Lubricating composition for timepiece and timepiece employing same

Abstract

A lubricating composition for a timepiece according to the present invention comprises: a base oil selected from among paraffinic hydrocarbon oils, ester oils, and ether oils or a base oil selected from among vegetable oils and derivatives thereof; a neutral phosphorous acid ester represented by general formula (b1); and pentavalent phosphoric acid esters represented by general formula (b2). Two or more of the pentavalent phosphoric acid esters are contained and the alkyl groups represented by Rb21 in the two or more pentavalent phosphoric acid esters differ from each other in the number of carbon atoms.

Description

Lubricating composition for watches and watches using the same

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

[0002] Patent Document 1 describes a lubricating oil composition for watches that includes a lubricant component (A) containing at least one base oil (A1) selected from a polyol ester (A-1), a paraffinic hydrocarbon oil (A-2) having 25 or more carbon atoms, and an ether oil (A-3), at least one anti-wear agent (B) selected from a neutral phosphate ester and a neutral phosphite ester, and an antioxidant (C).

[0003] International Publication No. 2014 / 115603

[0004] However, when the lubricating oil composition for watches of Patent Document 1 is applied to the sliding parts of a watch and the watch is operated, there is room for improvement in lubricating performance.

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

[0006] The watch lubricating 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 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 lubricating composition for a watch of the present invention exhibits high lubricating properties when applied to the sliding parts of a watch and used in operation.

[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 Lubricating Composition According to Embodiment 1> The watch lubricating composition according to Embodiment 1 contains a base oil, a neutral phosphite ester, and a pentavalent phosphate ester (a monophosphate ester or a diphosphate ester). Because a specific neutral phosphite ester and two or more specific pentavalent phosphate esters are used in combination, the watch lubricating composition according to Embodiment 1 exhibits high lubricating performance when applied to the sliding parts of a watch and used in operation.

[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. Furthermore, the kinematic viscosity of the paraffinic hydrocarbon oil at 100°C is preferably 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] [Neutral phosphite ester] The watch lubricating 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 lubricating performance of the watch lubricating oil composition. That is, when the above lubricating oil composition is used on sliding parts of a watch, 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 above lubricating oil composition can provide good lubrication even to sliding parts subjected to high pressure.

[0027]

[0028] In formula (b1), R b11 ~R b14 each independently represents an aliphatic hydrocarbon group having 10 to 16 carbon atoms.

[0029] ​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.

[0030] R b15 ~R b18 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0031] 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.

[0032] 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 group has a specific substituent, the film of the watch lubricating composition that is applied to the sliding part becomes stronger.

[0033] 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.

[0034] R b191 and R b192 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0035] 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.

[0036] 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 R b191 When is an ethyl group, R b192 is a straight or branched chain alkyl group having 2 to 3 carbon atoms.

[0037] The film of the watch lubricating 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.

[0038] From the viewpoint of wear resistance and extreme pressure properties, the neutral phosphite is preferably contained in an amount of 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the base oil.

[0039] [Pentavalent Phosphate Ester] The watch lubricating composition according to the first embodiment contains a pentavalent phosphate ester represented by the following general formula (b2) as a wear-resistant additive.

[0040]

[0041] In formula (b2), R b21 represents alkyl having 4 to 22 carbon atoms, and n represents an integer of 1 or 2.

[0042] The watch lubricating 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 from each other. The watch lubricating composition according to the first embodiment contains the specific neutral phosphite ester and two or more specific pentavalent phosphate esters, and therefore has excellent wear resistance and extreme pressure resistance, and can further improve the lubricating performance of the watch lubricating oil composition.

[0043] From the viewpoint of wear resistance and extreme pressure properties, in the above formula (b2), R b21 Preferably, R represents an alkyl group having 12 to 18 carbon atoms. That is, the watch lubricating 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 preferable that the alkyl groups represented by the following formula (I) have 12 to 18 carbon atoms and are different from each other.

[0044] More specifically, from the viewpoint of wear resistance and extreme pressure properties, in the watch lubricating composition according to embodiment 1, 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 37It 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 (a monophosphate ester and a diphosphate ester). The same applies to the pentavalent phosphate esters (B213) to (B218).

[0045] 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.

[0046] From the viewpoint of wear resistance and extreme pressure properties, the pentavalent phosphate ester is preferably contained in an amount of 0.1 parts by mass or more and 20 parts by mass or less in total per 100 parts by mass of the base oil.

[0047] [Viscosity Index Improver] The watch lubricating 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 lubricating oil composition. This is thought to be because the inclusion of a viscosity index improver makes the film of the watch lubricating composition adhered to the sliding parts stronger. Furthermore, conventional watch lubricating oil compositions sometimes contain fluororesins such as polytetrafluoroethylene to improve lubricating performance. However, the use of a viscosity index improver in the watch lubricating composition according to embodiment 1 allows the composition to exhibit lubricating performance equivalent to or better than that of conventional watch lubricating oil compositions without the addition of a fluororesin, which is also preferable from an environmental perspective.

[0048] Viscosity index improvers include olefin polymers, olefin oligomers, polyacrylates, polymethacrylates, polyalkylstyrenes, polyesters, isobutylene fumarate, styrene maleate esters, vinyl acetate fumarate esters.

[0049] 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.

[0050] 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.

[0051] When a viscosity index improver is used, from the viewpoint of lubrication performance, it is preferably contained in an amount of 0.1 parts by mass or more and 50 parts by mass or less, and more preferably 0.1 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the base oil.

[0052] [Antioxidant] The watch lubricating composition according to Embodiment 1 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 lubricating composition according to Embodiment 1 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 lubricating oil composition. In other words, it is possible to lubricate sliding parts for a long period of time. As the antioxidant, only a diphenylamine derivative, only a hindered amine compound, or only a 2,6-di-t-butylphenol derivative may be used. Furthermore, 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, using a hindered amine compound and a 6-di-t-butylphenol derivative in combination enables the sliding parts to be lubricated for a longer period of time. Furthermore, even when a watch lubricating 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 on 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.

[0053]

[0054] In formula (c1), R c11 and R c12 ​each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms.

[0055] 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.

[0056] 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.

[0057] 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).

[0058]

[0059] In formula (c2), R c21 and R c22 each independently represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0060] 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.

[0061] ​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.

[0062] R c23 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0063] 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.

[0064] 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.

[0065]

[0066] In formula (c3), R c31 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms.

[0067] ​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.

