JP2005290183A - Gear oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gear oil composition resistant to higher temperatures and withstanding operation under a higher load together with a tendency to a higher speed and a higher output as a gear oil in response to high efficiency and low cost because of requests for gears used for various kinds of industrial machines, specifically a gear oil having excellent energy-saving properties. <P>SOLUTION: The gear oil composition is obtained by including a component (A) and/or a component (B) in at least one kind selected from mineral oils, oils and fats and synthetic oils as a base oil. The component (A) is composed of at least one kind of compound represented by general formula (1) R<SP>1</SP>-CO-NR<SP>2</SP>-(CH<SB>2</SB>)<SB>n</SB>-COOX<SP>1</SP>(1), general formula (2) [R<SP>1</SP>-CO-NR<SP>2</SP>-(CH<SB>2</SB>)<SB>n</SB>-COO]<SB>m</SB>Y<SP>1</SP>(2) and general formula (3) [R<SP>1</SP>-CO-NR<SP>2</SP>-(CH<SB>2</SB>)<SB>n</SB>-COO]<SB>m</SB>-Z-(OH)<SB>m'</SB>(3). The component (B) is a compound represented by general formula (4) R<SP>3</SP>-CH<SB>2</SB>COOH (4). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gear oil, and more particularly to a gear oil excellent in energy saving.

  Although the improvement in efficiency and energy saving has been remarkably improved along with the development of the industry, the demand for these remains an eternal issue. High efficiency and low cost are also required for gears used in various industrial machines. Along with this trend, gear oils, combined with the trend toward higher speed and higher output, have been able to reduce loss energy and reduce oil temperature by reducing resistance in sliding parts from the viewpoint of energy saving in recent years. Performance has come to be demanded.

For example, Patent Documents 1 and 2 relating to gear oil disclose the blending of a sulfur-based extreme pressure additive and a phosphorus-based extreme pressure additive into gear oil.
However, the conventional gear oil does not always have sufficient energy saving performance when used in gears of recent industrial machines and the like. In other words, lubricating oils to which extreme pressure agents such as zinc dialkyldithiophosphate are added are widely used for applications that require high extreme pressure and wear resistance. However, these conventional extreme pressure agents alone can save energy. The solution is not enough and a solution is strongly desired.
Japanese Patent Laid-Open No. 10-259394 JP-A-9-208976

  The present invention is intended to improve the energy saving performance that is lacking in gear oils used for gears in recent industrial machines and the like.

As a result of intensive studies to solve the above object, the present inventors have found that the above-mentioned problems can be solved by adding the following components to a predetermined base oil, and have completed the present invention.
That is, the present invention is a gear oil composition comprising at least one selected from mineral oil, fat and oil and synthetic oil as a base oil, and containing the component (A) and / or the component (B), The component comprises at least one compound represented by the following general formulas (1) to (3),
R ¹ —CO—NR ² — (CH ₂ ) _n —COOX ¹ (1)
(In the formula, R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, X ¹ is hydrogen, and an alkyl group having 1 to 30 carbon atoms. Or an alkenyl group having 1 to 30 carbon atoms, and n represents an integer of 1 to 4.)
[R1-CO-NR2- (CH 2) n -COO] m Y 1 (2)
Wherein R ^{1 is} an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, Y ¹ is an alkali metal or alkaline earth metal, and n is 1 An integer of ˜4, m is 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.
^{[R 1 -CO-NR 2 -} (CH 2) n -COO] m -Z- (OH) m '(3)
(Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, and Z is a hydroxyl group of a polyhydric alcohol having 2 or more valences) And m represents an integer of 1 or more, m ′ represents an integer of 0 or more, m + m ′ represents a valence of Z, and n represents an integer of 1 to 4.)
The component (B) is a compound represented by the following general formula (4).
It relates to the gear oil composition.
R ³ —CH ₂ COOH Formula (4)
(In the formula, R ³ represents an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms, or a group represented by the general formula (5).)
R ⁴ —C ₆ H ₄ O— (5)
(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms or hydrogen.)

  The gear oil composition of the present invention is excellent in energy saving. For this reason, gears used in various industrial machines with high efficiency and low cost can be combined with the trend toward higher speed and higher output as gear oil, enabling more energy-saving operation.

In the gear oil composition of the present invention, at least one selected from mineral oils, fats and oils and synthetic oils is used as the base oil.
Here, as mineral oil, solvent debris, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining is performed on the lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of crude oil. And paraffinic or naphthenic mineral oils obtained by applying a suitable combination of one or more purification means such as sulfuric acid washing and clay treatment. Further, it is also possible to use a wax isomerized base oil, a base oil produced by a technique for isomerizing GTL WAX (Gas Liquid Wax), and the like.
Examples of the fats and oils include beef tallow, lard, sunflower oil, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, and hydrogenated products thereof.

Synthetic oils include, for example, poly α-olefins (ethylene-propylene copolymers, polybutenes, 1-octene oligomers, 1-decene oligomers and hydrides thereof), alkylbenzenes, alkylnaphthalenes, monoesters (butyl). Stearate, octyl laurate), diester (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sepacate, etc.), polyester (trimellitic acid ester, etc.), polyol ester (Trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol Lumpur, polyphenyl ether, dialkyl diphenyl ether, phosphate ester (tricresyl phosphate, etc.), fluorine-containing compound (perfluoropolyether, fluorinated polyolefin and the like), silicone oils and the like.
Among these base oils, preferred are mineral oil, poly α-olefin, polyol ester, and polyoxyalkylene glycol.
As a base oil of the gear oil composition of the present invention, the above base oils may be used alone or in combination of two or more.

The kinematic viscosity of these base oils is not particularly limited and is arbitrary, but the lower limit value of the 40 ° C. kinematic viscosity is 10 mm ² / s or more, preferably 20 mm ² / s or more, more preferably from the viewpoint of pitting resistance. Is 40 mm ² / s or more, most preferably 60 mm ² / s or more, and the upper limit is 10,000 mm ² / s or less, preferably 5000 mm ² / s or less, more preferably 1000 mm from the viewpoint of low friction loss due to stirring resistance. ² / s or less. The viscosity index is also arbitrary, but the lower limit is 80 or more, preferably 90 or more, from the viewpoint of suppressing oil film deterioration at high temperatures. In general, the value is 500 or less. Furthermore, although the pour point is also arbitrary, the pour point is usually preferably −5 ° C. or less, more preferably −15 ° C. or less from the viewpoint of low temperature characteristics.

(A) component:
The gear oil composition of the present invention contains the component (A), the component (B), or both as essential components.
That is, the component (A) added for improving the frictional properties is composed of at least one of the compounds represented by the following general formulas (1) to (3).
R ¹ —CO—NR ² — (CH ₂ ) _n —COOX ¹ (1)
(In the formula, R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, X ¹ is hydrogen, and an alkyl group having 1 to 30 carbon atoms. Or an alkenyl group having 1 to 30 carbon atoms, and n represents an integer of 1 to 4.)
[R ¹ —CO—NR ² — (CH ₂ ) _n —COO] _m Y ¹ (2)
Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, Y ¹ is an alkali metal or an alkaline earth metal, and n is (An integer of 1 to 4, m represents 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.)
^{[R 1 -CO-NR 2 -} (CH 2) n -COO] m -Z- (OH) m '(3)
(Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, and Z is a hydroxyl group of a polyhydric alcohol having 2 or more valences) And m represents an integer of 1 or more, m ′ represents an integer of 0 or more, m + m ′ represents a valence of Z, and n represents an integer of 1 to 4.)

In general formulas (1) to (3), R ¹ represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms. From the viewpoint of solubility in base oil, the alkyl group or alkenyl group must have 6 or more carbon atoms, preferably 7 or more carbon atoms, and more preferably 8 or more carbon atoms. Further, from the viewpoint of storage stability and the like, it is necessary that the alkyl group or alkenyl group has 30 or less carbon atoms, preferably 24 or less carbon atoms, and more preferably 20 or less carbon atoms. Specific examples of such alkyl groups and alkenyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Alkyl groups such as heptadecyl group, octadecyl group, nonadecyl group, icosyl group (these alkyl groups may be linear or branched); hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group Group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group and the like alkenyl groups (these alkenyl groups may be linear or branched, and the position of the double bond) Are also optional)

In general formulas (1) to (3), R ² represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of storage stability and the like, it is necessary that the alkyl group has 4 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms. In general formulas (1) to (3), n represents an integer of 1 to 4. From the viewpoint of storage stability and the like, it is necessary to be an integer of 4 or less, preferably 3 or less, and more preferably 2 or less.

In General Formula (1), X ¹ represents hydrogen, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 1 to 30 carbon atoms. The alkyl group or alkenyl group represented by X ¹ needs to have 30 or less carbon atoms from the viewpoint of storage stability and the like, preferably 20 or less carbon atoms, and more preferably 10 or less carbon atoms. preferable. Specific examples of such an alkyl group or alkenyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. (These alkyl groups may be linear or branched); alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group (these alkenyl groups) May be linear or branched, and the position of the double bond is arbitrary). Moreover, it is preferable that it is an alkyl group from points, such as being excellent in sludge resistance. X ¹ is preferably hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms from the viewpoint of improving the friction characteristics, improving the durability of the friction characteristics effect, and the like. It is more preferably hydrogen or an alkyl group having 1 to 20 carbon atoms, and even more preferably hydrogen or an alkyl group having 1 to 10 carbon atoms.

In the general formula (2), Y ¹ represents an alkali metal or an alkaline earth metal, and specific examples include sodium, potassium, magnesium, calcium and the like. Among these, alkaline earth metals are preferable from the viewpoint of improving the sustainability of the friction characteristic effect. In the general formula (2), m represents ¹ when Y ¹ is an alkali metal, and 2 when Y is an alkaline earth metal.

  In general formula (3), Z represents the residue except the hydroxyl group of the polyhydric alcohol more than bivalence. Specific examples of such polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2- Octanediol, 1,8-octanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol Divalent alcohols such as glycerin, 2- (hydroxymethyl) -1,3-propanediol, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3 -Propanetriol, 2-methyl-2,3,4- Tantriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4 -Trihydric alcohols such as dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane; pentaerythritol, erythritol, 1, 2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, sorbitan Tetrahydric alcohols such as adonitol, arabitol, xylitol, triglycerin, etc .; dipentaerythritol Le, sorbitol, mannitol, iditol, inositol, dulcitol, talose, hexavalent alcohols such as allose, polyglycerin or their dehydrated condensates and the like.

  In the general formula (3), m is an integer of 1 or more, m ′ is an integer of 0 or more, and m + m ′ is the same as the valence of Z. That is, all of the hydroxyl groups of the polyhydric alcohol of Z may be substituted, or only a part thereof may be substituted.

The component (A) is at least one compound selected from the general formulas (1) to (3). From the viewpoint of improving the durability of the friction characteristic effect, the general formulas (1) and (1) It is preferably at least one compound selected from 2). Further, only one compound selected from the general formulas (1) to (3) may be used alone, or a mixture of two or more compounds may be used.
As a preferable example of the compound represented by the general formula (1), N-oleoyl sarcosine in which R ¹ is an alkenyl group having 17 carbon atoms, R ² is a methyl group, X ¹ is hydrogen, and n is 1 is used. Can be mentioned.

