CN1273571C - Lubricating oil composition - Google Patents

Abstract

Lubricating oil compositions particularly suitable for automatic transmissions comprising a lubricating base oil, (A) a boron-containing ashless dispersant in an amount of 0.004 to 0.05 percent by mass in terms of boron, based on the total mass of the composition, (B) an alkaline earth metal-based detergent with a base number of 0 to 500 mgKOH/g in an amount of 0.01 percent by mass or more in terms of an alkaline earth metal, based on the total mass of the composition, and (C) a sulfur-based additive in an amount of 0.01 to 0.3 percent by mass in terms of sulfur, based on the total mass of the composition and having excellent anti-wear properties and improved fatigue life by inhibiting pitching.

Description

lubricating oil composition

technical field

The present invention relates to a lubricating oil composition, particularly a lubricating oil composition which is excellent in wear resistance and has a long fatigue life, and is suitable for use in automobile transmissions.

Background technique

An automatic transmission for an automobile includes a torque converter, a planetary gear, a bearing, a wet clutch, and a hydraulic control device for controlling these elements. However, in recent years, due to the development of high-power engines and the progress of downsizing automatic transmissions, automatic transmissions have been able to tolerate greater loads. It is required that the lubricating oil filled in this kind of transmission device, that is, the transmission oil, has excellent extreme pressure and anti-wear properties, while maintaining high lubricity and long fatigue life. the ability to lubricate surface defects).

In order to meet these requirements, it is known, for example, to blend sulfur-based or phosphorus-based additives excellent in extreme pressure and anti-wear properties in lubricating oils such as automotive transmission oils. Although sulfur-based additives have excellent extreme pressure properties, they cannot avoid corrosion wear and abrasion due to their strong interaction with metal surfaces, and problems arise when used alone. Phosphorus-based additives, on the other hand, have less corrosive wear and abrasion than sulfur-based additives due to their weaker interaction with metal surfaces, but are often lacking when used alone in automatic transmissions that are required to exhibit extreme pressure properties under severe conditions. Avoid extreme pressure problems of galling or surface peeling.

In view of the foregoing, it is an object of the present invention to provide a lubricating oil composition particularly suitable as a transmission oil for vehicles, which is excellent in anti-wear properties and inhibits seizure, resulting in improved fatigue life.

Summary of the invention

After extensive investigation and research, it was found that the use of a specific combination of boron-containing ashless dispersants, alkaline earth metal-based detergents, and sulfur-based additives resulted in lubricating oils with improved antiwear properties and inhibited seizure leading to improved fatigue life combination.

That is, the present invention provides a lubricating oil composition comprising a lubricating base oil, (A) a boron-containing ashless dispersant whose content is 0.004 to 0.05% (by mass) in terms of boron based on the total amount of the composition, (B) An alkaline earth metal-based detergent having a base number of 0 to 500 mgKOH/g in an alkaline earth metal content of 0.01% by mass or more in the total amount of the substance, and (C) an alkaline earth metal content in terms of sulfur based on the total amount of the composition 0.01 to 0.3% by mass of sulfur-based additives.

In the present invention, component (A) is preferably boron compound-modified succinimide.

Component (B) is preferably alkaline earth metal calcium or alkaline earth metal magnesium.

Component (B) is preferably a sulfonate or salicylate.

Component (C) is preferably selected from (C-1) thiazole compounds, (C-2) thiadiazole compounds, (C-3) dithiocarbamate compounds, (C-4) disulfide At least one compound of molybdenum carbamate compound, (C-5) dihydrocarbyl polysulfide, and (C-6) sulfurized ester compound.

The lubricating oil composition is preferably used in transmissions for automobiles.

Detailed description of the invention

The present invention is described in more detail below.

(1) base oil

The lubricating base oil used in the present invention may be any of the mineral and/or synthetic base oils commonly used as lubricating oil base oils.

Examples of mineral base oils include paraffinic or naphthenic oils, which may be produced by subjecting lubricating oil fractions produced by atmospheric distillation or vacuum distillation of crude oil to a process selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, Obtained by one or more refining processes of hydrorefining, sulfuric acid washing and clay treatment; and n-paraffin.