[0068] From the viewpoint of extending the life of the watch lubricating oil composition, when using only a diphenylamine derivative, it is preferably used in an amount of 0.01 to 3 parts by mass per 100 parts by mass of base oil, and when using only a hindered amine compound, it is preferably used in an amount of 0.01 to 3 parts by mass per 100 parts by mass of base oil. When using a 2,6-di-t-butylphenol derivative, it is preferably used in an amount of 0.01 to 3 parts by mass per 100 parts by mass of base oil. Furthermore, from the viewpoint of extending the life of the watch lubricating oil composition, when using a diphenylamine derivative and a hindered amine compound in combination, it is preferably used in an amount of 0.01 to 1.5 parts by mass of each per 100 parts by mass of base oil. 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 to 1.5 parts by mass per 100 parts by mass of base oil, from the viewpoint of extending the life of the watch lubricating oil composition.

[0069] [Metal Deactivator] The watch lubricating 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 lubricating composition according to embodiment 1 is used in a watch composed of watch parts containing copper, it is preferable to contain a metal deactivator from the viewpoint of corrosion prevention. The metal deactivators may be used alone or in combination of two or more. Benzotriazole or its derivatives are preferred as the metal deactivator.

[0070] 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).

[0071]

[0072]

[0073] 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.

[0074] When a metal deactivator is used, it is preferably used in an amount of 0.01 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the base oil from the viewpoint of corrosion prevention.

[0075] The watch lubricating 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 include colorants. When a colorant is used, it is preferable to use it in an amount of more than 0 parts by mass and not more than 0.1 parts by mass per 100 parts by mass of the base oil.

[0076] ​​The watch lubricating composition according to embodiment 1 preferably has a kinematic viscosity (JIS K2283-1979) of 30,000 cSt or less and 1.5 cSt or more in the temperature range of -40°C to 100°C. Furthermore, the watch lubricating composition according to embodiment 1 preferably exhibits a weight change of 3% by weight or less when left at 90°C for 1,000 hours. Furthermore, when the watch lubricating composition according to embodiment 1 contains a metal deactivator, when copper corrosion resistance is evaluated in a copper corrosion test (test time: 2 hours, test temperature: 100°C) in accordance with JIS K 2513:2000, the copper corrosion standard judgment value (discoloration number) is preferably 1 or less. In order to exhibit suitable lubricating performance, the watch lubricating composition according to embodiment 1 preferably has a kinematic viscosity, weight change, and copper corrosion resistance evaluation within the above-mentioned ranges. When the watch lubricating composition according to embodiment 1 contains the above-mentioned components in the preferred amounts, the kinematic viscosity, weight change, and copper corrosion resistance evaluation can usually be adjusted to fall within the above-mentioned ranges.

[0077] The watch lubricating composition according to the first embodiment can be prepared by appropriately mixing the above-mentioned components.

[0078] <Watch lubricating composition according to embodiment 2> The watch lubricating composition according to embodiment 2 is the same as the watch lubricating composition according to embodiment 1, and achieves the same effects, 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.

[0079] 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 lubricating compositions. This also broadens the range of components that can be added to watch lubricating 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.

[0080] 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.

[0081] 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 fatty acids (A3), hydrocarbons (A5) obtained by reducing fatty acids (A3), saturated hydrocarbons (A6) obtained by hydrogenating unsaturated hydrocarbons contained in hydrocarbons (A5), and polymers (A7) obtained by polymerizing unsaturated fatty acids contained in fatty acids (A3) and / or unsaturated hydrocarbons contained in hydrocarbons (A5). Similar to vegetable oils, derivatives have a distribution of hydrocarbon group lengths, which facilitates the dissolution of components added to watch lubricating compositions. This also broadens the range of components that can be added to watch lubricating compositions. Furthermore, derivatives themselves exhibit excellent lubricity. This is believed to be due to the distribution of hydrocarbon group lengths within the derivatives. Furthermore, 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, which is advantageous in that they are 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.

[0082] 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 suitable 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 lubricating composition. Furthermore, among the polymers (A7), polymers obtained by polymerizing unsaturated hydrocarbons contained in the hydrocarbons (A5) are resistant to deterioration and are therefore preferred 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.

[0083]

[0084] In the above formula (a2), R a21 represents a saturated or unsaturated hydrocarbon group having 5 to 21 carbon atoms.

[0085] 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.

[0086] 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.

[0087] ​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.

[0088] 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.

[0089] 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.

[0090] <Watch and Clock According to the Embodiments> In the watch and clock according to the embodiments, the watch lubricating composition (watch lubricating composition according to Embodiment 1 or Embodiment 2) is adhered to the sliding parts. Therefore, the sliding parts are suitably lubricated. Examples of sliding parts include a wheel train, which is a collection of gears for driving the hour, minute, and second hands, and a sliding part such as a lever. Furthermore, materials for the watch components that make up the watch 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 watch and clock according to the embodiments, the sliding parts are suitably lubricated because the watch lubricating composition described above is used. Furthermore, even in watches with complex structures subject to high loads, the sliding parts are suitably lubricated because the watch lubricating composition described above is used. As mentioned above, in the case of watches that are made up of watch components containing copper, it is preferable to add a metal deactivator to the watch lubricating composition from the perspective of corrosion prevention.

[0091] The watch according to the embodiment is obtained by applying the watch lubricating composition to the sliding part. For example, the watch lubricating composition may be applied directly to the sliding part. Alternatively, the watch lubricating composition may be dispersed in an organic solvent such as hexane, the resulting solution may be applied to the sliding part, and the organic solvent may then be evaporated to apply the watch lubricating composition to the sliding part. In this case, the watch lubricating composition can be applied as a thinner film.

[0092] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. [Examples] [Example 1-1-1] A paraffinic hydrocarbon oil, specifically a 1-decene trimer, was used as the base oil. This 1-decene trimer had a kinematic viscosity at 100°C in the range of 2 cSt to 100 cSt and had 30 carbon atoms. In addition, 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (R in the above formula (b1)) was used as the neutral phosphite. b11 ~R b14 = tridecyl group, R b15 , Rb17 = methyl group, R b16 , R b18 = t-butyl group, R b191 = hydrogen atom, R b192 = n-propyl group). 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 the pentavalent phosphate ester (B212) and the pentavalent phosphate ester (B218) was used. This mixture contained 70% by mass of the pentavalent phosphate ester (B212), 10% by mass of the pentavalent phosphate ester (B214), 10% by mass of the pentavalent phosphate ester (B216), and 10% by mass of the pentavalent phosphate ester (B218), when the total of the four pentavalent phosphate esters was taken as 100% by mass. The neutral phosphite was mixed with the mixture of the pentavalent phosphate esters in an amount of 5 parts by mass per 100 parts by mass of the base oil, to produce a watch lubricating composition (1-1-1).