  The upper limit of the content when the component (A) in the gear oil of the present invention is blended is 5% by mass, preferably 2% by mass, more preferably 1% by mass based on the total amount of the composition. When the content exceeds 5% by mass, further improvement in friction characteristics corresponding to the content is not observed, and storage stability is lowered, which is not preferable. On the other hand, the lower limit of the content when the component (A) is blended is 0.001% by mass, preferably 0.003% by mass, and more preferably 0.005% by mass based on the total amount of the composition. When the content of the component (A) is less than 0.001% by mass, the effect of improving the friction characteristics is not observed, which is not preferable.

(B) component:
In the present invention, the gear oil composition contains component (A), component (B), or both as essential components.
Here, the component (B) is a compound represented by the following general formula (4).
R ³ —CH ₂ COOH Formula (4)
(In the formula, R ³ represents an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms, or a group represented by the general formula (5).)
R ⁴ —C ₆ H ₄ O— (5)
(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms or hydrogen.)

In General Formula (4), R ³ represents an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms, or a group represented by General Formula (5). The alkyl group represented by R ³ needs to have 7 to 29 carbon atoms. In view of solubility in the base oil, it is necessary that the number of carbon atoms is 7 or more, and it is preferable that the number of carbon atoms is 9 or more. Further, from the viewpoint of storage stability and the like, it is necessary to have 29 or less carbon atoms, preferably 22 or less carbon atoms, and more preferably 19 or less carbon atoms. Specific examples of such alkyl groups include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl group and the like (these alkyl groups may be linear or branched).

The alkenyl group represented by R ³ needs to have 7 to 29 carbon atoms. In view of solubility in the base oil, it is necessary that the number of carbon atoms is 7 or more, and it is preferable that the number of carbon atoms is 9 or more. Further, from the viewpoint of storage stability and the like, it is necessary to have 29 or less carbon atoms, preferably 22 or less carbon atoms, and more preferably 19 or less carbon atoms. Specific examples of such alkenyl groups include heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, A nonadecenyl group and the like (these alkenyl groups may be linear or branched).

In general formula (5), R ⁴ represents an alkyl group having 1 to 20 carbon atoms or hydrogen. The alkyl group represented by R ⁴ needs to have 20 or less carbon atoms from the viewpoint of storage stability and the like, preferably 19 or less carbon atoms, and more preferably 15 or less carbon atoms. Moreover, it is preferable that it is C3 or more from points, such as the solubility to base oil, and it is more preferable that it is C5 or more. In the case where R ⁴ is an alkyl group, the substitution position is arbitrary, but the para-position or meta-position is preferred, and the para-position is more preferred from the viewpoint of excellent frictional properties. In General Formula (4), R ³ is represented by General Formula (5), as described above, whether it is an alkyl group having 7 to 29 carbon atoms or an alkenyl group having 7 to 29 carbon atoms. Although it may be a group, it is preferably a group represented by the general formula (5) from the standpoint of superior friction characteristics.

  In the oil composition of the present invention, the content when the component (B) is blended may be less than 5% by mass based on the total amount of the composition because sludge resistance may decrease when blended in a large amount. Preferably, it is 1% by mass or less, more preferably 0.5% by mass or less. On the other hand, the lower limit content when the component (B) is blended is preferably 0.001% by mass or more on the basis of the total amount of the composition from the viewpoint of sufficiently exerting the effect of improving the friction characteristics. It is more preferably 0.003% by mass or more, and even more preferably 0.005% by mass or more.

Next, optional components that can be blended in the present invention will be described.
Component (C):
In the gear oil composition of the present invention, a sulfur-based extreme pressure agent is preferably used as the optional component (C) from the viewpoint of improving extreme pressure.
Specific examples of the sulfur-based extreme pressure agent include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl (poly) sulfide, thiadiazole compounds, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, dialkylthiodipropionates. Examples thereof include compounds, sulfide mineral oil, zinc dithiophosphate compounds, zinc dithiocarbamate compounds, molybdenum dithiophosphates and molybdenum dithiocarbamates. These sulfur type extreme pressure agents may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  Sulfurized fats and oils are obtained by reacting sulfur and sulfur-containing compounds with fats and oils (lard oil, whale oil, vegetable oil, fish oil, etc.), and the sulfur content is not particularly limited, but is generally 5 to 30% by mass. Those are preferred. Specific examples thereof include sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil, sulfurized rice bran oil, and mixtures thereof.

  Examples of sulfurized fatty acids include sulfurized oleic acid, and examples of sulfurized esters include reaction of unsaturated fatty acids (including oleic acid, linoleic acid, or fatty acids extracted from the above-mentioned animal and vegetable oils) and various alcohols. And the like obtained by sulfiding the unsaturated fatty acid ester obtained by mixing with an arbitrary method, specifically, for example, methyl sulfide oleate, sulfurized rice bran fatty acid octyl, and a mixture thereof. Can be mentioned.

Examples of the sulfurized olefin include a compound represented by the following general formula (6).
This compound is obtained by reacting an olefin having 2 to 15 carbon atoms or a dimer to tetramer thereof with a sulfurizing agent such as sulfur or sulfur chloride, and propylene, isobutene, diisobutene and the like are preferable.

R ⁵ -S _a -R ⁶ (6)
[Wherein, R ⁵ represents an alkenyl group having 2 to 15 carbon atoms, R ⁶ represents an alkyl group or alkenyl group having 2 to 15 carbon atoms, and a represents an integer of 1 to 8. ]
Dihydrocarbyl (poly) sulfide is a compound represented by the following general formula (7). Here, when R ⁷ and R ⁸ are alkyl groups, they may be referred to as alkyl sulfides.

_{^{R 7 -S b -R 8 (7}} )
[Wherein, R ⁷ and R ⁸ may be the same or different and each represents a chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents an alkylaryl group of -20 or an arylalkyl group of 7-20 carbon atoms, and b represents an integer of 1-8. ]
As R ⁷ and R ⁸ in the general formula (7), specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or Branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched Undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group A linear or branched alkyl group such as a linear or branched octadecyl group, a linear or branched nonadecyl group, a linear or branched icosyl group; an aryl group such as a phenyl group or a naphthyl group; a tolyl group ( Includes all structural isomers , Ethylphenyl group (including all structural isomers), linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), Linear or branched pentylphenyl group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (all structural isomers) Straight chain or branched octylphenyl group (including all structural isomers), straight chain or branched nonylphenyl group (including all structural isomers), straight chain or branched decylphenyl group (all ), Linear or branched undecylphenyl group (including all structural isomers), linear or branched dodecylphenyl group (including all structural isomers), xylyl group (all Including structural isomers), ethyl Methylphenyl group (including all structural isomers), diethylphenyl group (including all structural isomers), di (straight or branched) propylphenyl group (including all structural isomers), di (direct Chain or branched) butylphenyl group (including all structural isomers), methylnaphthyl group (including all structural isomers), ethylnaphthyl group (including all structural isomers), linear or branched propyl Naphthyl group (including all structural isomers), linear or branched butyl naphthyl group (including all structural isomers), dimethylnaphthyl group (including all structural isomers), ethylmethylnaphthyl group (all Including structural isomers), diethyl naphthyl group (including all structural isomers), di (linear or branched) propyl naphthyl group (including all structural isomers), di (straight or branched) butyl Naphthyl group (all Alkylaryl groups such as isomers); arylalkyl groups such as benzyl, phenylethyl groups (including all isomers), and phenylpropyl groups (including all isomers); . Among these, R ⁷ and R ⁸ in the general formula (7), propylene, 1-butene or an alkyl group has been 3 to 18 carbon atoms derived from isobutylene, or an aryl group having a carbon number of 6-8, alkyl An aryl group or an arylalkyl group is preferable. Examples of these groups include isopropyl group, branched hexyl group derived from propylene dimer (including all branched isomers), and propylene trimer. Branched nonyl groups derived from the body (including all branched isomers), branched dodecyl groups derived from the propylene tetramer (including all branched isomers), 5 quantities of propylene Branched pentadecyl groups derived from the body (including all branched isomers), branched octadecyl groups derived from the propylene hexamer (including all branched isomers), sec Branched octyl group derived from butyl group, tert-butyl group, 1-butene dimer (including all branched isomers), branched octyl group derived from isobutylene dimer (all ), Branched dodecyl groups derived from 1-butene trimer (including all branched isomers), branched dodecyl groups derived from isobutylene trimer (Including all branched isomers), branched hexadecyl group derived from 1-butene tetramer (including all branched isomers), branched derived from isobutylene tetramer Alkyl groups such as hexadecyl group (including all branched isomers); phenyl group, tolyl group (including all structural isomers), ethylphenyl group (including all structural isomers), xylyl group (all (Including structural isomers) Groups; arylalkyl groups such as benzyl group and phenylethyl group (including all isomers).

Furthermore, R ⁷ and R ⁸ in the general formula (7) are each independently a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene from the viewpoint of improving the processing efficiency and tool life. It is more preferable that it is a branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene.

  Examples of the dihydrocarbyl (poly) sulfide represented by the general formula (7) include dibenzyl polysulfide, various dinonyl polysulfides, various didodecyl polysulfides, various dibutyl polysulfides, various dioctyl polysulfides, diphenyl polysulfide, dicyclohexyl polysulfide, and these. A mixture etc. can be mentioned preferably.

  Examples of the thiadiazole compound include 1,3,4-thiadiazole represented by the following general formula (8), 1,2,4-thiadiazole compound represented by the following general formula (9), and the following general formula (10). The 1,4,5-thiadiazole compound represented by these is mentioned.

［式中、Ｒ^９及びＲ^１０は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜２０の炭化水素基を示し、ｃ及びｄは同一でも異なっていてもよく、それぞれ０〜８の整数を示す］

[Wherein, R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; c and d may be the same or different; Indicates an integer]

  Specific examples of such thiadiazole compounds include 2,5-bis (n-hexyldithio) -1,3,4-thiadiazole, 2,5-bis (n-octyldithio) -1,3,4-thiadiazole. 2,5-bis (n-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (1,1,3,3-tetramethylbutyldithio) -1,3,4-thiadiazole, 3, 5-bis (n-hexyldithio) -1,2,4-thiadiazole, 3,5-bis (n-octyldithio) -1,2,4-thiadiazole, 3,5-bis (n-nonyldithio) -1 , 2,4-thiadiazole, 3,5-bis (1,1,3,3-tetramethylbutyldithio) -1,2,4-thiadiazole, 4,5-bis (n-hexyldithio) -1,2 , 3-thiadiazole, 4 5-bis (n-octyldithio) -1,2,3-thiadiazole, 4,5-bis (n-nonyldithio) -1,2,3-thiadiazole, 4,5-bis (1,1,3,3) Preferred examples include -tetramethylbutyldithio) -1,2,3-thiadiazole and a mixture thereof.

  Examples of the alkylthiocarbamoyl compound include compounds represented by the following general formula (11).

［式中、Ｒ^１１〜Ｒ^１４は同一でも異なっていてもよく、それぞれ炭素数１〜２０のアルキル基を示し、ｅは１〜８の整数を示す。］
このようなアルキルチオカルバモイル化合物の具体例としては、ビス（ジメチルチオカルバモイル）モノスルフィド、ビス（ジブチルチオカルバモイル）モノスルフィド、ビス（ジメチルチオカルバモイル）ジスルフィド、ビス（ジブチルチオカルバモイル）ジスルフィド、ビス（ジアミルチオカルバモイル）ジスルフィド、ビス（ジオクチルチオカルバモイル）ジスルフィドおよびこれらの混合物などを好ましく挙げることができる。

[Wherein, R ^{11 to} R ¹⁴ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, and e represents an integer of 1 to 8. ]
Specific examples of such alkylthiocarbamoyl compounds include bis (dimethylthiocarbamoyl) monosulfide, bis (dibutylthiocarbamoyl) monosulfide, bis (dimethylthiocarbamoyl) disulfide, bis (dibutylthiocarbamoyl) disulfide, and bis (diamil). Preferred examples include thiocarbamoyl) disulfide, bis (dioctylthiocarbamoyl) disulfide, and mixtures thereof.

