1-3-6) was prepared in the same manner as in Example 1-3-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass %, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass %, and the diphenylamine derivative (1) was contained in an amount of 0.01 mass %.

[0142] Example 1-3-7 A watch grease composition (1-3-7) was prepared in the same manner as in Example 1-3-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass %, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass %, and the diphenylamine derivative (1) was contained in an amount of 3 mass %.

[0143] Examples 1-3-8 to 1-3-12 Watch grease compositions (1-3-8) to (1-3-12) were prepared in the same manner as in Example 1-3-1, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0144] Example 1-3-13 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), and a diphenylamine derivative (1) were added to grease (1-1) to obtain a watch grease composition (1-3-13). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (2), and the diphenylamine derivative (1) were contained in amounts of 5% by mass, 10% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0145] Example 1-3-14 A watch grease composition (1-3-14) was prepared in the same manner as in Example 1-3-13, except that the neutral phosphite ester (1) was contained in an amount of 5 mass %, the mixture of pentavalent phosphate esters (2) was contained in an amount of 10 mass %, and the diphenylamine derivative (1) was contained in an amount of 0.01 mass %.

[0146] Example 1-3-15 A watch grease composition (1-3-15) was prepared in the same manner as in Example 1-3-13, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the mixture of pentavalent phosphate esters (2) was contained in an amount of 10 mass%, and the diphenylamine derivative (1) was contained in an amount of 3 mass%.

[0147] Examples 1-3-16 to 1-3-20 Watch grease compositions (1-3-16) to (1-3-20) were prepared in the same manner as in Example 1-3-13, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0148] Example 1-3-21 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-3-21). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), and the hindered amine compound (1) were contained in amounts of 5% by mass, 10% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0149] Examples 1-3-22 to 1-3-27 Watch grease compositions (1-3-22) to (1-3-27) were prepared in the same manner as in Example 1-3-21, except that hindered amine compounds (2) to (7) were used instead of the hindered amine compound (1).

[0150] Example 1-3-28 A watch grease composition (1-3-28) was prepared in the same manner as in Example 1-3-21, except that the neutral phosphite ester (1) was contained in an amount of 5% by mass, the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass, and the hindered amine compound (1) was contained in an amount of 0.01% by mass.

[0151] Example 1-3-29 A watch grease composition (1-3-29) was prepared in the same manner as in Example 1-3-21, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the mixture of pentavalent phosphate esters (1) was contained in an amount of 10 mass%, and the hindered amine compound (1) was contained in an amount of 3 mass%.

[0152] Examples 1-3-30 to 1-3-34 Watch grease compositions (1-3-30) to (1-3-34) were prepared in the same manner as in Example 1-3-21, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0153] Example 1-3-35 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-3-35). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (2), and the hindered amine compound (1) were contained in amounts of 5% by mass, 10% by mass, and 0.5% by mass, respectively, based on 100% by mass of the watch grease composition.

[0154] Example 1-3-36 A watch grease composition (1-3-36) was prepared in the same manner as in Example 1-3-35, except that the neutral phosphite ester (1) was contained in an amount of 5% by mass, the mixture of pentavalent phosphate esters (2) was contained in an amount of 10% by mass, and the hindered amine compound (1) was contained in an amount of 0.01% by mass.

[0155] Example 1-3-37 A watch grease composition (1-3-37) was prepared in the same manner as in Example 1-3-35, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the mixture of pentavalent phosphate esters (2) was contained in an amount of 10 mass%, and the hindered amine compound (1) was contained in an amount of 3 mass%.

[0156] Examples 1-3-38 to 1-3-42 Watch grease compositions (1-3-38) to (1-3-42) were prepared in the same manner as in Example 1-3-35, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0157] Example 1-3-43 A watch grease composition (1-3-43) was obtained by adding a neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a diphenylamine derivative (1), and a hindered amine compound (1) to a grease (1-1). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0158] Example 1-3-44 A watch grease composition (1-3-44) was prepared in the same manner as in Example 1-3-43, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass%, the diphenylamine derivative (1) was contained in an amount of 0.01 mass%, and the hindered amine compound (1) was contained in an amount of 0.01 mass%.

[0159] Example 1-3-45 A watch grease composition (1-3-45) was prepared in the same manner as in Example 1-3-43, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass%, the diphenylamine derivative (1) was contained in an amount of 1.5 mass%, and the hindered amine compound (1) was contained in an amount of 1.5 mass%.