[0093] Examples 1-1-2 to 1-1-7 Instead of 4,4′-butylidenebis(3-methyl-6-t-butylphenylditridecyl phosphite) as the neutral phosphite, a compound represented by the formula (b1) above in which R b11 ~R b14 , R b15 , R b17 , R b16 , R b18 , R b191 , R b192However, watch lubricating compositions (1-1-2) to (1-1-7) were prepared in the same manner as in Example 1-1-1, except that compounds having the groups in Table 1-1 were used.

[0094]

[0095] [Example 1-1-8] A watch lubricating composition (1-1-8) was prepared in the same manner as in Example 1-1-1, except that the amount of the neutral phosphite ester was 0.1 parts by mass and the amount of the pentavalent phosphate ester mixture was 0.1 parts by mass.

[0096] [Example 1-1-9] A watch lubricating composition (1-1-9) was prepared in the same manner as in Example 1-1-1, except that the amount of neutral phosphite ester was 15 parts by mass and the amount of the pentavalent phosphate ester mixture was 20 parts by mass.

[0097] Example 1-1-10 A watch lubricating composition (1-1-10) was prepared in the same manner as in Example 1-1-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0098] Examples 1-1-11 to 1-1-16 In place of 4,4′-butylidenebis(3-methyl-6-t-butylphenylditridecyl phosphite) as the neutral phosphite, a compound represented by the formula (b1) above in which R b11 ~R b14 , R b15 , R b17 , R b16 , R b18 , R b191 , R b192 ​However, watch lubricating compositions (1-1-1) to (1-1-16) were prepared in the same manner as in Example 1-1-10, except that compounds having the groups in Table 1-2 were used.

[0099]

[0100] [Example 1-1-17] A watch lubricating composition (1-1-17) was prepared in the same manner as in Example 1-1-10, except that the amount of the neutral phosphite ester was 0.1 parts by mass and the amount of the pentavalent phosphate ester mixture was 0.1 parts by mass.

[0101] Example 1-1-18 A watch lubricating composition (1-1-18) was prepared in the same manner as in Example 1-1-10, except that the amount of neutral phosphite ester was 15 parts by mass and the amount of the pentavalent phosphate ester mixture was 20 parts by mass.

[0102] Example 1-2-1 A watch lubricating composition (1-2-1) was prepared in the same manner as in Example 1-1-1, except that a viscosity index improver was used. Specifically, an ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name LUCANT (registered trademark) HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Furthermore, 5 parts by mass of the neutral phosphite, 10 parts by mass of the pentavalent phosphate ester mixture, and 5 parts by mass of the viscosity index improver were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition (1-2-1).

[0103] Example 1-2-2 A watch lubricating composition (1-2-2) was prepared in the same manner as in Example 1-2-1, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0104] ​Example 1-2-3 A watch lubricating composition (1-2-3) was prepared in the same manner as in Example 1-2-1, except that a viscosity index improver containing polymethacrylate and mineral oil as its main components (manufactured by Sanyo Chemical Industries, Ltd., product name: Aclub 806T) was used instead of a co-oligomer of ethylene and α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600) as the viscosity index improver.

[0105] Example 1-2-4 A watch lubricating composition (1-2-4) was prepared in the same manner as in Example 1-2-1, except that the amount of the viscosity index improver was changed to 0.1 parts by mass.

[0106] Example 1-2-5 A watch lubricating composition (1-2-5) was prepared in the same manner as in Example 1-2-1, except that the amount of the viscosity index improver was changed to 50 parts by mass.

[0107] Example 1-2-6 A watch lubricating composition (1-2-6) was prepared in the same manner as in Example 1-2-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0108] Example 1-2-7 A watch lubricating composition (1-2-7) was prepared in the same manner as in Example 1-2-6, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0109] Example 1-2-8 A watch lubricating composition (1-2-8) was prepared in the same manner as in Example 1-2-6, except that a viscosity index improver containing polymethacrylate and mineral oil as main components (manufactured by Sanyo Chemical Industries, Ltd., product name: Aclub 806T) was used instead of a co-oligomer of ethylene and α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600) as the viscosity index improver.

[0110] Example 1-2-9 A watch lubricating composition (1-2-9) was prepared in the same manner as in Example 1-2-6, except that the amount of the viscosity index improver was changed to 0.1 parts by mass.

[0111] Example 1-2-10 A watch lubricating composition (1-2-10) was prepared in the same manner as in Example 1-2-6, except that the amount of the viscosity index improver was changed to 50 parts by mass.

[0112] Example 1-3-1 A watch lubricating composition (1-3-1) was prepared in the same manner as in Example 1-1-1, except that a diphenylamine derivative was used as the antioxidant. Specifically, Irganox (registered trademark) L57, a product of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Furthermore, 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, and 0.5 parts by mass of the antioxidant were mixed with 100 parts by mass of the base oil to prepare watch lubricating composition (1-3-1).

[0113] Examples 1-3-2 to 1-3-5 In place of the product name Irganox L57 manufactured by Ciba Specialty Chemicals Co., Ltd. as a diphenylamine derivative, c11 ~R c12 Lubricating compositions (1-3-2) to (1-3-5) for watches were prepared in the same manner as in Example 1-3-1, except that compounds in which p, p, and q are groups shown in Table 3-1 were used.

[0114]

[0115] ​Example 1-3-6 A watch lubricating composition (1-3-6) was prepared in the same manner as in Example 1-3-1, except that the amount of the diphenylamine derivative was 0.01 parts by mass.

[0116] Example 1-3-7 A watch lubricating composition (1-3-7) was prepared in the same manner as in Example 1-3-1, except that the amount of the diphenylamine derivative was 3 parts by mass.

[0117] Example 1-3-8 A watch lubricating composition (1-3-8) was prepared in the same manner as in Example 1-3-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0118] Example 1-3-9 A watch lubricating composition (1-3-9) was prepared in the same manner as in Example 1-3-8, except that the amount of the diphenylamine derivative was 0.01 parts by mass.

[0119] Example 1-3-10 A watch lubricating composition (1-3-10) was prepared in the same manner as in Example 1-3-8, except that the amount of the diphenylamine derivative was 3 parts by mass.

[0120] Example 1-3-11 A watch lubricating composition (1-3-11) was prepared in the same manner as in Example 1-1-1, except that a hindered amine compound was used as the antioxidant. Specifically, 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) was used. A watch lubricating composition (1-3-11) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, and 0.5 parts by mass of the antioxidant with respect to 100 parts by mass of the base oil.