  Examples of the alkylthiocarbamate compound include compounds represented by the following general formula (12).

［式中、Ｒ^１５〜Ｒ^１８は同一でも異なっていてもよく、それぞれ炭素数１〜２０のアルキル基を示し、Ｒ^１９は炭素数１〜１０のアルキル基を示す。］
このようなアルキルチオカーバメート化合物の具体例としては、メチレンビス（ジブチルジチオカーバメート）、メチレンビス［ジ（２−エチルヘキシル）ジチオカーバメート］などを好ましく挙げることができる。

[Wherein, R ^{15 to} R ¹⁸ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms, and R ¹⁹ represents an alkyl group having 1 to 10 carbon atoms. ]
Preferable examples of such alkylthiocarbamate compounds include methylenebis (dibutyldithiocarbamate), methylenebis [di (2-ethylhexyl) dithiocarbamate] and the like.

  Further, examples of the thioterpene compound include a reaction product of phosphorus pentasulfide and pinene, and examples of the dialkylthiodipropionate compound include dilauryl thiodipropionate, distearyl thiodipropionate, and a mixture thereof. be able to.

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, the mineral oil used in the sulfide mineral oil according to the present invention is not particularly limited. Specifically, specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is used as a solvent. Examples thereof include paraffinic mineral oil, naphthenic mineral oil, and the like, which are refined by appropriately combining purification treatments such as deblocking, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. In addition, as the elemental sulfur, any form such as a lump, powder, molten liquid, etc. may be used, but when powdered or molten liquid elemental sulfur is used, it is efficiently dissolved in the base oil. Is preferable. In addition, molten liquid elemental sulfur has the advantage that the melting operation can be performed in a very short time because the liquids are mixed together, but it must be handled above the melting point of elemental sulfur, heating equipment, etc. It is not always easy to handle because it requires special equipment and is handled in a high temperature atmosphere. On the other hand, powdery simple sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Moreover, although there is no restriction | limiting in particular in the sulfur content in the sulfide mineral oil concerning this invention, Preferably it is 0.05-1.0 mass% normally on the basis of the sulfide mineral oil whole quantity, More preferably, it is 0.1-0. 5% by mass.

The zinc dithiophosphate compound, the zinc dithiocarbamate compound, the molybdenum dithiophosphate and the molybdenum dithiocarbamate are respectively represented by the following general formulas (13) to (16).
:

Expression (13) in ^{~ (16), R 20,} R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R ³³ , R ³⁴ and R ³⁵ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X ² and X ³ each represent an oxygen atom or a sulfur atom]
The compound represented by these is meant.

^{Wherein, R 20, R 21, R} 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33, R 34 and ^{R 35} Specific examples of the hydrocarbon group represented by: methyl group, ethyl group, propyl group (including all branched isomers), butyl group (including all branched isomers), pentyl group (including All branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers), nonyl Groups (including all branched isomers), decyl groups (including all branched isomers), undecyl groups (including all branched isomers), dodecyl groups (including all branched isomers) , Tridecyl group (including all branched isomers), tetradecyl Groups (including all branched isomers), pentadecyl groups (including all branched isomers), hexadecyl groups (including all branched isomers), heptadecyl groups (including all branched isomers) , Octadecyl group (including all branched isomers), nonadecyl group (including all branched isomers), icosyl group (including all branched isomers), heicosyl group (including all branched isomers) Alkyl groups such as docosyl group (including all branched isomers), tricosyl group (including all branched isomers), tetracosyl group (including all branched isomers); cyclopentyl group, cyclohexyl Group, cycloalkyl group such as cycloheptyl group; methylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethyl Clopentyl group (including all substituted isomers), propylcyclopentyl group (including all branched isomers, including substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (including all substituted isomers) Substituted isomers), butylcyclopentyl group (all branched isomers, including substituted isomers), methylpropylcyclopentyl group (including all branched isomers, substituted isomers), diethylcyclopentyl group (all Substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (Including all substituted isomers), propylcyclohexyl groups (all Branched isomers, including substituted isomers, methylethylcyclohexyl group (including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), butylcyclohexyl group (all branched isomers, Substituted isomers), methylpropylcyclohexyl group (including all branched isomers, including substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers) ), Methylcycloheptyl group (including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group (including All branched isomers, including substituted isomers), methylethylcycloheptyl group (all substituted isomers) ), Trimethylcycloheptyl group (including all substituted isomers), butylcycloheptyl group (including all branched isomers, including substituted isomers), methylpropylcycloheptyl group (including all branched isomers), Substituted isomers), diethylcycloheptyl group (including all substituted isomers), dimethylethylcycloheptyl group (including all substituted isomers) and other alkyl cycloalkyl groups; phenyl group, naphthyl group and other aryls Group; tolyl group (including all substituted isomers), xylyl group (including all substituted isomers), ethylphenyl group (including all substituted isomers), propylphenyl group (all branched isomers, Substituted isomers), methylethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers) ), Butylphenyl group (including all branched and substituted isomers), methylpropylphenyl group (including all branched and substituted isomers), and diethylphenyl group (including all substituted isomers) Dimethylethylphenyl group (including all substituted isomers), pentylphenyl group (including all branched isomers, including substituted isomers), hexylphenyl group (including all branched isomers, substituted isomers) ), Heptylphenyl group (including all branched isomers, substituted isomers), octylphenyl group (including all branched isomers, substituted isomers), nonylphenyl group (all branched isomers, Substituted isomers), decylphenyl group (including all branched isomers, including substituted isomers), undecylphenyl group (including all branched isomers, including substituted isomers), dodecylphenyl Group (including all branched isomers, substituted isomers), tridecylphenyl group (including all branched isomers, substituted isomers), tetradecylphenyl group (all branched isomers, substituted isomers) ), Pentadecylphenyl group (including all branched and substituted isomers), hexadecylphenyl group (including all branched and substituted isomers), heptadecylphenyl group (including all branched isomers) Alkylaryl groups such as branched isomers, including substituted isomers, octadecylphenyl groups (including all branched isomers and substituted isomers); benzyl groups, phenethyl groups, phenylpropyl groups (all branched isomers) And arylalkyl groups such as phenylbutyl group (including all branched isomers).

  In the gear oil composition of the present invention, the content of the sulfur-based extreme pressure agent as the component (C) is arbitrary, but the lower limit on the basis of the total amount of the composition from the viewpoint of improving the extreme pressure of the obtained gear oil composition. The value is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. In addition, from the point that the effect of commensurate with the addition amount is not obtained even if blended more than that, the upper limit value of the content of the sulfur extreme pressure agent is preferably 10% by mass or less based on the total amount of the composition, It is more preferably 5% by mass or less, still more preferably 3% by mass or less, and most preferably 1% by mass or less.

(D) component:
In the gear oil composition of the present invention, an epoxy compound can be blended as the component (D) although it is an optional component from the viewpoint of sludge suppression. The following are mentioned as an epoxy compound.
(1) Phenyl glycidyl ether type epoxy compound,
(2) Alkyl glycidyl ether type epoxy compound (3) Glycidyl ester type epoxy compound (4) Allyl oxirane compound (5) Alkyl oxirane compound (6) Alicyclic epoxy compound (7) Epoxidized fatty acid monoester (8) Epoxidation Vegetable oil

  (1) Specific examples of the phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. As used herein, the alkylphenyl glycidyl ether includes those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl glycidyl. Ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl A glycidyl ether etc. can be illustrated as a preferable thing.

  (2) Specific examples of the alkyl glycidyl ether type epoxy compound include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol di Examples thereof include glycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether and the like.

(3) Specifically as a glycidyl ester type epoxy compound, the following general formula (17):

[Wherein R ³⁶ represents a hydrocarbon group having 1 to 18 carbon atoms]
The compound represented by these is mentioned.

In the above formula (17), R ³⁶ represents a hydrocarbon group having 1 to 18 carbon atoms. Examples of such a hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, C5-C7 cycloalkyl group, C6-C18 alkylcycloalkyl group, C6-C10 aryl group, C7-C18 alkylaryl group, C7-C18 arylalkyl group, etc. Is mentioned. Among these, an alkylphenyl group having an alkyl group having 5 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a phenyl group, and an alkyl group having 1 to 4 carbon atoms is preferable.

  Among the glycidyl ester type epoxy compounds, preferred examples include glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl-tert-butyl benzoate, glycidyl acrylate, glycidyl methacrylate, and the like.

  (4) Specific examples of the allyloxirane compound include 1,2-epoxystyrene, alkyl-1,2-epoxystyrene, and the like.

  (5) Specific examples of the alkyloxirane compound include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1 , 2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1, 2,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyicosane and the like.

(6) As an alicyclic epoxy compound, the following general formula (18):

And a compound in which the carbon atom constituting the epoxy group directly constitutes an alicyclic ring.

  Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.

  (7) Specific examples of the epoxidized fatty acid monoester include esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.

  (8) Specific examples of epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.

  When the epoxy compound as the component (D) is blended in the gear oil composition of the present invention, the blending amount is not particularly limited, but is usually based on the total amount of the gear oil composition (the sum of the base oil and all blended additives). It is desirable to add an epoxy compound in such an amount that the content is 0.1 to 5.0% by mass, and more preferably 0.2 to 2.0% by mass.

(E) component:
Although it is an optional component, from the viewpoint of oxidation stability, the gear oil composition of the present invention includes (EA) a phenolic antioxidant, (HB) an amine antioxidant, Or both can be contained.
As the (EA) phenolic antioxidant, any phenolic compound used as an antioxidant for lubricating oils can be used, and is not particularly limited. For example, the following general formula One or more alkylphenol compounds selected from the compounds represented by (19) or the general formula (20) are preferred.

In the general formula (19), R ³⁷ represents an alkyl group having 1 to 4 carbon atoms, R ³⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³⁹ represents a hydrogen atom, or 1 to 4 carbon atoms. A group represented by the following general formula (19-i) or a group represented by the following general formula (19-ii).

In the general formula (19-i), R ⁴⁰ represents an alkylene group having 1 to 6 carbon atoms, and R ⁴¹ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms.

In the general formula ^{(19-ii), R 43} represents an alkylene group having 1 to 6 carbon ^{atoms, R 43} represents an alkyl group having 1 to 4 carbon ^{atoms, R 44} is a hydrogen atom or 1 to 4 carbon atoms An alkyl group is shown.

In the general formula (20), R ⁴⁵ and R ⁴⁹ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ⁴⁶ and R ⁵⁰ each independently represent a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. Represents an alkyl group, R ⁴⁷ and R ⁴⁸ each independently represent an alkylene group having 1 to 6 carbon atoms, and X ⁴ represents an alkylene group having 1 to 18 carbon atoms or the following general formula (20-i). The group to be shown is shown.

In the general formula (20-i), R ⁵¹ and R ⁵² each independently represent an alkylene group having 1 to 6 carbon atoms.