[0160] Examples 1-3-46 to 1-3-50 Watch grease compositions (1-3-46) to (1-3-50) were prepared in the same manner as in Example 1-3-43, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0161] Example 1-3-51 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-3-51). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (2), the diphenylamine derivative (1), and the hindered amine compound (1) were contained in amounts of 5% by mass, 10% by mass, 0.5% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0162] Examples 1-3-52 to 1-3-56 Watch grease compositions (1-3-52) to (1-3-56) were prepared in the same manner as in Example 1-3-51, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0163] Example 1-4-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to a grease (1-1) to obtain a watch grease composition (1-4-1). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0164] Example 1-4-2 A watch grease composition (1-4-2) was prepared in the same manner as in Example 1-4-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass %, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass %, the viscosity index improver (1) was contained in an amount of 0.1 mass %, the diphenylamine derivative (1) was contained in an amount of 0.01 mass %, and the hindered amine compound (1) was contained in an amount of 0.01 mass %.

[0165] Example 1-4-3 A watch grease composition (1-4-3) was prepared in the same manner as in Example 1-4-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the pentavalent phosphate ester mixture (1) in an amount of 10 mass%, the viscosity index improver (1) in an amount of 50 mass%, the diphenylamine derivative (1) in an amount of 1.5 mass%, and the hindered amine compound (1) in an amount of 1.5 mass%.

[0166] Example 1-4-4 A watch grease composition (1-4-4) was prepared in the same manner as in Example 1-4-1, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0167] Examples 1-4-5 to 1-4-6 Watch grease compositions (1-4-5) to (1-4-6) were prepared in the same manner as in Examples 1-4-2 to 1-4-3, except that viscosity index improver (2) was used instead of viscosity index improver (1).

[0168] Examples 1-4-7 to 1-4-11 Grease compositions for watches (1-4-7) to (1-4-11) were prepared in the same manner as in Example 1-4-1, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0169] Examples 1-4-12 to 1-4-16 Watch grease compositions (1-4-12) to (1-4-16) were prepared in the same manner as in Example 1-4-4, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0170] Example 1-4-17 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-4-17). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (2), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0171] Example 1-4-18 A watch grease composition (1-4-18) was prepared in the same manner as in Example 1-4-17, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the mixture of pentavalent phosphate esters (2) was contained in an amount of 10 mass%, the viscosity index improver (1) was contained in an amount of 0.1 mass%, the diphenylamine derivative (1) was contained in an amount of 0.01 mass%, and the hindered amine compound (1) was contained in an amount of 0.01 mass%.

[0172] Example 1-4-19 A watch grease composition (1-4-19) was prepared in the same manner as in Example 1-4-17, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the pentavalent phosphate ester mixture (2) was contained in an amount of 10 mass%, the viscosity index improver (1) was contained in an amount of 50 mass%, the diphenylamine derivative (1) was contained in an amount of 1.5 mass%, and the hindered amine compound (1) was contained in an amount of 1.5 mass%.

[0173] Example 1-4-20 A watch grease composition (1-4-20) was prepared in the same manner as in Example 1-4-17, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0174] Examples 1-4-21 to 1-4-22 Watch grease compositions (1-4-21) to (1-4-22) were prepared in the same manner as in Examples 1-4-18 to 1-4-19, except that viscosity index improver (2) was used instead of viscosity index improver (1).

[0175] Examples 1-4-23 to 1-4-27 Watch grease compositions (1-4-23) to (1-4-27) were prepared in the same manner as in Example 1-4-17, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0176] Examples 1-4-28 to 1-4-32 Watch grease compositions (1-4-28) to (1-4-32) were prepared in the same manner as in Example 1-4-20, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0177] Example 1-5-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), and a viscosity index improver (1) were added to a grease (1-1) to obtain a watch grease composition (1-5-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), the metal deactivator (1), and the viscosity index improver (1) were contained in amounts of 5% by mass, 10% by mass, 0.05% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0178] Example 1-5-2 A watch grease composition (1-5-2) was prepared in the same manner as in Example 1-5-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass %, the mixture of pentavalent phosphate esters (1) was contained in an amount of 10 mass %, the metal deactivator (1) was contained in an amount of 0.01 mass %, and the viscosity index improver (1) was contained in an amount of 5 mass %.