[0121] Examples 1-3-12 to 1-3-17 In place of bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate as the hindered amine compound, compounds having R c21 ~R c23 Lubricating compositions for watches (1-3-12) to (1-3-17) were prepared in the same manner as in Example 1-3-11, except that compounds having a group in Table 3-2 were used.

[0122]

[0123] Example 1-3-18 A watch lubricating composition (1-3-18) was prepared in the same manner as in Example 1-3-11, except that the amount of the hindered amine compound was 0.01 parts by mass.

[0124] Example 1-3-19 A watch lubricating composition (1-3-19) was prepared in the same manner as in Example 1-3-11, except that the amount of the hindered amine compound was changed to 3 parts by mass.

[0125] Example 1-3-20 A watch lubricating composition (1-3-20) was prepared in the same manner as in Example 1-3-11, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0126] Example 1-3-21 A watch lubricating composition (1-3-21) was prepared in the same manner as in Example 1-3-20, except that the amount of the hindered amine compound was 0.01 parts by mass.

[0127] Example 1-3-22 A watch lubricating composition (1-3-22) was prepared in the same manner as in Example 1-3-20, except that the amount of the hindered amine compound was changed to 3 parts by mass.

[0128] Example 1-3-23 A watch lubricating composition (1-3-23) was prepared in the same manner as in Example 1-1-1, except that a diphenylamine derivative and a hindered amine compound were used as the antioxidants. Specifically, Irganox L57, a product name of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group) was used. A watch lubricating composition (1-3-23) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound relative to 100 parts by mass of the base oil.

[0129] Example 1-3-24 A watch lubricating composition (1-3-24) was prepared in the same manner as in Example 1-3-23, except that the amount of the diphenylamine derivative was 0.01 part by mass and the amount of the hindered amine compound was 0.01 part by mass.

[0130] Example 1-3-25 A watch lubricating composition (1-3-25) was prepared in the same manner as in Example 1-3-23, except that the amount of the diphenylamine derivative was 1.5 parts by mass and the amount of the hindered amine compound was 1.5 parts by mass.

[0131] Example 1-3-26 A watch lubricating composition (1-3-26) was prepared in the same manner as in Example 1-3-23, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0132] Example 1-4-1 A watch lubricating composition (1-4-1) was prepared in the same manner as in Example 1-1-1, except that a viscosity index improver and a diphenylamine derivative and a hindered amine compound were used as antioxidants. Specifically, an ethylene and α-olefin cooligomer (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. The diphenylamine derivative was IRGANOX L57, trade name, manufactured by Ciba Specialty Chemicals Corporation. The hindered amine compound was bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23= 1,8-octylene group). A watch lubricating composition (1-4-1) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 5 parts by mass of a viscosity index improver, 0.5 parts by mass of a diphenylamine derivative, and 0.5 parts by mass of a hindered amine compound relative to 100 parts by mass of the base oil.

[0133] Example 1-4-2 A watch lubricating composition (1-4-2) was prepared in the same manner as in Example 1-4-1, except that the amount of the viscosity index improver was 0.1 parts by mass, the amount of the diphenylamine derivative was 0.01 parts by mass, and the amount of the hindered amine compound was 0.01 parts by mass.

[0134] Example 1-4-3 A watch lubricating composition (1-4-3) was prepared in the same manner as in Example 1-4-1, except that the amount of the viscosity index improver was 50 parts by mass, the amount of the diphenylamine derivative was 1.5 parts by mass, and the amount of the hindered amine compound was 1.5 parts by mass.

[0135] Example 1-4-4 A watch lubricating composition (1-4-4) was prepared in the same manner as in Example 1-4-1, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0136] Example 1-4-5 A watch lubricating composition (1-4-5) was prepared in the same manner as in Example 1-4-4, except that the amount of the viscosity index improver was 0.1 parts by mass, the amount of the diphenylamine derivative was 0.01 parts by mass, and the amount of the hindered amine compound was 0.01 parts by mass.

[0137] Example 1-4-6 A watch lubricating composition (1-4-6) was prepared in the same manner as in Example 1-4-4, except that the amount of the viscosity index improver was 50 parts by mass, the amount of the diphenylamine derivative was 1.5 parts by mass, and the amount of the hindered amine compound was 1.5 parts by mass.

[0138] Example 1-4-7 A watch lubricating composition (1-4-7) was prepared in the same manner as in Example 1-4-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0139] Example 1-4-8 A watch lubricating composition (1-4-8) was prepared in the same manner as in Example 1-4-7, except that the amount of the viscosity index improver was 0.1 parts by mass, the amount of the diphenylamine derivative was 0.01 parts by mass, and the amount of the hindered amine compound was 0.01 parts by mass.

[0140] Example 1-4-9 A watch lubricating composition (1-4-9) was prepared in the same manner as in Example 1-4-7, except that the amount of the viscosity index improver was 50 parts by mass, the amount of the diphenylamine derivative was 1.5 parts by mass, and the amount of the hindered amine compound was 1.5 parts by mass.

[0141] Example 1-4-10 A watch lubricating composition (1-4-10) was prepared in the same manner as in Example 1-4-7, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0142] [Example 1-4-11] A watch lubricating composition (1-4-11) was prepared in the same manner as in Example 1-4-10, except that the amount of the viscosity index improver was 0.1 parts by mass, the amount of the diphenylamine derivative was 0.01 parts by mass, and the amount of the hindered amine compound was 0.01 parts by mass.

[0143] Example 1-4-12 A watch lubricating composition (1-4-12) was prepared in the same manner as in Example 1-4-10, except that the amount of the viscosity index improver was 50 parts by mass, the amount of the diphenylamine derivative was 1.5 parts by mass, and the amount of the hindered amine compound was 1.5 parts by mass.

[0144] Example 1-5-1 A watch lubricating composition (1-5-1) was prepared in the same manner as in Example 1-1-1, except that a metal deactivator and a viscosity index improver were used. Specifically, benzotriazole was used as the metal deactivator. An ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: Lucant HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Furthermore, 5 parts by mass of the neutral phosphite, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, and 5 parts by mass of the viscosity index improver were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition (1-5-1).

[0145] Example 1-5-2 A watch lubricating composition (1-5-2) was prepared in the same manner as in Example 1-5-1, except that the amount of the metal deactivator was changed to 0.01 parts by mass.

[0146] Example 1-5-3 A watch lubricating composition (1-5-3) was prepared in the same manner as in Example 1-5-1, except that the amount of the metal deactivator was changed to 3 parts by mass.

[0147] Example 1-5-4 A watch lubricating composition (1-5-4) was prepared in the same manner as in Example 1-5-1, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0148] Example 1-5-5 A watch lubricating composition (1-5-5) was prepared in the same manner as in Example 1-5-4, except that the amount of the metal deactivator was changed to 0.01 parts by mass.