There are no particular restrictions on synthetic base oils. However, examples of synthetic base oils include poly-α-olefins such as 1-octene oligomers, 1-decene oligomers, and ethylene-propylene oligomers and hydrogenated products thereof; isobutylene oligomers and hydrogenated products thereof; Isoparaffins; alkylbenzenes; alkylnaphthalenes; diesters such as bis(tridecyl)glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, Thirteen) esters, and di-2-ethylhexyl sebacate; polyol esters such as trimethylolpropane octanoate, trimethylolpropane nonanoate, pentaerythritol-2-ethylhexanoate, and pentaerythritol nonanoate; polyoxyalkylene glycols; dialkyldiphenyl ethers; and polyphenylene ethers.

The kinematic viscosity of the lubricating base oil is not particularly limited. However, the kinematic viscosity of the lubricating base oil at 100°C is preferably 1 to 20 mm ² /s, more preferably 2 to 10 mm ² /s.

(2)(A) Boron-containing ashless dispersant

Component (A) of the lubricating oil composition of the present invention is a boron-containing ashless dispersant.

It is important that component (A) contains boron. In the case of using an ashless dispersant that does not contain boron as component (A), the object of the present invention cannot be achieved because it not only cannot suppress the fatigue caused by seizing or surface peeling, but even with the component (B) described later ) and (C) are also ineffective in terms of wear resistance and oxidation stability when used in combination.

Although the boron content in component (A) can be selected arbitrarily, in order to have excellent fatigue life and wear resistance, the lower limit is preferably 0.2% (mass), more preferably 0.4% (mass), and the upper limit is 4% ( mass), more preferably 2.5% (mass).

Specific examples of component (A) include products modified with boron compounds, such as nitrogen-containing compounds and derivatives thereof having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule. Any one or more selected from these compounds may be blended.

The alkyl or alkenyl group may be linear or branched, preferably a branched alkyl group derived from an oligomer of olefins such as propylene, 1-butene, and isobutylene or a low copolymer of ethylene and propylene or Alkenyl.

Although the carbon number of the alkyl or alkenyl group is optional, it is preferably 40 to 400, more preferably 60 to 350 carbon atoms. Alkyl or alkenyl groups having less than 40 carbon atoms impair the solubility of the compound in the base oil, while alkyl or alkenyl groups having more than 400 carbon atoms impair the cold flow of the resulting lubricating oil composition sex.

Specific examples of nitrogen-containing compounds are one or more selected from the following compounds:

(A-1) succinimide or derivatives thereof having at least one alkyl or alkenyl group having 40 to 400 carbon atoms per molecule;

(A-2) benzylamine or derivatives thereof having at least one alkyl or alkenyl group having 40 to 400 carbon atoms per molecule; and

(A-3) A polyamine or a derivative thereof having at least one alkyl or alkenyl group having 40 to 400 carbon atoms per molecule.

(A-1) The specific example of succinimide is the compound shown in the following formula:

In formula (1), R ¹ is an alkyl or alkenyl group having 40 to 400, preferably 60 to 350, carbon atoms, and a is an integer of 1 to 5, preferably 2 to 4.

In formula (2), R ² and R ³ are independently an alkyl or alkenyl group having 40 to 400, preferably 60 to 350, carbon atoms, and b is an integer of 0 to 4, preferably 1 to 3.

Succinimide is classified into monosuccinimide represented by formula (1) in which succinic anhydride is added to one end of polyamine and disuccinimide represented by formula (2) in which succinic anhydride is added to both ends of polyamine. In the present invention, both types of succinimides and mixtures thereof can be used as component (A).

(A-2) The specific example of benzylamine is the compound shown in the following formula:

In formula (3), R ⁴ is an alkyl or alkenyl group having 40 to 400, preferably 60 to 350, carbon atoms, and c is an integer of 1 to 5, preferably 2 to 4.