In the general formula (19), specific examples of R ³⁷ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Although mentioned, a tert- butyl group is preferable from the point which is excellent in oxidation stability. Examples of R ³⁸ include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above, and a methyl group or a tert-butyl group is preferable from the viewpoint of excellent oxidation stability.

In the general formula (19), when R ³⁹ is an alkyl group having 1 to 4 carbon atoms, specifically, as R ³⁹ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a tert-butyl group, and the like can be mentioned. From the viewpoint of excellent oxidation stability, a methyl group or an ethyl group is preferable.

Among the alkylphenol compounds represented by the general formula (19), 2,6-di-tert-butyl-p-cresol is particularly preferable as a compound when R ³⁹ is an alkyl group having 1 to 4 carbon atoms. 2,6-di-tert-butyl-4-ethylphenol and mixtures thereof.

In the case where R ³⁹ in the general formula (19) is a group represented by the general formula (19-i), the alkylene group having 1 to 6 carbon atoms represented by R ⁴⁰ in the general formula (19-i) is: It may be linear or branched. Specifically, for example, methylene group, methylmethylene group, ethylene group (dimethylene group), ethylmethylene group, propylene group (methylethylene group), trimethylene group, linear chain Or a branched butylene group, a linear or branched pentylene group, a linear or branched hexylene group, etc. are mentioned.

R ⁴⁰ is an alkylene group having 1 to 2 carbon atoms, specifically, for example, a methylene group, a methylmethylene group, an ethylene group (dimethylene group), in that the compound represented by the general formula (19) can be produced with few reaction steps. Etc. are more preferable.

On the other hand, the alkyl group or alkenyl group having 1 to 24 carbon atoms represented by R ⁴¹ in the general formula (19-i) may be linear or branched, and specifically includes, for example, methyl group, ethyl group Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group Group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group and the like (these alkyl groups may be linear or branched); vinyl group, propenyl group, isopropenyl group, butenyl group, Pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dopenyl Decenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, octadecadienyl group, nonadecenyl group, icocenyl group, heicosenyl group, dococenyl group, tricocenyl group, tetracocenyl group, etc. The alkenyl group may be linear or branched, and the position of the double bond is arbitrary).

R ⁴¹ is an alkyl group having 4 to 18 carbon atoms, specifically, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, because of its excellent solubility in base oil. Alkyl groups such as undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group (these alkyl groups may be linear or branched) and have 6 carbon atoms. A linear or branched alkyl group having ˜12 is more preferable, and a branched alkyl group having 6 to 12 carbon atoms is particularly preferable.

Among the phenol compounds represented by the general formula (19), when R ³⁹ is a group represented by the general formula (19-i), R ⁴⁰ in the general formula (19-i) is carbon. More preferably, it is an alkylene group having 1 or 2 and R ⁴¹ is a linear or branched alkyl group having 6 to 12 carbon atoms, and R ⁴⁰ in the general formula (19-i) is 1 to 2 carbon atoms. Particularly preferred is an alkylene group having 2 and R ⁴¹ is a branched alkyl group having 6 to 12 carbon atoms.

  More specific examples of the more preferable compound include (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate n-hexyl, (3-methyl-5-tert-butyl-4-hydroxyphenyl) isohexyl acetate, N-heptyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, isoheptyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, (3-methyl-5-tert-butyl) -4-hydroxyphenyl) acetic acid n-octyl, (3-methyl-5-tert-butyl-4-hydroxyphenyl) isooctyl acetate, (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetic acid 2-ethylhexyl , (3-Methyl-5-tert-butyl-4-hydroxyphenyl) acetic acid n-no , Isononyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, n-decyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, (3-methyl-5-tert -Butyl-4-hydroxyphenyl) isodecyl acetate, (3-methyl-5-tert-butyl-4-hydroxyphenyl) n-undecyl acetate, (3-methyl-5-tert-butyl-4-hydroxyphenyl) isoundecyl acetate N-dodecyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, isododecyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) acetate, (3-methyl-5-tert- N-hexyl butyl-4-hydroxyphenyl) propionate, (3-methyl-5-tert-butyl) 4-Hydroxyphenyl) isohexyl propionate, n-heptyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, (3-methyl-5-tert-butyl-4-hydroxyphenyl) propion Isoheptyl acid, n-octyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, isooctyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, (3-methyl- 5-tert-butyl-4-hydroxyphenyl) propionic acid 2-ethylhexyl, (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionic acid n-nonyl, (3-methyl-5-tert-butyl- 4-hydroxyphenyl) isononyl propionate, (3-methyl N-decyl til-5-tert-butyl-4-hydroxyphenyl) propionate, isodecyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, (3-methyl-5-tert-butyl- 4-hydroxyphenyl) n-undecyl propionate, (3-methyl-5-tert-butyl-4-hydroxyphenyl) isoundecyl propionate, (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate n -Dodecyl, isododecyl (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, (3,5-di-tert-butyl-4-hydroxyphenyl) acetate n-hexyl, (3,5-di-) -Tert-butyl-4-hydroxyphenyl) isohexyl acetate, (3,5- -Tert-butyl-4-hydroxyphenyl) acetic acid n-heptyl, (3,5-di-tert-butyl-4-hydroxyphenyl) isoheptyl acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) N-octyl acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid 2-ethylhexyl, (3,5- N-nonyl di-tert-butyl-4-hydroxyphenyl) acetate, isononyl (3,5-di-tert-butyl-4-hydroxyphenyl) acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) ) N-decyl acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) isodecyl acetate, (3,5-di-) tert-butyl-4-hydroxyphenyl) acetic acid n-undecyl, (3,5-di-tert-butyl-4-hydroxyphenyl) isoundecyl acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid n-dodecyl, (3,5-di-tert-butyl-4-hydroxyphenyl) isododecyl acetate, (3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-hexyl, (3,5- Di-tert-butyl-4-hydroxyphenyl) isohexyl propionate, n-heptyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, (3,5-di-tert-butyl-4- Hydroxyphenyl) isoheptyl propionate, (3,5-di-tert-butyl-4-hydroxypheny N) -octyl propionate, (3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, 2-ethylhexyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N-nonyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isononyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, (3,5-di-tert -Butyl-4-hydroxyphenyl) n-decyl propionate, (3,5-di-tert-butyl-4-hydroxyphenyl) isodecyl propionate, (3,5-di-tert-butyl-4-hydroxyphenyl) N-undecyl propionate, (3,5-di-tert-butyl-4-hydroxyphenyl) propiate Isoundecylate, n-dodecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isododecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and mixtures thereof Etc.

In the case where R ³⁹ in the general formula (19) is a group represented by the general formula (19-ii), R ⁴² in the general formula (19-ii) represents an alkylene group having 1 to 6 carbon atoms. . The alkylene group may be linear or branched, and specific examples include various alkylene groups exemplified above for R ⁴⁰ . R ⁴² is an alkylene group having 1 to 3 carbon atoms, specifically, for example, a methylene group, a methylmethylene group, ethylene, because the compound of the general formula (19) can be produced with few reaction steps and its raw materials are easily available. A group (dimethylene group), ethylmethylene group, propylene group (methylethylene group), trimethylene group and the like are more preferable. Specific examples of R ⁴³ in the general formula (19-ii) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Although a butyl group etc. are mentioned, A tert-butyl group is preferable from the point which is excellent in oxidation stability. Examples of R ⁴⁴ include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above, and a methyl group or a tert-butyl group is preferable from the viewpoint of excellent oxidation stability.

Of the alkylphenol compounds represented by the general formula (19), specific examples of preferred compounds in the case where R ³⁹ is a group represented by the general formula (19-ii) include bis (3, 5-di-tert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-di-tert-butyl-4-hydroxyphenyl) ethane, 1,2-bis (3,5-di-) tert-butyl-4-hydroxyphenyl) ethane, 1,1-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 1,2-bis (3,5-di-tert-butyl- 4-hydroxyphenyl) propane, 1,3-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy) Siphenyl) propane, and mixtures thereof.

On the other hand, in the general formula (20), R ⁴⁵ and R ⁴⁹ are each independently an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-Butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like are shown, and from the viewpoint of excellent oxidation stability, both are preferably tert-butyl groups. R ⁴⁶ and R ⁵⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above. From the viewpoint of excellent oxidation stability, each is independently a methyl group or tert. -It is preferably a butyl group.

In the general formula (20), the alkylene group having 1 to 6 carbon atoms, which represents R ⁴⁷ and R ⁴⁸ , may be linear or branched. ^The various alkylene groups mentioned above about ⁴⁰ are mentioned. R ⁴⁷ and R ⁴⁸ are each independently an alkylene group having 1 to 2 carbon atoms in that the compound represented by the general formula (20) can be produced in a reaction process with few compounds and the raw material is easily available. Specifically, for example, a methylene group, a methylmethylene group, an ethylene group (dimethylene group) and the like are more preferable.

Further, in the general formula (20), the alkylene group having 1 to 18 carbon atoms representing X ⁴ specifically includes, for example, a methylene group, a methylmethylene group, an ethylene group (dimethylene group), an ethylmethylene group, and a propylene group. (Methylethylene group), trimethylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group , Octadecylene groups and the like (these alkylene groups may be linear or branched). From the viewpoint of easy availability of raw materials, an alkylene group having 1 to 6 carbon atoms, specifically, for example, a methylene group , Methylmethylene group, ethylene group (dimethylene group), ethylmethylene group, pro Pyrene group (methylethylene group), trimethylene group, butylene group, pentylene group, hexylene group and the like (these alkylene groups may be linear or branched) are more preferable, ethylene group (dimethylene group), trimethylene group, A linear alkylene group having 2 to 6 carbon atoms such as a linear butylene group (tetramethylene group, linear pentylene group (pentamethylene group), linear hexylene group (hexamethylene group), etc. is particularly preferred. Of the alkylphenol compounds represented, a compound represented by the following formula (21) is particularly preferable as a compound when X ⁴ is an alkylene group having 1 to 18 carbon atoms.

In addition, when X ⁴ in the general formula (20) is a group represented by the general formula (20-i), 1 to 1 carbon atoms represented by R ⁵¹ and R ⁵² in the general formula (20-i) The alkylene group 6 may be linear or branched, and specific examples include various alkylene groups as described above for R ⁴⁰ individually. R ⁵¹ and R ⁵² are each independently an alkylene group having 1 to 3 carbon atoms, specifically, for example, a methylene group, methyl, and the like, since the raw materials for producing the compound of the general formula (20) are easily available. More preferred are methylene group, ethylene group (dimethylene group), ethylmethylene group, propylene group (methylethylene group), trimethylene group and the like. Among the alkylphenols represented by the general formula (20), a compound represented by the following formula (22) is particularly preferable as a compound when X ⁴ is a group represented by the general formula (20-i). It is.

  As a matter of course, the (HA) component of the optional component of the present invention is one compound selected from alkylphenol compounds represented by the general formula (19) and the general formula (20). May be used alone, or a mixture of two or more compounds selected from the above in an arbitrary mixing ratio may be used.

  The upper limit of the component (EA) in the gear oil composition of the present invention is 3% by mass, preferably 2% by mass, more preferably 1% by mass based on the total amount of the composition. Even if the content exceeds 3% by mass, oxidation stability sufficient to meet the content and further improvement of the sludge formation inhibiting effect are not observed, and solubility in the base oil decreases, which is not preferable.

  On the other hand, the lower limit of the content of the component (EA) is 0.01% by mass, preferably 0.1% by mass, and more preferably 0.2% by mass based on the total amount of the composition. When the content of the component (EA) is less than 0.01% by mass, the effect of addition is not seen, and the oxidation stability and sludge generation suppressing effect of the gear oil composition may be deteriorated. It is not preferable.