[0149] Example 1-5-6 A watch lubricating composition (1-5-6) was prepared in the same manner as in Example 1-5-4, except that the amount of the metal deactivator was changed to 3 parts by mass.

[0150] Example 1-5-7 A watch lubricating composition (1-5-7) was prepared in the same manner as in Example 1-5-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0151] Example 1-5-8 A watch lubricating composition (1-5-8) was prepared in the same manner as in Example 1-5-7, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0152] Example 1-5-9 A watch lubricating composition (1-5-9) was prepared in the same manner as in Example 1-1-1, except that a metal deactivator and a diphenylamine derivative and a hindered amine compound were used as antioxidants. Specifically, benzotriazole was used as the metal deactivator. Irganox L57, a product name of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group). A watch lubricating composition (1-5-9) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound.

[0153] Example 1-5-10 A watch lubricating composition (1-5-10) was prepared in the same manner as in Example 1-5-9, except that the following mixture was used as the pentavalent phosphate ester: 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 37A 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.

[0154] Example 1-5-11 A watch lubricating composition (1-5-11) was prepared in the same manner as in Example 1-1-1, except that a metal deactivator, a viscosity index improver, and a diphenylamine derivative and a hindered amine compound were used as antioxidants. Specifically, benzotriazole was used as the metal deactivator. An ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. An Irganox L57 product name manufactured by Ciba Specialty Chemicals Corporation was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group). A watch lubricating composition (1-5-11) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, 5 parts by mass of the viscosity index improver, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound.

[0155] Example 1-5-12 A watch lubricating composition (1-5-12) was prepared in the same manner as in Example 1-5-11, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0156] Example 1-5-13 A watch lubricating composition (1-5-13) was prepared in the same manner as in Example 1-5-11, except that the amount of the metal deactivator was 0.01 parts by mass, the amount of the viscosity index improver was 0.1 parts by mass, the amount of the diphenylamine derivative was 0.01 parts by mass, and the amount of the hindered amine compound was 0.01 parts by mass.

[0157] Example 1-5-14 A watch lubricating composition (1-5-14) was prepared in the same manner as in Example 1-5-11, except that the amount of the metal deactivator was 3 parts by mass, the amount of the viscosity index improver was 50 parts by mass, the amount of the diphenylamine derivative was 1.5 parts by mass, and the amount of the hindered amine compound was 1.5 parts by mass.

[0158] Example 1-5-15 A watch lubricating composition (1-5-15) was prepared in the same manner as in Example 1-5-11, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0159] Example 1-5-16 A watch lubricating composition (1-5-16) was prepared in the same manner as in Example 1-5-12, except that the following mixture was used as the pentavalent phosphate ester: 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 37A 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.

[0160] Example 1-6-1 A watch lubricating composition (1-6-1) was prepared in the same manner as in Example 1-1-1, except that a hindered amine compound and a 2,6-di-t-butylphenol derivative were used as antioxidants. Specifically, 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). 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.) was used as the 2,6-di-t-butylphenol derivative. Furthermore, 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.5 parts by mass of the hindered amine compound, and 0.5 parts by mass of the 2,6-di-t-butylphenol derivative were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition (1-6-1).

[0161] Example 1-6-2 A watch lubricating composition (1-6-2) was prepared in the same manner as in Example 1-6-1, except that the amount of the hindered amine compound was 0.01 parts by mass and the amount of the 2,6-di-t-butylphenol derivative was 0.01 parts by mass.

[0162] Example 1-6-3 A watch lubricating composition (1-6-3) was prepared in the same manner as in Example 1-6-1, except that the amount of the hindered amine compound was 1.5 parts by mass and the amount of the 2,6-di-t-butylphenol derivative was 1.5 parts by mass.

[0163] Example 1-6-4 A watch lubricating composition (1-6-4) was prepared in the same manner as in Example 1-6-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0164] Example 1-6-5 A watch lubricating composition (1-6-5) was prepared in the same manner as in Example 1-1-1, except that a viscosity index improver and a hindered amine compound and a 2,6-di-t-butylphenol derivative were used as antioxidants. Specifically, a cooligomer of ethylene and α-olefin (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23= 1,8-octylene group). 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.) was used as the 2,6-di-t-butylphenol derivative. Furthermore, 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 5 parts by mass of a viscosity index improver, 0.5 parts by mass of a hindered amine compound, and 0.5 parts by mass of a 2,6-di-t-butylphenol derivative were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition (1-6-5).

[0165] Example 1-6-6 A watch lubricating composition (1-6-6) was prepared in the same manner as in Example 1-6-5, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0166] Example 1-6-7 A watch lubricating composition (1-6-7) was prepared in the same manner as in Example 1-6-5, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0167] Example 1-6-8 A watch lubricating composition (1-6-8) was prepared in the same manner as in Example 1-6-6, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0168] Example 1-6-9 A watch lubricating composition (1-6-9) was prepared in the same manner as in Example 1-1-1, except that a metal deactivator, a viscosity index improver, and a hindered amine compound and a 2,6-di-t-butylphenol derivative were used as antioxidants. Specifically, benzotriazole was used as the metal deactivator. An ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23= 1,8-octylene group). 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.) was used as the 2,6-di-t-butylphenol derivative. Furthermore, 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, 5 parts by mass of the viscosity index improver, 0.5 parts by mass of the hindered amine compound, and 0.5 parts by mass of the 2,6-di-t-butylphenol derivative were mixed together to prepare a watch lubricating composition (1-6-9).

[0169] Example 1-6-10 A watch lubricating composition (1-6-10) was prepared in the same manner as in Example 1-6-9, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0170] Example 1-6-11 A watch lubricating composition (1-6-11) was prepared in the same manner as in Example 1-6-9, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0171] Example 1-6-12 A watch lubricating composition (1-6-12) was prepared in the same manner as in Example 1-6-10, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0172] Example 2-1-1 An ester oil, specifically a polyol ester oil, was used as the base oil. This polyol ester oil was a mixed ester of neopentyl glycol and caprylic and capric acids. 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (R in the above formula (b1)) was used as the neutral phosphite. 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). 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 the pentavalent phosphate ester (B212) and the pentavalent phosphate ester (B218) was used. This mixture contained 70% by mass of the pentavalent phosphate ester (B212), 10% by mass of the pentavalent phosphate ester (B214), 10% by mass of the pentavalent phosphate ester (B216), and 10% by mass of the pentavalent phosphate ester (B218), when the total of the four pentavalent phosphate esters was taken as 100% by mass. The neutral phosphite was mixed with the mixture of the pentavalent phosphate esters in an amount of 5 parts by mass per 100 parts by mass of the base oil, to produce a watch lubricating composition (2-1-1).