The production method of benzylamine is not particularly limited. But as an example, one of said benzylamines can be produced by reacting polyolefins such as propylene oligomers, polybutenes, or ethylene-α-olefin copolymers with phenol to give alkylphenols, which are then reacted with formaldehyde Mannich reaction with polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or pentaethylenehexamine.

(A-3) Specific examples of polyamines are compounds represented by the following formula:

In formula (4), R ⁵ is an alkyl or alkenyl group having 40 to 400, preferably 60 to 350 carbon atoms, and d is an integer of 1 to 5, preferably 2 to 4.

The production method of the polyamine is not particularly limited. For example, one of the polyamines can be produced by chlorinating polyolefins such as propylene oligomers, polybutene, or ethylene-α-olefin copolymers and then reacting them with ammonia or polyamines such as ethylenediamine, di Ethylenetriamine, triethylenetetramine, tetraethylenepentamine, or pentaethylenehexamine.

Specific examples of the derivatives of the nitrogen-containing compound are any one of the above-mentioned nitrogen-containing compounds with a monocarboxylic acid (fatty acid) having 2 to 30 carbon atoms or a polycarboxylic acid having 2 to 30 carbon atoms such as oxalic acid, A carboxylic acid-modified compound obtained by reacting phthalic acid, trimellitic acid or pyromellitic acid to neutralize or amidate the remaining amino groups and/or imino groups in whole or in part; Sulfur-modified compounds obtained by reacting sulfur compounds; and mixtures thereof.

Component (A) used in the present invention is a compound obtained by modifying any of the above nitrogen-containing compounds or derivatives thereof with a boron compound.

The method of modifying the nitrogen compound or its derivatives with a boron compound is not particularly limited. Thus, any suitable method may be employed. For example, any one of the above-mentioned nitrogen compounds or their derivatives is reacted with a boron compound such as boric acid, borate, or borate to make the remaining amino and/or imino groups in the nitrogen-containing compound or its derivatives all or Partially neutralized or amidated.

Specific examples of boron compounds used therein are orthoboric acid, metaboric acid, and tetraboric acid. Examples of borates are alkali metal, alkaline earth metal, or ammonium salts of boric acid. More specific examples are lithium borates such as lithium metaborate, lithium tetraborate, lithium pentaborate, and lithium perborate, sodium borates such as sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, and octaborate. Sodium borates, potassium borates such as potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate, calcium borates such as calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate, and hexaborate Calcium borates, magnesium borates such as magnesium metaborate, magnesium diborate, trimagnesium tetraborate, pentamagnesium tetraborate, and magnesium hexaborate, and ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, and ammonium octaborate. Examples of boric acid esters are esters of boric acid with alkyl alcohols having 1 to 6 carbon atoms, more specifically monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate , triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, and tributyl borate.

Preferably used for component (A) is to make (A-1) as the above-mentioned nitrogen-containing compound have at least one alkane having 40 to 400 carbon atoms per molecule with the above-mentioned boron compound for the purpose of improving fatigue life and wear resistance. Modified succinimides of groups or alkenyl groups; and mixtures thereof.

The lower limit content of one or more components (A) in the lubricating oil composition of the present invention is 0.004% (mass), preferably 0.005% (mass) in terms of boron based on the total amount of the composition, and the upper limit is based on the total amount of the composition. The amount is 0.05% by mass, preferably 0.02% by mass, more preferably 0.015% by mass, particularly preferably 0.010% by mass in terms of boron. Component (A) below the lower limit is ineffective in wear resistance, while component (A) above the upper limit shortens the fatigue life of the resulting composition.

(3)(B) Metal-based detergents

Component (B) used in the present invention is an alkaline earth metal based detergent.

The base number of component (B) is 0 to 500 mgKOH/g, preferably 0 to 400 mgKOH/g. Component (B) having a base number exceeding 500 mgKOH/g is structurally unstable and impairs storage stability of the resulting oil composition. The term "base number" as used herein represents the base number measured by perchloric acid potentiometric titration in accordance with JIS K2501 (1992) Part 7 "Petroleum products and lubricants - Determination of neutralization value".