[0179] Example 1-5-3 A watch grease composition (1-5-3) was prepared in the same manner as in Example 1-5-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass %, the mixture of pentavalent phosphate esters (1) was contained in an amount of 10 mass %, the metal deactivator (1) was contained in an amount of 3 mass %, and the viscosity index improver (1) was contained in an amount of 5 mass %.

[0180] Examples 1-5-4 to 1-5-8 Watch grease compositions (1-5-4) to (1-5-8) were prepared in the same manner as in Example 1-5-1, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0181] Example 1-5-9 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), and a viscosity index improver (2) were added to grease (1-1) to obtain a watch grease composition (1-5-9). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), the metal deactivator (1), and the viscosity index improver (2) were contained in amounts of 5% by mass, 10% by mass, 0.05% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0182] Example 1-5-10 A watch grease composition (1-5-10) was prepared in the same manner as in Example 1-5-9, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the mixture of pentavalent phosphate esters (1) was contained in an amount of 10 mass%, the metal deactivator (1) was contained in an amount of 0.01 mass%, and the viscosity index improver (2) was contained in an amount of 5 mass%.

[0183] Example 1-5-11 A watch grease composition (1-5-11) was prepared in the same manner as in Example 1-5-9, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the mixture of pentavalent phosphate esters (1) was contained in an amount of 10 mass%, the metal deactivator (1) was contained in an amount of 3 mass%, and the viscosity index improver (2) was contained in an amount of 5 mass%.

[0184] Examples 1-5-12 to 1-5-16 Watch grease compositions (1-5-12) to (1-5-16) were prepared in the same manner as in Example 1-5-9, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0185] Example 1-5-17 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a metal deactivator (1), and a viscosity index improver (1) were added to grease (1-1) to obtain a watch grease composition (1-5-17). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (2), the metal deactivator (1), and the viscosity index improver (1) were contained in amounts of 5% by mass, 10% by mass, 0.05% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0186] Examples 1-5-18 to 1-5-22 Watch grease compositions (1-5-18) to (1-5-22) were prepared in the same manner as in Example 1-5-17, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0187] Example 1-5-23 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a metal deactivator (1), and a viscosity index improver (2) were added to grease (1-1) to obtain a watch grease composition (1-5-23). ​​These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (2), 0.05% by mass of the metal deactivator (1), and 5% by mass of the viscosity index improver (2) per 100% by mass of the watch grease composition.

[0188] Examples 1-5-24 to 1-5-28 Watch grease compositions (1-5-24) to (1-5-28) were prepared in the same manner as in Example 1-5-23, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0189] Example 1-5-29 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-5-29). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 0.05% by mass of the metal deactivator (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0190] Examples 1-5-30 to 1-5-34 Watch grease compositions (1-5-30) to (1-5-34) were prepared in the same manner as in Example 1-5-29, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0191] Example 1-5-35 A watch grease composition (1-5-35) was obtained by adding a neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a metal deactivator (1), a diphenylamine derivative (1), and a hindered amine compound (1) to a grease (1-1). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (2), 0.05% by mass of the metal deactivator (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0192] Examples 1-5-36 to 1-5-40 Watch grease compositions (1-5-36) to (1-5-40) were prepared in the same manner as in Example 1-5-35, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0193] Example 1-5-41 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-5-41). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 0.05% by mass of the metal deactivator (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0194] Examples 1-5-42 to 1-5-46 Watch grease compositions (1-5-42) to (1-5-46) were prepared in the same manner as in Example 1-5-41, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0195] Example 1-5-47 A watch grease composition (1-5-47) was obtained by adding a neutral phosphite ester (1), a pentavalent phosphate ester mixture (1), a metal deactivator (1), a viscosity index improver (2), a diphenylamine derivative (1), and a hindered amine compound (1) to a grease (1-1). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the pentavalent phosphate ester mixture (1), 0.05% by mass of the metal deactivator (1), 5% by mass of the viscosity index improver (2), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0196] Examples 1-5-48 to 1-5-52 Watch grease compositions (1-5-48) to (1-5-52) were prepared in the same manner as in Example 1-5-47, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0197] Example 1-5-53 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a metal deactivator (1), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (1-1) to obtain a watch grease composition (1-5-53). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (2), 0.05% by mass of the metal deactivator (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0198] Examples 1-5-54 to 1-5-58 Watch grease compositions (1-5-54) to (1-5-58) were prepared in the same manner as in Example 1-5-53, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0199] Example 1-5-59: A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a metal deactivator (1), a viscosity index improver (2), a diphenylamine derivative (1), and a hindered amine compound (1) were added to a grease (1-1) to obtain a watch grease composition (1-5-59). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (2), 0.05% by mass of the metal deactivator (1), 5% by mass of the viscosity index improver (2), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0200] Examples 1-5-60 to 1-5-64 Watch grease compositions (1-5-60) to (1-5-64) were prepared in the same manner as in Example 1-5-59, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0201] Example 1-6-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a hindered amine compound (1), and a 2,6-di-t-butylphenol derivative (1) were added to a grease (1-1) to obtain a watch grease composition (1-6-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), the hindered amine compound (1), and the 2,6-di-t-butylphenol derivative (1) were contained in amounts of 5% by mass, 10% by mass, 0.5% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0202] Example 1-6-2 A watch grease composition (1-6-2) was prepared in the same manner as in Example 1-6-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass%, the hindered amine compound (1) was contained in an amount of 0.01 mass%, and the 2,6-di-t-butylphenol derivative (1) was contained in an amount of 0.01 mass%.