[0173] Example 2-1-2 A watch lubricating composition (2-1-2) was prepared in the same manner as in Example 2-1-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0174] Example 2-2-1 A watch lubricating composition (2-2-1) was prepared in the same manner as in Example 2-1-1, except that a viscosity index improver was used. Specifically, an ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Furthermore, 5 parts by mass of the neutral phosphite, 10 parts by mass of the pentavalent phosphate ester mixture, and 5 parts by mass of the viscosity index improver were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition (2-2-1).

[0175] Example 2-2-2 A watch lubricating composition (2-2-2) was prepared in the same manner as in Example 2-2-1, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0176] Example 2-2-3 A watch lubricating composition (2-2-3) was prepared in the same manner as in Example 2-2-1, except that a viscosity index improver containing polymethacrylate and mineral oil as its main components (manufactured by Sanyo Chemical Industries, Ltd., product name: Aclub 806T) was used instead of a co-oligomer of ethylene and α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600) as the viscosity index improver.

[0177] Example 2-2-4 A watch lubricating composition (2-2-4) was prepared in the same manner as in Example 2-2-1, except that the following mixture was used as the pentavalent phosphate ester: 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 37A 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.

[0178] Example 2-2-5 A watch lubricating composition (2-2-5) was prepared in the same manner as in Example 2-2-4, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0179] Example 2-2-6 A watch lubricating composition (2-2-6) was prepared in the same manner as in Example 2-2-4, except that a viscosity index improver containing polymethacrylate and mineral oil as main components (manufactured by Sanyo Chemical Industries, Ltd., product name: Aclub 806T) was used instead of a co-oligomer of ethylene and α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600) as the viscosity index improver.

[0180] Example 2-3-1 A watch lubricating composition (2-3-1) was prepared in the same manner as in Example 2-1-1, except that a diphenylamine derivative was used as the antioxidant. Specifically, Irganox L57, a product of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Furthermore, 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, and 0.5 parts by mass of the antioxidant were mixed with 100 parts by mass of the base oil to prepare watch lubricating composition (2-3-1).

[0181] Example 2-3-2 A watch lubricating composition (2-3-2) was prepared in the same manner as in Example 2-3-1, except that the following mixture was used as the pentavalent phosphate ester: b21 is an alkyl group having 13 carbon atoms (C 13 H27 -), 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.

[0182] Example 2-3-3 A watch lubricating composition (2-3-3) was prepared in the same manner as in Example 2-1-1, except that a hindered amine compound was used as the antioxidant. Specifically, 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) was used. A watch lubricating composition (2-3-3) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, and 0.5 parts by mass of the antioxidant with respect to 100 parts by mass of the base oil.

[0183] Example 2-3-4 A watch lubricating composition (2-3-4) was prepared in the same manner as in Example 2-3-3, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0184] Example 2-3-5 A watch lubricating composition (2-3-5) was prepared in the same manner as in Example 2-1-1, except that a diphenylamine derivative and a hindered amine compound were used as the antioxidants. Specifically, Irganox L57, a product name of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group) was used. A watch lubricating composition (2-3-5) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound relative to 100 parts by mass of the base oil.

[0185] Example 2-3-6 A watch lubricating composition (2-3-6) was prepared in the same manner as in Example 2-3-5, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0186] Example 2-4-1 A watch lubricating composition (2-4-1) was prepared in the same manner as in Example 2-1-1, except that a viscosity index improver and a diphenylamine derivative and a hindered amine compound were used as antioxidants. Specifically, an ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. The diphenylamine derivative was IRGANOX L57, trade name, manufactured by Ciba Specialty Chemicals Corporation. The hindered amine compound was bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group) was used. A watch lubricating composition (2-4-1) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 5 parts by mass of a viscosity index improver, 0.5 parts by mass of a diphenylamine derivative, and 0.5 parts by mass of a hindered amine compound relative to 100 parts by mass of the base oil.

[0187] Example 2-4-2 A watch lubricating composition (2-4-2) was prepared in the same manner as in Example 2-4-1, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0188] Example 2-4-3 A watch lubricating composition (2-4-3) was prepared in the same manner as in Example 2-4-1, except that the following mixture was used as the pentavalent phosphate ester: b21 is an alkyl group having 13 carbon atoms (C 13 H 27 -), and a pentavalent phosphate ester (B213) in which Rb21 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.

[0189] Example 2-4-4 A watch lubricating composition (2-4-4) was prepared in the same manner as in Example 2-4-3, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0190] Example 2-5-1 A watch lubricating composition (2-5-1) was prepared in the same manner as in Example 2-1-1, except that a metal deactivator and a viscosity index improver were used. Specifically, benzotriazole was used as the metal deactivator. An ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: Lucant HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Furthermore, 5 parts by mass of the neutral phosphite, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, and 5 parts by mass of the viscosity index improver were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition (2-5-1).

[0191] Example 2-5-2 A watch lubricating composition (2-5-2) was prepared in the same manner as in Example 2-5-1, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0192] Example 2-5-3 A watch lubricating composition (2-5-3) was prepared in the same manner as in Example 2-5-1, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0193] Example 2-5-4 A watch lubricating composition (2-5-4) was prepared in the same manner as in Example 2-5-2, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0194] Example 2-5-5 A watch lubricating composition (2-5-5) was prepared in the same manner as in Example 2-1-1, except that a metal deactivator and a diphenylamine derivative and a hindered amine compound were used as antioxidants. Specifically, benzotriazole was used as the metal deactivator. Irganox L57, a product name of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group). A watch lubricating composition (2-5-5) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound.

[0195] Example 2-5-6 A watch lubricating composition (2-5-6) was prepared in the same manner as in Example 2-5-5, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0196] Example 2-5-7 A watch lubricating composition (2-5-7) was prepared in the same manner as in Example 2-1-1, except that a metal deactivator, a viscosity index improver, and a diphenylamine derivative and a hindered amine compound were used as antioxidants. Specifically, benzotriazole was used as the metal deactivator. An ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: LUCANT HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. An Irganox L57 product, trade name, manufactured by Ciba Specialty Chemicals Corporation was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group). A watch lubricating composition (2-5-7) was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester mixture, 0.05 parts by mass of the metal deactivator, 5 parts by mass of the viscosity index improver, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound.

[0197] Example 2-5-8 A watch lubricating composition (2-5-8) was prepared in the same manner as in Example 2-5-7, except that a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-2000) was used as the viscosity index improver instead of a cooligomer of ethylene and an α-olefin (manufactured by Mitsui Chemicals, Inc., product name: LUCANT HC-600). This viscosity index improver had a kinematic viscosity of 2000 cSt at 100°C.