In the present invention, the use of component (B) not only improves the performance of inhibiting fatigue caused by seizure or surface peeling and wear resistance, but also optimizes the friction performance of the wet clutch, thereby suppressing the decrease in strength of the wet clutch due to repeated compression.

A specific example of component (B) is one or more metal-based detergents selected from:

(B-1) an alkaline earth metal sulfonate with a base value of 0 to 500 mgKOH/g;

(B-2) an alkaline earth metal salicylate with a base number of 0 to 500 mgKOH/g; and

(B-3) Alkaline earth metal phenate having a base value of 0 to 500 mgKOH/g.

(B-1) Specific examples of alkaline earth metal sulfonates are alkaline earth metal salts of alkylaromatic sulfonic acids obtained by sulfonating alkylaromatic compounds having a molecular weight of 100 to 1500, preferably 200 to 700, particularly preferably magnesium salt and/or calcium salts. Specific examples of alkylaromatic sulfonic acids are petroleum sulfonic acids and synthetic sulfonic acids.

The petroleum sulfonic acid may be a petroleum sulfonic acid obtained by sulfonation of an alkylaromatic compound contained in a lubricant fraction of mineral oil or a petroleum sulfonic acid by-produced in the production of white oil. Synthetic sulfonic acid can be obtained by sulfonating straight-chain or branched-chain alkylbenzene (which can be a by-product of an alkylbenzene production plant as a detergent raw material) or by alkylating polyolefins into benzene or making di Sulfonated nonylnaphthalene. The sulfonating agent used for sulfonating the alkylaromatic compound is not particularly limited. But generally oleum and sulfuric acid are used.

(B-2) Examples of alkaline earth metal salicylates are alkaline earth metal salts of alkyl salicylic acids having at least one linear or branched chain alkyl group containing 4 to 30, preferably 6 to 18 carbon atoms, preferably magnesium salt and/or calcium salts.

(B-3) A specific example of an alkaline earth metal phenate is an alkylphenol sulfide obtained by reacting an alkylphenol with sulfur and having at least one linear or branched alkyl group containing 4 to 30, preferably 6 to 18 atoms, or Alkaline earth metal salts, preferably magnesium and/or calcium salts, of the Mannich reaction products obtained by reacting such alkylphenols with formaldehyde.

As long as the base number of the component (B), alkaline earth metal sulfonate, alkaline earth metal salicylate or alkaline earth metal phenate, is in the range of 0 to 500 mgKOH/g, it may be produced by alkylaromatic sulfonic acid, alkane Alkaline salicylic acid, alkylphenol, alkylphenol sulfide, or Mannich reaction products of alkylphenol are reacted directly with alkaline earth metal salts such as oxides or hydroxides of alkaline earth metals (such as magnesium and/or calcium) or with alkaline earth Substitution of metal salts for alkylaromatic sulfonic acids, alkylsalicylic acids, alkylphenols, alkylphenol sulfides, or Mannich reaction products of alkylphenols that have been converted to alkali metal salts such as sodium or potassium salts Sexual (positive) salt. Component (B) may also be a basic salt obtained by heating the above normal salt together with an excess of alkaline earth metal salt or alkaline earth metal base (alkaline earth metal hydroxide or oxide) in the presence of water. Component (B) may also be an overbased calcium salt obtained by reacting the above normal salt with an alkaline earth metal base in the presence of carbon dioxide gas.

These reactions are typically carried out in solvents including aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as xylene, or lubricating base oil light ends. Metal-based detergents are commercially available in diluted form with lubricating base oil light fractions. Preference is given to using metal-based detergents with a metal content in the range of 1.0 to 20% by mass, preferably 2.0 to 16% by mass.

In the present invention, among the compounds listed above, calcium sulfonate, calcium salicylate, magnesium sulfonate, and magnesium salicylate are preferably used. However, the use of calcium sulfonate is particularly preferred because it further enhances the wear resistance and fatigue life of the resulting lubricating oil composition.