[0203] Example 1-6-3 A watch grease composition (1-6-3) was prepared in the same manner as in Example 1-6-1, except that the neutral phosphite ester (1) was contained in an amount of 5 mass%, the pentavalent phosphate ester mixture (1) was contained in an amount of 10 mass%, the hindered amine compound (1) was contained in an amount of 1.5 mass%, and the 2,6-di-t-butylphenol derivative (1) was contained in an amount of 1.5 mass%.

[0204] Examples 1-6-4 to 1-6-8 Watch grease compositions (1-6-4) to (1-6-8) were prepared in the same manner as in Example 1-6-1, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0205] Example 1-6-9: A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a hindered amine compound (1), and a 2,6-di-t-butylphenol derivative (1) were added to a grease (1-1) to obtain a watch grease composition (1-6-9). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (2), the hindered amine compound (1), and the 2,6-di-t-butylphenol derivative (1) were contained in amounts of 5% by mass, 10% by mass, 0.5% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0206] Examples 1-6-10 to 1-6-14 Watch grease compositions (1-6-10) to (1-6-14) were prepared in the same manner as in Example 1-6-9, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0207] Example 1-6-15 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a viscosity index improver (1), a hindered amine compound (1), and a 2,6-di-t-butylphenol derivative (1) were added to grease (1-1) to obtain a watch grease composition (1-6-15). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the hindered amine compound (1), and 0.5% by mass of the 2,6-di-t-butylphenol derivative (1) per 100% by mass of the watch grease composition.

[0208] Examples 1-6-16 to 1-6-20 Watch grease compositions (1-6-16) to (1-6-20) were prepared in the same manner as in Example 1-6-15, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0209] Example 1-6-21 A watch grease composition (1-6-21) was prepared in the same manner as in Example 1-6-15, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0210] Example 1-6-22 A watch grease composition (1-6-22) was prepared in the same manner as in Example 1-6-15, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0211] Example 1-6-23 A watch grease composition (1-6-23) was prepared in the same manner as in Example 1-6-22, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0212] Example 1-6-24 A watch grease composition (1-6-24) was obtained by adding a neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), a viscosity index improver (1), a hindered amine compound (1), and a 2,6-di-t-butylphenol derivative (1) to a grease (1-1). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 0.05% by mass of the metal deactivator (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the hindered amine compound (1), and 0.5% by mass of the 2,6-di-t-butylphenol derivative (1) per 100% by mass of the watch grease composition.

[0213] Examples 1-6-25 to 1-6-29 Watch grease compositions (1-6-25) to (1-6-29) were prepared in the same manner as in Example 1-6-24, except that greases (1-2) to (1-6) were used instead of grease (1-1).

[0214] Example 1-6-30 A watch grease composition (1-6-30) was prepared in the same manner as in Example 1-6-24, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0215] Example 1-6-31 A watch grease composition (1-6-31) was prepared in the same manner as in Example 1-6-24, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0216] Example 1-6-32 A watch grease composition (1-6-32) was prepared in the same manner as in Example 1-6-31, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0217] Example 2-1-1 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (1) were added to a grease (2-1) to obtain a watch grease composition (2-1-1). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0218] Examples 2-1-2 to 2-1-6 Grease compositions for watches (2-1-2) to (2-1-6) were prepared in the same manner as in Example 2-1-1, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0219] Example 2-1-7 A watch grease composition (2-1-7) was prepared in the same manner as in Example 2-1-1, except that the mixture of pentavalent phosphate esters (2) was used instead of the mixture of pentavalent phosphate esters (1).