[0198] Example 2-5-9 A watch lubricating composition (2-5-9) was prepared in the same manner as in Example 2-5-7, except that the following mixture was used as the pentavalent phosphate ester: b21 is an alkyl group having 13 carbon atoms (C 13 H27 -), 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.

[0199] Example 2-5-10 A watch lubricating composition (2-5-10) was prepared in the same manner as in Example 2-5-8, except that the following mixture was used as the pentavalent phosphate ester: 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.

[0200] Example 3-1-1 An ether oil, specifically an alkyl-substituted diphenyl ether (manufactured by Matsumura Oil Research Institute Co., Ltd., product name: MORESCO-HILUBE LB32) was used as the base oil. In addition, 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (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).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 the pentavalent phosphate ester (B212) and the pentavalent phosphate ester (B218) was used. This mixture contained 70% by mass of the pentavalent phosphate ester (B212), 10% by mass of the pentavalent phosphate ester (B214), 10% by mass of the pentavalent phosphate ester (B216), and 10% by mass of the pentavalent phosphate ester (B218), when the total of the four pentavalent phosphate esters was taken as 100% by mass. The neutral phosphite was mixed with the mixture of the pentavalent phosphate esters in an amount of 5 parts by mass per 100 parts by mass of the base oil, to produce a watch lubricating composition (3-1-1).

[0201] [Examples 3-1-2 to 3-5-10] Watch lubricating compositions (3-1-2) to (3-5-10) were prepared in the same manner as in Examples 2-1-2 to 2-5-10, except that the base oil in Examples 2-1-2 to 2-5-10 was changed to an ether oil, specifically an alkyl-substituted diphenyl ether (manufactured by Matsumura Oil Research Institute Co., Ltd., product name: MORESCO-HILUBE LB32).

[0202] Example 4-1-1 A vegetable oil, specifically coconut oil (kinematic viscosity at 40°C (JIS K 2283) 27.55 cSt, manufactured by Kaneda Co., Ltd.) was used as the base oil. In addition, 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (R b11 ~R b14 = tridecyl group, Rb15 , R b17 = methyl group, R b16 , R b18 = t-butyl group, R b191 = hydrogen atom, R b192 = n-propyl group). 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 the pentavalent phosphate ester (B212) and the pentavalent phosphate ester (B218) was used. This mixture contained 70% by mass of the pentavalent phosphate ester (B212), 10% by mass of the pentavalent phosphate ester (B214), 10% by mass of the pentavalent phosphate ester (B216), and 10% by mass of the pentavalent phosphate ester (B218), when the total of the four pentavalent phosphate esters was taken as 100% by mass. The neutral phosphite was mixed with the mixture of the pentavalent phosphate esters in an amount of 5 parts by mass per 100 parts by mass of the base oil, to produce a watch lubricating composition (4-1-1).

[0203] [Examples 4-1-2 to 4-5-10] Watch lubricating compositions (4-1-2) to (4-5-10) were prepared in the same manner as in Examples 2-1-2 to 2-5-10, except that the base oil in Examples 2-1-2 to 2-5-10 was changed to a vegetable oil, specifically coconut oil (kinematic viscosity at 40°C (JIS K 2283) 27.55 cSt, manufactured by Kaneda Co., Ltd.).

[0204] Example 5-1-1 A vegetable oil derivative was used as the base oil, 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). Furthermore, 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (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). 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 37A mixture of the pentavalent phosphate ester (B212) and the pentavalent phosphate ester (B218) was used. This mixture contained 70% by mass of the pentavalent phosphate ester (B212), 10% by mass of the pentavalent phosphate ester (B214), 10% by mass of the pentavalent phosphate ester (B216), and 10% by mass of the pentavalent phosphate ester (B218), when the total of the four pentavalent phosphate esters was taken as 100% by mass. The neutral phosphite was mixed with the mixture of the pentavalent phosphate esters in an amount of 5 parts by mass per 100 parts by mass of the base oil, to produce a watch lubricating composition (5-1-1).

[0205] Examples 5-1-2 to 5-5-10 Watch lubricating compositions (5-1-2) to (5-5-10) were prepared in the same manner as in Examples 2-1-2 to 2-5-10, except that the base oil in Examples 2-1-2 to 2-5-10 was changed to a vegetable oil derivative, specifically a hydroisomerization product (CAS number: 2241366-04-9) (product name: SynNova 4, manufactured by Novvi LLC, kinematic viscosity at 40°C (JIS K 2283) 19 cSt) of a hydrogenation reaction 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).

[0206] Example 6-1-1: A vegetable oil derivative, specifically oligomerization products of 1-tetradecene and 1-dodecene, hydrogenated, C24-84 fraction (CAS number: 883233-93-0), was used as the base oil. 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (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).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 the pentavalent phosphate ester (B212) and the pentavalent phosphate ester (B218) was used. This mixture contained 70% by mass of the pentavalent phosphate ester (B212), 10% by mass of the pentavalent phosphate ester (B214), 10% by mass of the pentavalent phosphate ester (B216), and 10% by mass of the pentavalent phosphate ester (B218), when the total of the four pentavalent phosphate esters was taken as 100% by mass. The neutral phosphite was mixed with the mixture of the pentavalent phosphate esters in an amount of 5 parts by mass per 100 parts by mass of the base oil, to produce a watch lubricating composition (6-1-1).

[0207] [Examples 6-1-2 to 6-5-10] Watch lubricating compositions (6-1-2) to (6-5-10) were prepared in the same manner as in Examples 2-1-2 to 2-5-10, except that the base oil in Examples 2-1-2 to 2-5-10 was changed to a vegetable oil derivative, specifically, oligomerization products of 1-tetradecene and 1-dodecene, hydrogenated, C24-84 fraction (CAS number: 883233-93-0).

[0208] Comparative Example 1-1-1 A paraffinic hydrocarbon oil, specifically a 1-decene trimer, was used as the base oil. This 1-decene trimer had a kinematic viscosity at 100°C in the range of 2 cSt to 100 cSt and had 30 carbon atoms. Furthermore, 4,4'-butylidenebis(3-methyl-6-t-butylphenylditridecylphosphite) (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) was used. 100 parts by mass of the base oil was mixed with 5 parts by mass of the neutral phosphite to prepare a lubricating composition for a watch.