  As the (E-B) amine-based antioxidant in the (E) component that can be added as an optional component, any amine-based compound used as an antioxidant for lubricating oils can be used, and is particularly limited. However, it is selected from, for example, (Np-alkyl) phenyl-α-naphthylamine represented by the following general formula (23) or p, p′-dialkyldiphenylamine represented by the general formula (24) One type or two or more types of aromatic amines are preferable.

In the general formula (23), R ⁵³ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.

In the general formula (24), R ⁵⁴ and R ⁵⁵ each independently represent an alkyl group having 1 to 16 carbon atoms.

In the general formula (23) representing (Np-alkyl) phenyl-α-naphthylamine, R ⁵³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 16 carbon atoms. When the number of carbon atoms in R ⁵³ exceeds 16, the proportion of the functional group in the molecule is small, and the antioxidant ability may be weakened. Specific examples of the alkyl group for R ⁵³ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, A tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group and the like (these alkyl groups may be linear or branched).

Among the compounds represented by the general formula (23), when R ⁵³ is an alkyl group, a branched alkyl group having 8 to 16 carbon atoms is preferable because of its excellent solubility of the oxidation product itself in the base oil. Further, a branched alkyl group having 8 to 16 carbon atoms derived from an oligomer of an olefin having 3 or 4 carbon atoms is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene, and isobutylene. From the viewpoint of excellent solubility of the oxidation product itself in the base oil, Propylene or isobutylene is preferred.

When (Np-alkyl) phenyl-α-naphthylamine represented by the above general formula (23) is used as the amine-based antioxidant (EB) component, R ⁵³ is a hydrogen molecule or a dimer of isobutylene. Branched octyl group derived from propylene, branched nonyl group derived from propylene trimer, branched dodecyl group derived from isobutylene trimer, branched dodecyl group derived from propylene tetramer Or a branched pentadecyl group derived from a pentamer of propylene is particularly preferred, a branched octyl group derived from a hydrogen molecule or a dimer of isobutylene, a branched dodecyl group or propylene derived from a trimer of isobutylene The branched dodecyl group derived from the tetramer of is particularly preferred.

When Np-alkylphenyl-α-naphthylamine in which R ⁵³ is an alkyl group is used as the aromatic amine represented by the general formula (23), this Np-alkylphenyl-α-naphthylamine is commercially available. A thing may be used. Further, phenyl-α-naphthylamine and an alkyl halide having 1 to 16 carbon atoms, an olefin having 2 to 16 carbon atoms, or an olefin oligomer having 2 to 16 carbon atoms and phenyl-α-naphthylamine using a Friedel-Crafts catalyst. It can be easily synthesized by reacting. Specific examples of Friedel-Crafts catalysts used here include metal halides such as aluminum chloride, zinc chloride, and iron chloride; sulfuric acid, phosphoric acid, phosphorus pentoxide, boron fluoride, acidic clay, activated clay, etc. Or an acidic catalyst.

On the other hand, in the general formula (24) representing p, p′-dialkyldiphenylamine, R ⁵⁴ and R ⁵⁵ each independently represents an alkyl group having 1 to 16 carbon atoms. When one or both of R ⁵⁴ and R ⁵⁵ are hydrogen atoms, they themselves may precipitate as sludge due to oxidation. On the other hand, when the number of carbon atoms exceeds 16, the proportion of functional groups in the molecule is small. Therefore, the antioxidant ability may be weakened.

Specific examples of R ⁵⁴ and R ⁵⁵ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, A tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group and the like (these alkyl groups may be linear or branched). Among these, as R ⁵⁴ and R ⁵⁵ , a branched alkyl group having 3 to 16 carbon atoms is preferable from the viewpoint of excellent solubility of the oxidation product itself in the base oil, and further an olefin having 3 or 4 carbon atoms, Alternatively, a branched alkyl group having 3 to 16 carbon atoms derived from the oligomer is more preferable. Specific examples of the olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene, and isobutylene, but the solubility of its own oxidation product in a lubricating base oil is excellent. From the viewpoint, propylene or isobutylene is preferable.

When p, p′-dialkyldiphenylamine represented by the above general formula (24) is used as the amine-based antioxidant (EB) component, R ⁵⁴ and R ⁵⁵ are isopropyl groups derived from propylene, and isobutylene. A tert-butyl group derived, a branched hexyl group derived from a dimer of propylene, a branched octyl group derived from a dimer of isobutylene, a branched nonyl group derived from a trimer of propylene, A branched dodecyl group derived from a trimer of isobutylene, a branched dodecyl group derived from a tetramer of propylene or a branched pentadecyl group derived from a pentamer of propylene is particularly preferred, and is derived from isobutylene. Derived from tert-butyl group, branched hexyl group derived from propylene dimer, isobutylene dimer Branched octyl, branched nonyl group derived from propylene trimer, is a branched dodecyl group derived from a tetramer of a branched dodecyl or propylene derived from a trimer of isobutylene particularly preferred.

  A commercially available product may be used as p, p'-dialkyldiphenylamine represented by the general formula (24). Further, similarly to the Np-alkylphenyl-α-naphthylamine represented by the general formula (23), diphenylamine and a halogenated alkyl compound having 1 to 16 carbon atoms, an olefin having 2 to 16 carbon atoms, or 2 to 2 carbon atoms. It can be easily synthesized by reacting 16 olefins or their oligomers with diphenylamine using a Friedel-Crafts catalyst. As the Friedel-Crafts catalyst in this case, specifically, for example, metal halides and acidic catalysts listed in the synthesis of Np-alkylphenyl-α-naphthylamine are used. As a matter of course, the component (H) as an optional component of the present invention includes one compound selected from the aromatic amines represented by the general formula (23) and the general formula (24). You may use independently, Furthermore, you may use the mixture etc. in the arbitrary mixing ratios of 2 or more types of compounds chosen from the above.

  The upper limit of the content of the (EB) amine-based antioxidant in the gear oil composition of the present invention is 3% by mass, preferably 2% by mass, more preferably 1% by mass based on the total amount of the composition. . Even if the content exceeds 3% by mass, further improvement in oxidation stability and sludge formation inhibiting effect commensurate with the content is not seen, and solubility in the base oil decreases, which is not preferable. On the other hand, the lower limit of the content of (EB) amine-based antioxidant is 0.01% by mass, preferably 0.1% by mass, and more preferably 0.2% by mass, based on the total amount of the composition. . (EB) When the content of the amine-based antioxidant is less than 0.01% by mass, the effect of addition is not seen, and the oxidation stability and sludge formation suppressing effect of the gear oil composition may be deteriorated. This is not preferable.

(F) component:
Although it is an optional component, in order to improve the extreme pressure of the gear oil composition of the present invention, (F) a phosphorus compound may be contained as component (F).
Specific examples of the phosphorus compound that can be contained herein include phosphoric acid esters such as phosphoric acid monoesters, phosphoric acid diesters, and phosphoric acid triesters; phosphorous acid monoesters, phosphorous acid diesters, Examples thereof include phosphites such as phosphite triesters; salts of these phosphate esters and phosphites; and mixtures thereof. The above-mentioned phosphate esters and phosphites are compounds containing a hydrocarbon group usually having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms.

  Specific examples of the hydrocarbon group having 2 to 30 carbon atoms include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. (these alkyl groups may be linear or branched); butenyl group, pentenyl group, hexenyl group, heptenyl group Alkenyl groups such as octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group and octadecenyl group (these alkenyl groups may be linear or branched) Good, and the position of the double bond is arbitrary); C5-C7 cycloalkyl group such as pentyl group, cyclohexyl group, cycloheptyl group; methylcyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group Alkylcycloalkyl groups having 6 to 11 carbon atoms such as diethylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, and diethylcycloheptyl group (the substitution position of the alkyl group to the cycloalkyl group is also arbitrary) Aryl groups such as phenyl group and naphthyl group: tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptyl Each alkylaryl group having 7 to 18 carbon atoms such as an phenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, an undecylphenyl group, a dodecylphenyl group (the alkyl group may be linear or branched, The substitution position on the aryl group is also arbitrary); each arylalkyl group having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group (these alkyl groups) May be linear or branched).

  As the phosphorus compound (F) component as an optional component that may be contained, preferred compounds include, for example, monopropyl phosphate, monobutyl phosphate, monopentyl phosphate, monohexyl phosphate, monopeptyl phosphate, mono Phosphoric monoalkyl esters such as octyl phosphate (the alkyl group may be linear or branched); mono (alkyl) aryl phosphates such as monophenyl phosphate and monocresyl phosphate; dipropyl phosphate, dibutyl phosphate, Dialkyl phosphates such as dipentyl phosphate, dihexyl phosphate, dipeptyl phosphate, dioctyl phosphate (alkyl groups may be linear or branched); diphenyl phosphate, dicresyl phosphate Phosphoric acid di (alkyl) aryl esters such as tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tripeptyl phosphate, trioctyl phosphate, etc. May be branched); tri (alkyl) aryl phosphates such as triphenyl phosphate and tricresyl phosphate; monopropyl phosphite, monobutyl phosphite, monopentyl phosphite, monohexyl phosphite, monopeptyl phosphine Phosphite monoalkyl esters such as phyte and monooctyl phosphite (the alkyl group may be linear or branched); Monophenyl phosphite and monocresyl phosphite ) Aryl esters; dialkyl phosphites such as dipropyl phosphite, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, dipeptyl phosphite, dioctyl phosphite (the alkyl group may be linear or branched) Good); di (alkyl) aryl phosphites such as diphenyl phosphite and dicresyl phosphite; tripropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, tripeptyl phosphite, trioctyl Trialkyl phosphites such as phosphites (the alkyl group may be linear or branched); tri (alkyl) aryl phosphites such as triphenyl phosphites and tricresyl phosphites; and these Mixture etc. Is mentioned.

  Specific examples of the salts of the phosphoric acid esters and phosphite esters described above include phosphoric acid monoesters, phosphoric acid diesters, phosphorous acid monoesters, phosphorous acid diester esters, ammonia, carbon Examples include salts obtained by allowing a nitrogen-containing compound such as an amine compound containing only a hydrocarbon group of 1 to 8 or a hydroxyl group-containing hydrocarbon group in the molecule to act to neutralize part or all of the remaining acidic hydrogen. It is done.

  Specific examples of the nitrogen-containing compound include ammonia; monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, dimethylamine, methylethylamine, Alkylamines such as diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, etc. May be branched); monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine , Monoheptanolamine, monooctanolamine, monononanolamine, dimethanolamine, methanolethanolamine, diethanolamine, methanolpropanolamine, ethanolpropanolamine, dipropanolamine, methanolbutanolamine, ethanolbutanolamine, propanolbutanolamine, dibutanol And alkanolamines such as amines, dipentanolamines, dihexanolamines, diheptanolamines, dioctanolamines (the alkanol groups may be linear or branched); and mixtures thereof.

  As a matter of course, the phosphorus compound that may be contained as the component (F) is one compound selected from the above-mentioned phosphate esters, phosphites, and salts thereof. May be used alone, or a mixture of two or more compounds selected from the above in an arbitrary mixing ratio may be used.