[0220] Examples 2-1-8 to 2-1-12 Watch grease compositions (2-1-8) to (2-1-12) were prepared in the same manner as in Example 2-1-7, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0221] [Example 2-2-1] A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), and a viscosity index improver (1) were added to a grease (2-1) to obtain a watch grease composition (2-2-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), and the viscosity index improver (1) were contained in amounts of 5% by mass, 10% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0222] Example 2-2-2 A watch grease composition (2-2-2) was prepared in the same manner as in Example 2-2-1, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0223] Examples 2-2-3 to 2-2-7 Grease compositions for watches (2-2-3) to (2-2-7) were prepared in the same manner as in Example 2-2-1, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0224] Example 2-2-8 A watch grease composition (2-2-8) was prepared in the same manner as in Example 2-2-1, except that the mixture of pentavalent phosphate esters (2) was used instead of the mixture of pentavalent phosphate esters (1).

[0225] Example 2-2-9 A watch grease composition (2-2-9) was prepared in the same manner as in Example 2-2-8, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0226] Examples 2-2-10 to 2-2-14 Grease compositions for watches (2-2-10) to (2-2-14) were prepared in the same manner as in Example 2-2-8, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0227] Example 2-3-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), and a diphenylamine derivative (1) were added to a grease (2-1) to obtain a watch grease composition (2-3-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), and the diphenylamine derivative (1) were contained in amounts of 5% by mass, 10% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0228] Examples 2-3-2 to 2-3-6 Grease compositions for watches (2-3-2) to (2-3-6) were prepared in the same manner as in Example 2-3-1, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0229] Example 2-3-7 A watch grease composition (2-3-7) was prepared in the same manner as in Example 2-3-1, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0230] Examples 2-3-8 to 2-3-12 Watch grease compositions (2-3-8) to (2-3-12) were prepared in the same manner as in Example 2-3-7, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0231] Example 2-3-13 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), and a hindered amine compound (1) were added to grease (2-1) to obtain a watch grease composition (2-3-13). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), and the hindered amine compound (1) were contained in amounts of 5% by mass, 10% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0232] Examples 2-3-14 to 2-3-18 Grease compositions for watches (2-3-14) to (2-3-18) were prepared in the same manner as in Example 2-3-13, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0233] Example 2-3-19 A watch grease composition (2-3-19) was prepared in the same manner as in Example 2-3-13, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0234] Examples 2-3-20 to 2-3-24 Watch grease compositions (2-3-20) to (2-3-24) were prepared in the same manner as in Example 2-3-19, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0235] Example 2-3-25 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (2-1) to obtain a watch grease composition (2-3-25). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), the diphenylamine derivative (1), and the hindered amine compound (1) were contained in amounts of 5% by mass, 10% by mass, 0.5% by mass, and 0.5% by mass, respectively, per 100% by mass of the watch grease composition.

[0236] Examples 2-3-26 to 2-3-30 Watch grease compositions (2-3-26) to (2-3-30) were prepared in the same manner as in Example 2-3-25, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0237] Example 2-3-31 A watch grease composition (2-3-31) was prepared in the same manner as in Example 2-3-25, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0238] Examples 2-3-32 to 2-3-36 Watch grease compositions (2-3-32) to (2-3-36) were prepared in the same manner as in Example 2-3-31, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0239] Example 2-4-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to a grease (2-1) to obtain a watch grease composition (2-4-1). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0240] Example 2-4-2 A watch grease composition (2-4-2) was prepared in the same manner as in Example 2-4-1, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0241] Examples 2-4-3 to 2-4-7 Watch grease compositions (2-4-3) to (2-4-7) were prepared in the same manner as in Example 2-4-1, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0242] Examples 2-4-8 to 2-4-12 Watch grease compositions (2-4-8) to (2-4-12) were prepared in the same manner as in Example 2-4-2, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0243] Example 2-4-13 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (2), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (2-1) to obtain a watch grease composition (2-4-13). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (2), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0244] Example 2-4-14 A watch grease composition (2-4-14) was prepared in the same manner as in Example 2-4-13, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0245] Examples 2-4-15 to 2-4-19 Watch grease compositions (2-4-15) to (2-4-19) were prepared in the same manner as in Example 2-4-13, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0246] Examples 2-4-20 to 2-4-24 Watch grease compositions (2-4-20) to (2-4-24) were prepared in the same manner as in Example 2-4-14, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0247] Example 2-5-1 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), and a viscosity index improver (1) were added to a grease (2-1) to obtain a watch grease composition (2-5-1). These components were added so that the neutral phosphite ester (1), the mixture of pentavalent phosphate esters (1), the metal deactivator (1), and the viscosity index improver (1) were contained in amounts of 5% by mass, 10% by mass, 0.05% by mass, and 5% by mass, respectively, per 100% by mass of the watch grease composition.