[0209] [Comparative Example 1-1-2] A watch lubricating composition was prepared in the same manner as in Comparative Example 1-1-1, except that a pentavalent phosphate ester was used. Specifically, the pentavalent phosphate ester was a compound represented by the formula (b2) R b21 is an alkyl group having 18 carbon atoms (C 18 H 37 A pentavalent phosphate ester (B218) having a pH of 10-15 (-) was used. A lubricating composition for a watch was prepared by mixing 5 parts by mass of the neutral phosphite ester and 10 parts by mass of the pentavalent phosphate ester with 100 parts by mass of the base oil.

[0210] Comparative Example 1-1-3 A watch lubricating composition was prepared in the same manner as in Comparative Example 1-1-2, except that a viscosity index improver was used. Specifically, an ethylene and α-olefin co-oligomer (manufactured by Mitsui Chemicals, Inc., trade name: Lucant HC-600) was used as the viscosity index improver. This viscosity index improver had a kinematic viscosity of 600 cSt at 100°C. Furthermore, 5 parts by mass of the neutral phosphite, 10 parts by mass of the pentavalent phosphate, and 5 parts by mass of the viscosity index improver were mixed with 100 parts by mass of the base oil to prepare a watch lubricating composition.

[0211] Comparative Example 1-1-4 A watch lubricating composition was prepared in the same manner as in Comparative Example 1-1-2, except that a diphenylamine derivative and a hindered amine compound were used as the antioxidant. Specifically, Irganox L57, a product name of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group) was used. A lubricating composition for a watch was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound with 100 parts by mass of the base oil.

[0212] Comparative Example 1-1-5 A watch lubricating composition was prepared in the same manner as in Comparative Example 1-1-3, except that a diphenylamine derivative and a hindered amine compound were used as the antioxidant. Specifically, Irganox L57, a product name of Ciba Specialty Chemicals Co., Ltd., was used as the diphenylamine derivative. Bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl) decanedioate (R c21 , R c22 = n-octyl group, R c23 = 1,8-octylene group) was used. A lubricating composition for a watch was prepared by mixing 5 parts by mass of the neutral phosphite ester, 10 parts by mass of the pentavalent phosphate ester, 5 parts by mass of the viscosity index improver, 0.5 parts by mass of the diphenylamine derivative, and 0.5 parts by mass of the hindered amine compound relative to 100 parts by mass of the base oil.

[0213] [Evaluation method] <Watch operation test (1)> A mechanical watch movement manufactured by Citizen Watch Co., Ltd. TMFor (No. 9015), the prepared timepiece lubricating composition was applied to the gear train part (made of an Fe-based alloy), which is the sliding part. A hand-turning durability test was conducted for up to 32 years at room temperature (25°C) and -10°C at a speed of 64 times the normal speed, and the sliding part was observed before and after the test. Specifically, there were 13 samples for each model, and hand-turning durability tests were conducted for 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, and 32 years, respectively, and the sliding part was observed before and after the test. The sliding part was subjected to a force of 9700 N / m during operation. 2 The results of the observation were evaluated according to the criteria described below.

[0214] <Watch operation test (2)> Mechanical watch movement manufactured by Citizen Watch Co., Ltd. TM For the watch (No. 9015), the prepared watch lubricating composition was applied to the gear train (made of a Cu-based alloy), which is the sliding part. A hand-turning durability test was conducted for up to 32 years at room temperature (25°C) and -10°C at a speed of 64 times the normal speed, and the sliding part was observed before and after the test. Specifically, there were 13 samples for each model, and hand-turning durability tests were conducted for 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, and 32 years, respectively, and the sliding part was observed before and after the test. The sliding part was subjected to a force of 9700 N / m during operation. 2 The results of the observation were evaluated according to the criteria described below.

[0215] <Watch operation test (3)> Mechanical watch movement manufactured by Citizen Watch Co., Ltd. TMFor the watch No. 9015, the prepared watch lubricating composition was applied to the gear train (made of polyoxymethylene (POM)), which is the sliding part. A hand-turning durability test was conducted for up to 32 years at 64x speed under room temperature (25°C) conditions, and the sliding part was observed before and after the test. Specifically, there were 13 samples, and hand-turning durability tests were conducted for 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, and 32 years, respectively, and the sliding part was observed before and after the test. Note that the sliding part was subjected to a force of 9700 N / m during operation. 2 The results of the observation were evaluated according to the criteria described below.

[0216] [Evaluation Criteria] A sample was rated as passing if no color change or scraping marks were observed after the test. On the other hand, a sample was rated as failing if a color change to brown or other color, scraping marks, or scraped surface with wear particles were observed after the test. The prepared watch lubricating compositions were colorless and transparent before the test. Tables 5 to 11 show the evaluation results. The values ​​in the tables indicate that the sample passed the hand-twisting durability test up to the number of years indicated, but failed the hand-twisting durability test for a longer period than that number. For example, a value of 10 in the table indicates that the sample passed the 10-year hand-twisting durability test but failed the 12-year or longer hand-twisting durability test. However, a value of 32 in the table indicates that the sample passed the 32-year hand-twisting durability test. A value of 14 or higher in the table indicates that the sample exhibits high lubricating performance as a watch.

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224] ​​​​​​​

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234] The watch lubricating compositions obtained in the Examples all had a kinematic viscosity (JIS K2283-1979) of 30,000 cSt or less and 1.5 cSt or more in the temperature range of -40°C to 100°C. Furthermore, the watch lubricating compositions obtained in the Examples showed a weight change of 3% by weight or less when left at 90°C for 1,000 hours. Furthermore, when the watch lubricating compositions obtained in the Examples contained a metal deactivator, they were 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, and the standard copper plate corrosion rating (discoloration number) was 1.

[0235]

[0013] Based on 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 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 of the alkyl groups represented by the formula (I) is different.

[0236]

[0237] (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.

[0238]

[0239] (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 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 of the alkyl groups represented by the formula (I) is different.

[0240]

[0241] (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.

[0242]

[0243] (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 lubricating composition according to [1] or [2], further comprising a viscosity index improver. [5] The watch lubricating 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).

[0244]

[0245] (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.

[0246]

[0247] (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.

[0248]

[0249] (In formula (c3), R c31 represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms.) [6] The watch lubricating composition according to [1] or [2], further comprising a metal deactivator. [7] A watch having the watch lubricating composition according to [1] or [2] adhered to its sliding parts.​​​

Claims

1. A composition comprising a base oil selected from paraffinic hydrocarbon oils, ester oils, and ether oils, 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 of the alkyl groups 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 composition comprising a base oil selected from vegetable oils and derivatives thereof, 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 of the alkyl groups 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 watch lubricating composition according to claim 1 or 2, wherein represents an alkyl group having 12 to 18 carbon atoms.

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

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

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

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