  The upper limit of the content of the phosphorus compound in the gear oil composition of the present invention is 10% by mass, preferably 5% by mass, more preferably 3% by mass based on the total amount of the composition. Even if the content exceeds 5% by mass, no further improvement in lubricity corresponding to the content is observed and oxidation stability is lowered, which is not preferable. On the other hand, the lower limit of the phosphorus compound content is 0.01% by mass, preferably 0.05% by mass, and more preferably 0.1% by mass, based on the total amount of the composition. When the content of the phosphorus compound is less than 0.01% by mass, the effect of addition is hardly exhibited.

(G) component:
Although it is an optional component, an oily agent can be added to the gear oil composition of the present invention as the component (G) from the viewpoint of improving the friction characteristics.
Examples of the oily agent include ester oily agents, alcohol oily agents, carboxylic acid oily agents, ether oily agents, amine oily agents, and amide oily agents.

  The ester oily agent is obtained by reacting an alcohol and a carboxylic acid. The alcohol may be a monohydric alcohol or a polyhydric alcohol. The carboxylic acid may be a monobasic acid or a polybasic acid.

  As the monohydric alcohol constituting the ester oil-based agent, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. May be saturated, saturated or unsaturated. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecane Decanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecanol, linear or branched icosa Lumpur, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as linear or branched tetracosanol, and mixtures thereof.

  Moreover, as a polyhydric alcohol which comprises ester oiliness agent, a 2-10 valence is used normally, Preferably a 2-6 valence is used. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylol alkanes (trimethylol ethane, trimethylol propane, trimethylol butane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof That.

  Among these polyhydric alcohols, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3- Propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylol Methylol butane and the like, and dimers and tetramers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol , 1,2,3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols and mixtures thereof, such as mannitol and the like are preferable. Even more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof.

  The alcohol constituting the ester oil agent according to the component (G) of the present invention may be a monohydric alcohol or a polyhydric alcohol as described above. It is preferable that

  Of the acids constituting the ester oily agent according to the component (G) of the present invention, as the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used, and the fatty acid is linear or branched. It may be saturated or unsaturated. Specifically, for example, acetic acid, propionic acid, linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptane Acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecane Acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched heptadecane Acid, linear or branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, linear or branched Henicosanoic acid, linear or branched Saturated fatty acids such as cosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid, acrylic acid, linear or branched butenoic acid, linear or branched pentenoic acid, Linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenoic acid, linear or branched decenoic acid, Linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, Linear or branched hexadecenoic acid, linear or branched heptadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecene Acid, linear or branched Unsaturated fatty acids such as cocenoic acid, linear or branched heicosenoic acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid, and the like And the like.

  Examples of the polybasic acid include dibasic acid and trimellitic acid, and dibasic acid is preferable. The dibasic acid may be a chain dibasic acid or a cyclic dibasic acid. Further, in the case of a chain dibasic acid, it may be either linear or branched, and may be either saturated or unsaturated. The chain dibasic acid is preferably a chain dibasic acid having 2 to 16 carbon atoms. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear Or branched pentanedioic acid, linear or branched hexanedioic acid, linear or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched nonane diacid Acid, linear or branched decanedioic acid, linear or branched undecanedioic acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or Branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or branched hexadecanedioic acid, linear or branched hexenedioic acid, linear or branched heptenedioic acid Linear or branched octene diacid, linear or branched nonene diacid, linear or branched Branched decenedioic acid, linear or branched undecenedioic acid, linear or branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched tetradecenedioic acid And linear or branched heptacene diacid, linear or branched hexadecene diacid, and mixtures thereof. Examples of the cyclic dibasic acid include 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, and aromatic dicarboxylic acid. Among these, a chain dibasic acid is preferable from the viewpoint of stability.

  The acid constituting the ester oily agent may be a monobasic acid or a polybasic acid as described above, but a monobasic acid is preferred from the viewpoint that the effect of improving friction characteristics is more excellent.

  The combination of the alcohol and the acid in the ester-based oily agent is arbitrary and is not particularly limited, and examples thereof include esters by the following combinations (i) to (vii).

(I) ester of monohydric alcohol and monobasic acid (ii) ester of polyhydric alcohol and monobasic acid (iii) ester of monohydric alcohol and polybasic acid (iv) polyhydric alcohol and polybasic acid (V) Monohydric alcohol, mixed ester of polyhydric alcohol and polybasic acid (vi) Mixed ester of polyhydric alcohol and monobasic acid, polybasic acid (vii) Monohydric alcohol A mixed ester of a mixture of a polyhydric alcohol and a monobasic acid or polybasic acid.

  Each of the esters (ii) to (vii) may be a complete ester in which all of the hydroxyl groups of the polyhydric alcohol or the carboxyl groups of the polybasic acid are esterified, and some of them are hydroxyl groups or carboxyl groups. The remaining partial ester may be used, but the partial ester is preferable from the viewpoint of the effect of improving the friction characteristics.

  Among the esters (i) to (vii) above, (ii) an ester of a polyhydric alcohol and a monobasic acid is preferable. This ester has a very high effect of improving friction characteristics.

In the ester (ii), the number of carbon atoms of the monobasic acid is preferably 10 or more, more preferably 12 or more, and still more preferably 14 or more, from the viewpoint that the frictional characteristics are further improved.
In addition, the number of carbon atoms of the monobasic acid is preferably 28 or less, more preferably 26 or less, and still more preferably 24 or less, from the viewpoint of preventing precipitation. Examples of such esters include glycerin monooleate and sorbitan monooleate.

  Examples of the alcohol oil-based agent include alcohols exemplified in the description of the ester oil-based agent. The number of carbon atoms in the alcohol oil-based agent is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more, from the viewpoint of improving frictional characteristics. Moreover, since there exists a possibility that it may precipitate easily when carbon number is too large, 24 or less are preferable, 20 or less are more preferable, and 18 or less are the most preferable.

  The carboxylic acid oily agent may be a monobasic acid or a polybasic acid. Examples of such carboxylic acids include monobasic acids and polybasic acids exemplified in the description of the ester oily agent. Among these, a monobasic acid is preferable from the viewpoint of improving the friction characteristics. In addition, the number of carbon atoms of the carboxylic acid oil-based agent is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more from the viewpoint of improving the friction characteristics. Moreover, since there exists a possibility that it may precipitate easily when carbon number of a carboxylic acid oiliness agent is too large, 24 or less are preferable, 20 or less are more preferable, and 18 or less are the most preferable.

  Examples of ether oily agents include etherified products of 3 to 6 aliphatic polyhydric alcohols, bimolecular condensates or trimolecular condensates of 3 to 6 aliphatic polyhydric alcohols, and the like.

［式中、Ｒ^５６〜Ｒ^８０は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜１８の直鎖状もしくは分岐鎖状のアルキル基、アリル基、アラルキル基、−（Ｒ^aＯ）_n−Ｒ^b（Ｒ^aは炭素数２〜６のアルキレン基、Ｒ^bは炭素数１〜２０のアルキル基、アリル基、アラルキル基、ｎは１〜１０の整数を示す）で示されるグリコールエーテル残基を示す。］ The etherified product of a 3-6 valent aliphatic polyhydric alcohol is represented by the following general formulas (25)-(30), for example.

[Wherein R ^{56 to} R ⁸⁰ may be the same or different, and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, an allyl group, an aralkyl group, — (R ^a O ) _N -R ^b (R ^a is an alkylene group having 2 to 6 carbon atoms, R ^b is an alkyl group having 1 to 20 carbon atoms, an allyl group, an aralkyl group, and n is an integer of 1 to 10) Indicates an ether residue. ]

Specific examples of the 3-6 valent aliphatic polyhydric alcohol include glycerin, trimethylolpropane, erythritol, pentaerythritol, arabitol, sorbitol, mannitol and the like. R ^{77 to} R ¹⁰¹ in the general formulas (37) to (42) are methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, Various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, phenyl groups, benzyl groups, etc. Is mentioned. The etherified product also includes a partially etherified product in which a part of R ^{56 to} R ⁸⁰ is a hydrogen atom.

［式中、Ｒ^５６〜Ｒ^５８及びＲ^６６〜Ｒ^６９はそれぞれ式（２５）中のＲ^５６〜Ｒ^５８及び式（２８）中のＲ^６６〜Ｒ^６９と同一の定義内容を示す。］
３〜６価の脂肪族多価アルコールの二分子縮合物，三分子縮合物の具体例としては、ジグリセリン、ジトリメチロールプロパン、ジペンタエリスリトール、ジソルビトール、トリグリセリン、トリトリメチロールプロパン、トリペンタエリスリトール、トリソルビトールなどが挙げられる。 As the etherified product of a bimolecular condensate or a trimolecular condensate of a 3-6 valent aliphatic polyhydric alcohol, the same or different condensates of the compounds represented by the general formulas (25) to (30) are used. Is mentioned. For example, the bimolecular condensate of alcohol and the etherified product of trimolecular condensate represented by general formula (25) are represented by general formulas (31) and (32), respectively. Moreover, the etherified product of the alcohol bimolecular condensate and trimolecular condensate represented by the general formula (27) is represented by the general formulas (33) and (34), respectively.

^Wherein indicates the R 56 ^{to R 58} and the same definition as ^R 66 ^{to R 69} of ^R 56 ^{to R 58} and the formula (28) in ^R 66 ^{to R 69} each formula (25). ]
Specific examples of bimolecular and trimolecular condensates of 3-6 valent aliphatic polyhydric alcohols include diglycerin, ditrimethylolpropane, dipentaerythritol, disorbitol, triglycerin, tritrimethylolpropane, and tripentaerythritol. And trisorbitol.

Specific examples of the ether oily agents represented by the general formulas (25) to (34) include trihexyl ether of glycerin, dimethyl octyl triether of glycerin, di (methyloxyisopropylene) dodecyl triether of glycerin, and glycerin. Diphenyl octyl triether, di (phenyloxyisopropylene) dodecyl triether of glycerin, trihexyl ether of trimethylol propane, dimethyl octyl triether of trimethylol propane, di (methyloxy isopropylene) dodecyl triether of trimethylol propane, Tetrahexyl ether of pentaerythritol, trimethyloctyl tetraether of pentaerythritol, tri (methyloxyisopropylene) dodecylte of pentaerythritol Laether, Hexapropyl ether of sorbitol, Tetramethyloctylpentaether of sorbitol, Hexa (methyloxyisopropylene) ether of sorbitol, Tetrabutyl ether of diglycerin, Dimethyldioctyltetraether of diglycerin, Tri (methyloxyisopropylene) ) Dodecyl tetraether, triglycerol pentaethyl ether, triglycerol trimethyldioctylpentaether, triglycerol tetra (methyloxyisopropylene) decylpentaether, ditrimethylolpropane tetrabutylether, ditrimethylolpropane dimethyldioctyltetraether, Tri (methyloxyisopropylene) dodecyltetrae of ditrimethylolpropane Ter, tritrimethylolpropane pentaethyl ether, tritrimethylolpropane trimethyldioctylpentaether, tritrimethylolpropane tetra (methyloxyisopropylene) decylpentaether, dipentaerythritol hexapropylether, dipentaerythritol pentamethyloctylhexa Ether, dipentaerythritol hexa (methyloxyisopropylene) ether, tripentaerythritol octapropyl ether, tripentaerythritol pentamethyloctyl hexaether, tripentaerythritol hexa (methyloxyisopropylene) ether, disorbitol octater Methyl dioctyl deca ether, disorbitol deca (methyloxyisopropylate N) ether.
Among these, diphenyl octyl triether of glycerin, di (methyloxyisopropylene) dodecyl triether of trimethylolpropane, tetrahexyl ether of pentaerythritol, hexapropyl ether of sorbitol, dimethyldioctyl tetraether of diglycerin, triglycerin of triglycerin Tetra (methyloxyisopropylene) decyl pentaether, hexapentyl ether of dipentaerythritol, and pentamethyloctyl hexaether of tripentaerythritol are preferred.