[0248] Examples 2-5-2 to 2-5-6 Watch grease compositions (2-5-2) to (2-5-6) were prepared in the same manner as in Example 2-5-1, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0249] Example 2-5-7 A watch grease composition (2-5-7) was prepared in the same manner as in Example 2-5-1, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0250] Example 2-5-8 A watch grease composition (2-5-8) was prepared in the same manner as in Example 2-5-1, except that the mixture of pentavalent phosphate esters (2) was used instead of the mixture of pentavalent phosphate esters (1).

[0251] Example 2-5-9 A watch grease composition (2-5-9) was prepared in the same manner as in Example 2-5-8, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0252] Example 2-5-10 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (2-1) to obtain a watch grease composition (2-5-10). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 0.05% by mass of the metal deactivator (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0253] Examples 2-5-11 to 2-5-15 Grease compositions for watches (2-5-11) to (2-5-15) were prepared in the same manner as in Example 2-5-10, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0254] Example 2-5-16 A watch grease composition (2-5-16) was prepared in the same manner as in Example 2-5-10, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0255] Example 2-5-17 A neutral phosphite ester (1), a mixture of pentavalent phosphate esters (1), a metal deactivator (1), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to grease (2-1) to obtain a watch grease composition (2-5-17). These components were added so that the watch grease composition contained 5% by mass of the neutral phosphite ester (1), 10% by mass of the mixture of pentavalent phosphate esters (1), 0.05% by mass of the metal deactivator (1), 5% by mass of the viscosity index improver (1), 0.5% by mass of the diphenylamine derivative (1), and 0.5% by mass of the hindered amine compound (1) per 100% by mass of the watch grease composition.

[0256] Examples 2-5-18 to 2-5-22 Watch grease compositions (2-5-18) to (2-5-22) were prepared in the same manner as in Example 2-5-17, except that greases (2-2) to (2-6) were used instead of grease (2-1).

[0257] Example 2-5-23 A watch grease composition (2-5-23) was prepared in the same manner as in Example 2-5-17, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0258] Example 2-5-24 A watch grease composition (2-5-24) was prepared in the same manner as in Example 2-5-17, except that the pentavalent phosphate ester mixture (2) was used instead of the pentavalent phosphate ester mixture (1).

[0259] Example 2-5-25 A watch grease composition (2-5-25) was prepared in the same manner as in Example 2-5-24, except that the viscosity index improver (2) was used instead of the viscosity index improver (1).

[0260] Example 3-1-1 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (1) were added to grease (3-1) to obtain a watch grease composition (3-1-1). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0261] Examples 3-1-2 to 3-5-25 Watch grease compositions (3-1-2) to (3-5-25) were prepared in the same manner as in Examples 2-1-2 to 2-5-25, except that greases (3-1) to (3-6) were used instead of greases (2-1) to (2-6), respectively.

[0262] Example 4-1-1 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (1) were added to grease (4-1) to obtain a watch grease composition (4-1-1). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0263] Examples 4-1-2 to 4-5-25 Watch grease compositions (4-1-2) to (4-5-25) were prepared in the same manner as in Examples 2-1-2 to 2-5-25, except that greases (4-1) to (4-6) were used instead of greases (2-1) to (2-6), respectively.

[0264] Example 5-1-1 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (1) were added to grease (5-1) to obtain a watch grease composition (5-1-1). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0265] Examples 5-1-2 to 5-5-25 Watch grease compositions (5-1-2) to (5-5-25) were prepared in the same manner as in Examples 2-1-2 to 2-5-25, except that greases (5-1) to (5-6) were used instead of greases (2-1) to (2-6), respectively.