  In addition, (G-1) amine oily agent, (G-2) amide oily agent, etc. are mentioned as the oily agent as (G) component which can be used by this invention.

  Examples of (G-1) amine oily agents include monoamines, polyamines, alkanolamines, etc. Among these, monoamines are preferred from the viewpoint of improving frictional properties.

Specific examples of monoamines include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine (including all isomers), dipropylamine (including all isomers), Propylamine (including all isomers), monobutylamine (including all isomers), dibutylamine (including all isomers), tributylamine (including all isomers), monopentylamine (all including all isomers) Including isomers), dipentylamine (including all isomers), tripentylamine (including all isomers), monohexylamine (including all isomers), dihexylamine (including all isomers) ), Monoheptylamine (including all isomers), diheptylamine (including all isomers) ), Monooctylamine (including all isomers), dioctylamine (including all isomers), monononylamine (including all isomers), monodecylamine (including all isomers), monoundecyl (Including all isomers), monododecylamine (including all isomers), monotridecylamine (including all isomers), monotetradecylamine (including all isomers), monopentadecyl Amine (including all isomers), monohexadecylamine (including all isomers), monoheptadecylamine (including all isomers), monooctadecylamine (including all isomers), mononona Decylamine (including all isomers), monoicosylamine (including all isomers), monohenicosylamine (including all isomers), monodocosyl Min (including all isomers), monotricosylamine (including all isomers), dimethyl (ethyl) amine, dimethyl (propyl) amine (including all isomers), dimethyl (butyl) amine (all Isomers), dimethyl (pentyl) amine (including all isomers), dimethyl (hexyl) amine (including all isomers), dimethyl (heptyl) amine (including all isomers), dimethyl ( Octyl) amine (including all isomers), dimethyl (nonyl) amine (including all isomers), dimethyl (decyl) amine (including all isomers), dimethyl (undecyl) amine (all isomers) ), Dimethyl (dodecyl) amine (including all isomers), dimethyl (tridecyl) amine (including all isomers), dimethyl (tetradecyl) ) Amine (including all isomers), dimethyl (pentadecyl) amine (including all isomers), dimethyl (hexadecyl) amine (including all isomers), dimethyl (heptadecyl) amine (all isomers) ), Dimethyl (octadecyl) amine (including all isomers), dimethyl (nonadecyl) amine (including all isomers), dimethyl (icosyl) amine (including all isomers), dimethyl (henicosyl) Alkylamines such as amines (including all isomers), dimethyl (tricosyl) amine (including all isomers);
Monovinylamine, divinylamine, trivinylamine, monopropenylamine (including all isomers), dipropenylamine (including all isomers), tripropenylamine (including all isomers), monobutenylamine (Including all isomers), dibutenylamine (including all isomers), tributenylamine (including all isomers), monopentenylamine (including all isomers), dipentenylamine (all isomers) ), Tripentenylamine (including all isomers), monohexenylamine (including all isomers), dihexenylamine (including all isomers), monoheptenylamine (all isomers) ), Diheptenylamine (including all isomers), monooctenylamine (including all isomers), dioctenylamine (Including all isomers), monononenylamine (including all isomers), monodecenylamine (including all isomers), monoundecenyl (including all isomers), monododecenylamine (Including all isomers), monotridecenylamine (including all isomers), monotetradecenylamine (including all isomers), monopentadecenylamine (including all isomers), Monohexadecenylamine (including all isomers), monoheptadecenylamine (including all isomers), monooctadecenylamine (including all isomers), monononadecenylamine (all isomers) ), Monoicosenylamine (including all isomers), monohenicocenylamine (including all isomers), monodocosenylamine (including all isomers), Trichoderma cell (including all isomers) cycloalkenyl amines alkenyl amines, such as;
Dimethyl (vinyl) amine, dimethyl (propenyl) amine (including all isomers), dimethyl (butenyl) amine (including all isomers), dimethyl (pentenyl) amine (including all isomers), dimethyl ( Hexenyl) amine (including all isomers), dimethyl (heptenyl) amine (including all isomers), dimethyl (octenyl) amine (including all isomers), dimethyl (nonenyl) amine (all isomers) ), Dimethyl (decenyl) amine (including all isomers), dimethyl (undecenyl) amine (including all isomers), dimethyl (dodecenyl) amine (including all isomers), dimethyl (tridecenyl) Amine (including all isomers), dimethyl (tetradecenyl) amine (including all isomers), dimethyl (pen Decenyl) amine (including all isomers), dimethyl (hexadecenyl) amine (including all isomers), dimethyl (heptadecenyl) amine (including all isomers), dimethyl (octadecenyl) amine (all isomers) ), Dimethyl (nonadecenyl) amine (including all isomers), dimethyl (icosenyl) amine (including all isomers), dimethyl (henicosenyl) amine (including all isomers), dimethyl (tricosenyl) Monoamines having alkyl and alkenyl groups such as amines (including all isomers);
Monobenzylamine, (1-phenyltyl) amine, (2-phenylethyl) amine (also known as monophenethylamine), dibenzylamine, bis (1-phenethyl) amine, bis (2-phenylethylene) amine (also known as diphenethylamine) Aromatic substituted alkylamines such as
C5-C16 cycloalkylamines such as monocyclopentylamine, dicyclopentylamine, tricyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine;
Monoamines having an alkyl group and a cycloalkyl group, such as dimethyl (cyclopentyl) amine, dimethyl (cyclohexyl) amine, dimethyl (cycloheptyl) amine;
(Methylcyclopentyl) amine (including all substituted isomers), bis (methylcyclopentyl) amine (including all substituted isomers), (dimethylcyclopentyl) amine (including all substituted isomers), bis (dimethylcyclopentyl) ) Amine (including all substituted isomers), (ethylcyclopentyl) amine (including all substituted isomers), bis (ethylcyclopentyl) amine (including all substituted isomers), (methylethylcyclopentyl) amine ( All substituted isomers included), bis (methylethylcyclopentyl) amine (including all substituted isomers), (diethylcyclopentyl) amine (including all substituted isomers), (methylcyclohexyl) amine (all substituted isomers) Isomers), bis (methylcyclohexyl) amine (all substituted isomers) ), (Dimethylcyclohexyl) amine (including all substituted isomers), bis (dimethylcyclohexyl) amine (including all substituted isomers), (ethylcyclohexyl) amine (including all substituted isomers), bis (Ethylcyclohexyl) amine (including all substituted isomers), (Methylethylcyclohexyl) amine (including all substituted isomers), (Diethylcyclohexyl) amine (including all substituted isomers), (Methylcycloheptyl) ) Amine (including all substituted isomers), bis (methylcycloheptyl) amine (including all substituted isomers), (dimethylcycloheptyl) amine (including all substituted isomers), (ethylcycloheptylamine) (Including all substituted isomers), (methylethylcycloheptyl) amine (all substituted isomers) And alkyl cycloalkylamines such as (diethylcycloheptyl) amine (including all substituted isomers), etc. The monoamine also includes monoamines derived from fats and oils such as beef tallow amine. It is.

  Among the above-mentioned monoamines, alkylamine, monoamine having an alkyl group and an alkenyl group, monoamine having an alkyl group and a cycloalkyl group, cycloalkylamine and alkylcycloalkylamine are particularly preferable from the viewpoint of improving frictional properties, alkylamine, A monoamine having an alkyl group and an alkenyl group is more preferable.

  Although there is no restriction | limiting in particular about carbon number of a monoamine, It is preferable that it is 8 or more from the point of rust prevention property, and it is more preferable that it is 12 or more. Further, from the viewpoint of improving the friction characteristics, it is preferably 24 or less, and more preferably 18 or less.

  Further, the number of hydrocarbon groups bonded to the nitrogen atom in the monoamine is not particularly limited, but is preferably 1 or 2 and more preferably 1 from the viewpoint of improving the frictional characteristics.

  (G-2) Amide oil-based agent, amine compound containing only fatty acids having 6 to 30 carbon atoms and acid chlorides thereof, ammonia, hydrocarbon groups having 1 to 8 carbon atoms or hydroxyl group-containing hydrocarbon groups in the molecule An amide obtained by reacting a nitrogen-containing compound such as

  The fatty acid here may be a linear fatty acid or a branched fatty acid, and may be a saturated fatty acid or an unsaturated fatty acid. The carbon number is 6-30, preferably 9-24.

  Specific examples of the fatty acid include heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, Saturated fatty acids such as icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid and triacontyl group (these saturated fatty acids may be linear or branched) ); Heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid (including oleic acid), nonadecenoic acid, icosenic acid, Henicosenoic acid Unsaturated fatty acids such as docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic acid, heptacosenoic acid, octacosenoic acid, nonacenoic acid, triacontenoic acid (these unsaturated fatty acids may be linear or branched, The position of the heavy bond is also arbitrary); but the linear fatty acids derived from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, various fats and oils (coconut oil fatty acid etc.) A mixture of linear fatty acid and branched fatty acid synthesized by the oxo method or the like is preferably used.

  Specific examples of the nitrogen-containing compound to be reacted with the fatty acid include ammonia; monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, dimethylamine, Alkylamines such as methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, etc. May be chain or branched); monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexene Noramine, monoheptanolamine, monooctanolamine, monononanolamine, dimethanolamine, methanolethanolamine, diethanolamine, methanolpropanolamine, ethanolpropanolamine, dipropanolamine, methanolbutanolamine, ethanolbutanolamine, propanolbutanolamine, di Examples thereof include alkanolamines such as butanolamine, dipentanolamine, dihexanolamine, diheptanolamine and dioctanolamine (the alkanol group may be linear or branched); and mixtures thereof.

Specific examples of fatty acid amides include lauric acid amide, lauric acid diethanolamide, lauric acid monopropanolamide, myristic acid amide, myristic acid diethanolamide, myristic acid monopropanolamide, palmitic acid amide, palmitic acid diethanolamide, and palmitic acid. Acid monopropanolamide, stearic acid amide, stearic acid diethanolamide, stearic acid monopropanolamide, oleic acid amide, oleic acid diethanolamide, oleic acid monopropanolamide, coconut oil fatty acid amide, coconut oil fatty acid diethanolamide, coconut oil fatty acid mono Propanolamide, C12-13 synthetic mixed fatty acid amide, C12-13 synthetic mixed fatty acid diethanolamide, C12-13 synthetic blend Fatty acid mono-propanol amides, and mixtures thereof are particularly preferred.
Among the oily agents, preferred are a polyhydric alcohol partial ester and an aliphatic amide from the viewpoint of an effect of improving frictional properties.

  The content of the oily agent as the component (G) is arbitrary, but is preferably 0.01% by mass or more, more preferably 0.05%, based on the total amount of the composition, from the viewpoint of excellent effect of improving the friction characteristics. It is at least mass%, more preferably at least 0.1 mass%. In addition, the content is preferably 10% by mass or less, more preferably 7.5% by mass or less, and further preferably 5% by mass or less, based on the total amount of the composition, from the viewpoint of precipitation prevention.

(H) component:
Although it is an optional component, to the gear oil composition of the present invention, a triazole represented by the general formula (35) and / or a derivative thereof is added as the component (H) from the viewpoint of improving thermal and oxidation stability. Can do.

上式中、２つの点線はトリアゾール環に置換する同一または異なる置換基、好ましくは炭化水素基をそれぞれ表し、両者は互いに結合して環状基、たとえば縮合ベンゼン環を構成することができる。
トリアゾールおよび／またはその誘導体として好ましい化合物は、ベンゾトリアゾール及び／又はその誘導体である。

In the above formula, two dotted lines represent the same or different substituents substituted on the triazole ring, preferably a hydrocarbon group, respectively, and both can be bonded to each other to form a cyclic group, for example, a condensed benzene ring.
A preferable compound as triazole and / or a derivative thereof is benzotriazole and / or a derivative thereof.

  As said benzotriazole, the compound represented by following formula (36) is illustrated.

  Examples of the benzotriazole derivative include alkylbenzotriazole represented by the following general formula (37), (alkyl) aminoalkylbenzotriazole represented by the general formula (38), and the like.

In the above formula (37), R ⁸¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and x is 1 to 3, preferably 1 or 2. Indicates the number of Examples of R ⁸¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. As the alkylbenzotriazole represented by the formula (37), a compound in which R ⁸¹ is a methyl group or an ethyl group and x is 1 or 2 is particularly preferable from the viewpoint of excellent antioxidant properties. Examples thereof include triazole (tolyltriazole), dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole, and mixtures thereof.

In the above formula (38), R ⁸² represents a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, R ⁸³ represents a methylene group or an ethylene group, and R ⁸⁴ And R ^{85, which} may be the same or different, are a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. And y represents a number of 0 to 3, preferably 0 or 1. Examples of R ⁸² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. As R ⁸⁴ and R ⁸⁵ , for example, a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or A branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a linear or branched nonyl group, a linear or branched decyl group, Linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched Alkyl groups such as a hexadecyl group, a linear or branched heptadecyl group, and a linear or branched octadecyl group.

As the (alkyl) aminobenzotriazole represented by the above formula (38), R ⁸² is a methyl group, y is 0 or 1, and R ⁸³ is a methylene group or the an ethylene group, R ⁸⁴ and R ⁸⁵ is a straight-chain or branched dialkylaminoalkyl benzotriazole or dialkylaminoalkyl tolyltriazole or an alkyl group mixtures thereof having 1 to 12 carbon atoms are preferably used. Examples of these dialkylaminoalkylbenzotriazoles include dimethylaminomethylbenzotriazole, diethylaminomethylbenzotriazole, di (linear or branched) propylaminomethylbenzotriazole, and di (linear or branched) butylaminomethylbenzotriazole. , Di (straight or branched) pentylaminomethylbenzotriazole, di (straight or branched) hexylaminomethylbenzotriazole, di (straight or branched) heptylaminomethylbenzotriazole, di (straight or branched) ) Octylaminomethylbenzotriazole, di (straight or branched) nonylaminomethylbenzotriazole, di (straight or branched) decylaminomethylbenzotriazole, di (straight or branched) undecylaminomethylbenzotriazole, (Linear or branched) dodecylaminomethylbenzotriazole; dimethylaminoethylbenzotriazole, diethylaminoethylbenzotriazole, di (linear or branched) propylaminoethylbenzotriazole, di (linear or branched) butylaminoethylbenzo Triazole, di (straight or branched) pentylaminoethylbenzotriazole, di (straight or branched) hexylaminoethylbenzotriazole, di (straight or branched) heptylaminoethylbenzotriazole, di (straight or branched) Branch) Octylaminoethylbenzotriazole, Di (straight or branched) nonylaminoethylbenzotriazole, Di (straight or branched) decylaminoethylbenzotriazole, Di (straight or branched) undecylaminoethylbenzotriazole , Di (linear or straight Branched) dodecylaminoethyl benzotriazole; dimethylaminomethyltolyltriazole, diethylaminomethyltolyltriazole, di (linear or branched) propylaminomethyltolyltriazole, di (straight or branched) butylaminomethyltolyltriazole, di ( Linear or branched) pentylaminomethyltolyltriazole, di (linear or branched) hexylaminomethyltolyltriazole, di (straight or branched) heptylaminomethyltolyltriazole, di (linear or branched) octylamino Methyltolyltriazole, di (linear or branched) nonylaminomethyltolyltriazole, di (straight or branched) decylaminomethyltolyltriazole, di (straight or branched) undecylaminomethyltolyltriazole, di (direct Chain or branch) Silaminomethyltolyltriazole; dimethylaminoethyltolyltriazole, diethylaminoethyltolyltriazole, di (linear or branched) propylaminoethyltolyltriazole, di (linear or branched) butylaminoethyltolyltriazole, di (linear or Branched) pentylaminoethyltolyltriazole, di (straight or branched) hexylaminoethyltolyltriazole, di (straight or branched) heptylaminoethyltolyltriazole, di (straight or branched) octylaminoethyltolyltriazole , Di (linear or branched) nonylaminoethyl tolyl triazole, di (linear or branched) decylaminoethyl tolyl triazole, di (linear or branched) undecylaminoethyl tolyl triazole, di (linear or branched) Branch) Dodecylamino Tilt Lil triazole; or mixtures thereof.

  The content of the triazole and / or derivative thereof as the optional component (H) is arbitrary, but is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total amount of the composition. is there. When the amount is less than 0.001% by mass, the effect of improving thermal and oxidation stability due to the inclusion of triazole and / or a derivative thereof may be insufficient. Further, the content of triazole and / or a derivative thereof is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the total amount of the composition. When it exceeds 1.0 mass%, there is a possibility that it is economically disadvantageous because the effect of improving the thermal and oxidation stability sufficient for the content cannot be obtained.

Other optional ingredients:
In the present invention, as described above, a gear oil composition excellent in energy saving can be obtained only by adding the component (A) and / or the component (B) to the base oil. In addition, if necessary, various additives represented by rust inhibitors, metal deactivators, viscosity index improvers, cleaning dispersants, pour point depressants, antifoaming agents, etc., alone or in combination You may make it contain in combination.

  Specific examples of rust inhibitors include metal soaps such as fatty acid metal salts, lanolin fatty acid metal salts, and oxidized wax metal salts; partial alcohol esters such as sorbitan fatty acid esters; esters such as lanolin fatty acid esters; Examples thereof include sulfonates such as calcium sulfonate and barium sulfonate; oxidized wax; amines; phosphoric acid; In the present invention, one or two or more compounds arbitrarily selected from these rust inhibitors can be contained in any amount, but usually the content is the total amount of the oil composition. It is desirable that the content is 0.01 to 1% by mass.

  Specific examples of the metal deactivator include imidazole compounds as well as the benzotriazole compounds mentioned as the component (H). In the present invention, one or two or more compounds arbitrarily selected from these metal deactivators can be contained in any amount, but usually the content is determined by the oil composition. It is desirable that it is 0.001-1 mass% on the basis of the total amount of things.

  Specific examples of the viscosity index improver include copolymers of one or more monomers selected from various methacrylates or hydrogenated products thereof, ethylene-α-olefin copolymers (as α-olefins). Can be exemplified by propylene, 1-butene, 1-pentene, etc.) or hydrogenated products thereof, polyisobutylene or hydrogenated products thereof, styrene-diene hydrogenated copolymers and polyalkylstyrenes, etc. An agent etc. can be illustrated. Examples of the cleaning dispersant include alkenyl succinimide, sulfonate, salicylate, phenate and the like. One or two or more compounds arbitrarily selected from these viscosity index improvers and detergent dispersants can be contained in any amount, but the content is usually the total amount of the oil composition. It is desirable that the content is 0.01 to 10% by mass.

  Specific examples of the pour point depressant include copolymers of one or more monomers selected from various acrylic esters and methacrylic esters or hydrogenated products thereof. One kind or two or more kinds of compounds arbitrarily selected from these pour point depressants can be contained in any amount, and the content is usually 0.00 on the basis of the total amount of the oil composition. It is desirable that it is 01-5 mass%.

  Specific examples of the antifoaming agent include silicones such as dimethyl silicone and fluorosilicone. In the present invention, one or two or more compounds arbitrarily selected from these antifoaming agents can be contained in any amount, but usually the content is the total amount of the oil composition. It is desirable that it is 0.0001-0.05 mass% on the basis.

Use:
The gear oil composition of the present invention is used for various industrial machines, automobiles, railway vehicles, etc., but also as, for example, hydraulic fluid, turbine oil, compressor oil, slip guide surface oil, bearing oil, etc. Can be used.

The present invention will be further described below with reference to examples and comparative examples.
The types and amounts of the base oils tested and the additives added thereto are shown below. Moreover, the test method performed about each mix | blended lubricating oil composition is also shown below similarly. The obtained test results are summarized in Tables 1 to 3.

(IAE oil temperature)
In accordance with the IAE gear test specified in IP166 / 77 (92), the engine was operated at a rotational speed of 6000 rpm, an oil amount of 1250 ml, and a load of 80 lbs. The oil temperature of the gear box after 120 minutes was measured.
(Chimken test)
Based on JIS K2519, the OK load of each lubricating oil composition was measured.

(Base oil)
Base oil 1: solvent refined paraffinic mineral oil (kinematic viscosity 150mm ² / s (40 ° C), viscosity index 95)
Base oil 2: 1-decene oligomer (kinematic viscosity 150 mm ² / s (40 ° C.), viscosity index 140)
Base oil 3: Polyol ester obtained using a mixture of pentaerythritol and dipentaerythritol and a linear saturated fatty acid having 5 to 12 carbon atoms (kinematic viscosity 150 mm ² / s (40 ° C.), viscosity index 120)

(Additive)
(A) Component A1: N-oleoyl sarcosine (B) Component B1: Nonylphenoxyacetic acid (C) Component C1: 2,5-bis (n-nonyldithio) -1,3,4-thiadiazole C2: Zinc dioctyldithiophosphate (ZnDTP)
Other additives Amine: Dioctyldiphenylamine DBPC: Di-tertbutyl-p-cresol TCP: tricresyl phosphate

Claims (1)

Base oil is at least one selected from mineral oil, fat and synthetic oil,
A gear oil composition containing the component (A) and / or the component (B),
(A) component consists of at least 1 type of the compound represented by the following general formula (1)-(3),
R ¹ —CO—NR ² — (CH ₂ ) _n —COOX ¹ (1)
(In the formula, R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, X ¹ is hydrogen, and an alkyl group having 1 to 30 carbon atoms. Or an alkenyl group having 1 to 30 carbon atoms, and n represents an integer of 1 to 4.)
[R1-CO-NR2- (CH 2) n -COO] m Y 1 (2)
Wherein R ^{1 is} an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, Y ¹ is an alkali metal or alkaline earth metal, and n is 1 An integer of ˜4, m is 1 when Y is an alkali metal, and 2 when Y is an alkaline earth metal.
^{[R 1 -CO-NR 2 -} (CH 2) n -COO] m -Z- (OH) m '(3)
(Wherein R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, and Z is a hydroxyl group of a polyhydric alcohol having 2 or more valences) And m represents an integer of 1 or more, m ′ represents an integer of 0 or more, m + m ′ represents a valence of Z, and n represents an integer of 1 to 4.)
The component (B) is a compound represented by the following general formula (4).
The gear oil composition.
R ³ —CH ₂ COOH Formula (4)
(In the formula, R ³ represents an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms, or a group represented by the general formula (5).)
R ⁴ —C ₆ H ₄ O— (5)
(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms or hydrogen.)