[0266] Example 6-1-1 A neutral phosphite ester (1) and a mixture of pentavalent phosphate esters (1) were added to grease (6-1) to obtain a watch grease composition (6-1-1). These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the mixture of pentavalent phosphate esters (1) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0267] Examples 6-1-2 to 6-5-25 Watch grease compositions (6-1-2) to (6-5-25) were prepared in the same manner as in Examples 2-1-2 to 2-5-25, except that greases (6-1) to (6-6) were used instead of greases (2-1) to (2-6), respectively.

[0268] [Comparative Example 1-1-1] A neutral phosphite ester (1) was added to grease (1-1) to obtain a grease composition for a watch. These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass per 100% by mass of the grease composition for a watch.

[0269] Comparative Example 1-1-2: Grease (1-1) was prepared by adding neutral phosphite ester (1), R b21 is an alkyl group having 18 carbon atoms (C 18 H 37 A pentavalent phosphate ester (B218) (-) was added to obtain a watch grease composition. These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass and the pentavalent phosphate ester (B218) was contained in an amount of 10% by mass per 100% by mass of the watch grease composition.

[0270] Comparative Example 1-1-3: Grease (1-1) was prepared by adding neutral phosphite ester (1), R b21 is an alkyl group having 18 carbon atoms (C 18 H 37A pentavalent phosphate ester (B218) (-) and a viscosity index improver (1) were added to obtain a watch grease composition. These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass, the pentavalent phosphate ester (B218) in an amount of 10% by mass, and the viscosity index improver (1) in an amount of 5% by mass, per 100% by mass of the watch grease composition.

[0271] Comparative Example 1-1-4: Grease (1-1) was prepared by adding neutral phosphite ester (1), R b21 is an alkyl group having 18 carbon atoms (C 18 H 37 A pentavalent phosphate ester (B218) (-), a diphenylamine derivative (1), and a hindered amine compound (1) were added to obtain a watch grease composition. These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass, the pentavalent phosphate ester (B218) in an amount of 10% by mass, the diphenylamine derivative (1) in an amount of 0.5% by mass, and the hindered amine compound (1) in an amount of 0.5% by mass, per 100% by mass of the watch grease composition.

[0272] Comparative Example 1-1-5: Grease (1-1) was prepared by adding neutral phosphite ester (1), R b21 is an alkyl group having 18 carbon atoms (C 18 H 37 A pentavalent phosphate ester (B218) (-), a viscosity index improver (1), a diphenylamine derivative (1), and a hindered amine compound (1) were added to obtain a watch grease composition. These components were added so that the neutral phosphite ester (1) was contained in an amount of 5% by mass, the pentavalent phosphate ester (B218) in an amount of 10% by mass, the viscosity index improver (1), the diphenylamine derivative (1) in an amount of 0.5% by mass, and the hindered amine compound (1) in an amount of 0.5% by mass, per 100% by mass of the watch grease composition.

[0273] [Evaluation Method and Evaluation Results] Watches were produced by lubricating the slip mechanism of the sliding part of a watch movement (#2035, manufactured by Citizen Watch Co., Ltd., wheel train part: made of metal (mainly iron or mainly brass)) with the prepared watch grease compositions. These watches were subjected to a 15-year accelerated test of slip torque at room temperature and low temperature. Specifically, the accelerated test at room temperature was conducted at 25°C, with the crown pulled out to set the watch, and this crown was rotated continuously for 3 hours. The accelerated test at low temperature was conducted at -50°C, with the crown pulled out to set the watch, and this crown was rotated continuously for 3 hours. The torque reduction rates due to the accelerated tests at room temperature and low temperature were determined. The results are shown in Tables 5 to 11. A torque reduction rate of 10% or less can be said to provide excellent lubricating performance when applied to the sliding parts of a watch.

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288] ​​​​​​​​​​​​​​​

[0289]

[0290] When the watch grease compositions obtained in the Examples were all kept at 90°C for 1,000 hours, the weight change rate (evaporation rate) of the watch grease composition before and after keeping was 7% by weight or less. Furthermore, when the watch grease compositions obtained in the Examples were all subjected to a copper plate corrosion test (test time: 2 hours, test temperature: 100°C) in accordance with JIS K 2513:2000 to evaluate their copper plate corrosion resistance, the standard copper plate corrosion rating (discoloration number) was 1.

[0291]

[0013] In light of the above, the present invention relates to the following: [1] A composition comprising a base oil selected from paraffinic hydrocarbon oils, ester oils, and ether oils, a thickener, a neutral phosphite ester represented by the following general formula (b1), and a pentavalent phosphate ester represented by the following general formula (b2), wherein the pentavalent phosphate esters are of two or more types, and R in the two or more pentavalent phosphate esters is b21 The number of carbon atoms in each alkyl group represented by the formula (I) is different.

[0292]

[0293] (In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms; R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms; R b191 and R b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R b191 and R b192 The total number of carbon atoms is 1 to 5.

[0294]

[0295] (In formula (b2), R b21 ​​​represents an alkyl group having 4 to 22 carbon atoms, and n represents an integer of 1 or 2.) [2] A composition comprising a base oil selected from vegetable oils and derivatives thereof, a thickener, a neutral phosphite ester represented by the following general formula (b1), and a pentavalent phosphate ester represented by the following general formula (b2), wherein two or more types of pentavalent phosphate esters are included, and R in the two or more pentavalent phosphate esters is b21 The number of carbon atoms in each alkyl group represented by the formula (I) is different.

[0296]

[0297] (In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms; R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms; R b191 and R b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R b191 and R b192 The total number of carbon atoms is 1 to 5.

[0298]

[0299] (In formula (b2), R b21 represents an alkyl group having 4 to 22 carbon atoms, and n represents an integer of 1 or 2. [3] In the above formula (b2), R b21 represents an alkyl group having 12 to 18 carbon atoms. [4] The watch grease composition according to [1] or [2], further comprising a viscosity index improver. [5] The watch grease composition according to [1] or [2], further comprising an antioxidant selected from a diphenylamine derivative represented by the following general formula (c1), a hindered amine compound represented by the following general formula (c2), and a 2,6-di-t-butylphenol derivative represented by the following general formula (c3).

[0300] ​​​

[0301] (In formula (c1), R c11 and R c12 each independently represents a linear or branched 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 are not both 0.

[0302]

[0303] (In formula (c2), R c21 and R c22 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms; R c23 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0304]

[0305] (In formula (c3), R c31 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms.) [6] The watch grease composition according to [1] or [2], further comprising a metal deactivator. [7] A watch having the watch grease composition according to [1] or [2] adhered to a sliding part.​​

Claims

1. A lubricating oil composition comprising a base oil selected from paraffinic hydrocarbon oils, ester oils, and ether oils, a thickener, a neutral phosphite ester represented by the following general formula (b1), and a pentavalent phosphate ester represented by the following general formula (b2), wherein the pentavalent phosphate ester is comprised of two or more types, and R in the two or more pentavalent phosphate esters is b21 The number of carbon atoms in each alkyl group represented by the formula (I) is different. (In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms; R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms; R b191 and R b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R b191 and R b192 The total number of carbon atoms is 1 to 5. (In formula (b2), R b21 represents an alkyl group having 4 to 22 carbon atoms, and n represents an integer of 1 or 2.

2. A lubricating oil composition comprising a base oil selected from vegetable oils and derivatives thereof, a thickener, a neutral phosphite ester represented by the following general formula (b1), and a pentavalent phosphate ester represented by the following general formula (b2), wherein the pentavalent phosphate ester is comprised of two or more types, and R in the two or more pentavalent phosphate esters is b21 The number of carbon atoms in each alkyl group represented by the formula (I) is different. (In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms; R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms; R b191 and R b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms; R b191 and R b192 The total number of carbon atoms is 1 to 5. (In formula (b2), R b21 represents an alkyl group having 4 to 22 carbon atoms, and n represents an integer of 1 or 2.

3. In the above formula (b2), R b21 The grease composition for a watch according to claim 1 or 2, wherein represents an alkyl group having 12 to 18 carbon atoms.

4. The watch grease composition according to claim 1 or 2, further comprising a viscosity index improver.

5. The watch grease composition according to claim 1 or 2, further comprising an antioxidant selected from the group consisting of a diphenylamine derivative represented by the following general formula (c1), a hindered amine compound represented by the following general formula (c2), and a 2,6-di-t-butylphenol derivative represented by the following general formula (c3): (In formula (c1), R c11 and R c12 each independently represents a linear or branched 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 are not both 0. (In formula (c2), R c21 and R c22 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms; R c23 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. (In formula (c3), R c31 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

6. The watch grease composition according to claim 1 or 2, further comprising a metal deactivator.

7. A watch having the watch grease composition according to claim 1 or 2 attached to its sliding parts.

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