The lower limit content of component (B) is 0.01% by mass, preferably 0.015% by mass in terms of alkaline earth metal based on the total amount of the composition. The upper limit of component (B) is not particularly limited. However, the upper limit is preferably 0.2% by mass or less, particularly preferably 0.15% by mass or less in terms of alkaline earth metal based on the total weight of the composition. Component (B) in an amount below the lower limit cannot suppress fatigue caused by seizure or surface spalling even if combined with the above-mentioned component (A) and the following component (C), while the component (B) exceeds 0.2% (mass) will destroy the oxidation stability of the resulting composition.

(4) (C) sulfur-based additives

Component (C) of the lubricating oil composition of the present invention is a sulfur-based additive.

(C) Specific examples of sulfur-based additives are any one or more sulfur-based additives selected from the following:

(C-1) thiazole compounds,

(C-2) thiadiazole compounds,

(C-3) dithiocarbamate compounds,

(C-4) molybdenum dithiocarbamates,

(C-5) dihydrocarbyl polysulfides, and

(C-6) Sulfurized ester compounds.

Thiazole compounds preferably used in component (C-1) are compounds represented by the following formula:

In formula (5) and (6), R ⁶ and R ⁷ are independently hydrogen or a hydrocarbon group with 1 to 30 carbon atoms, R ⁸ is an alkyl group with 1 to 4 carbon atoms, and e, f and g are independently ground is an integer from 0 to 3.

Among these compounds, the benzothiazole compound represented by the formula (6) is particularly preferable. Examples of hydrocarbon groups having 1 to 30 carbon atoms for R and R in formulas ( ⁵ ) and ( ⁶ ) are alkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aryl, alkane Aryl, and Aralkyl.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl may all be straight or branched.

Specific examples of the cycloalkyl group include those having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl.

Specific examples of alkylcycloalkyl include those having 6 to 11 carbon atoms, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methyl Cyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcyclohexyl, methylethylcyclohexyl, and diethylcyclohexyl , where the alkyl group can be bonded at any position of the cycloalkyl group.

Specific examples of alkenyl groups include propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, Tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl, all can be straight or branched and the double bond position can change.

Specific examples of aryl include phenyl and naphthyl.

Examples of alkaryl groups include those having 7 to 18 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl phenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl, where the alkyl group can be straight or branched, and can be bonded at any position of the aryl group.

Specific examples of the aralkyl group include those having 7 to 12 carbon atoms, such as benzyl, phenethyl, phenylpropyl, phenbutyl, phenpentyl, and phenylhexyl, wherein the alkyl group may be straight-chain or Branched.

Thiadiazole compounds preferably used in component (C-2) are 1,3,4-thiadiazole compounds, 1,2,4-thiadiazole compounds, and 1,4,5- Thiadiazole compounds:

In the formulas (7), (8) and (9), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ may be the same or different, independently hydrogen or carbon atoms having 1 to 30 carbon atoms Hydrocarbyl, h, i, j, k, l, and m may be the same or different, and are independently an integer of 0 to 8.

Examples of hydrocarbon groups having 1 to 30 carbon atoms for R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in formulas (7), (8) and (9) are alkyl, cycloalkane radical, alkylcycloalkyl, alkenyl, aryl, alkaryl, and aralkyl.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl may all be straight or branched.

Specific examples of the cycloalkyl group include those having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl.

Specific examples of alkylcycloalkyl include those having 6 to 11 carbon atoms, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methyl Cyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcyclohexyl, methylethylcyclohexyl, and diethylcyclohexyl , where the alkyl group can be bonded at any position of the cycloalkyl group.

Specific examples of alkenyl groups include propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, Tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl, all can be straight or branched and the double bond position can change.

Specific examples of aryl include phenyl and naphthyl.

Examples of alkaryl groups include those having 7 to 18 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl phenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl, where the alkyl group can be straight or branched, and can be bonded at any position of the aryl group.

Specific examples of the aralkyl group include those having 7 to 12 carbon atoms, such as benzyl, phenethyl, phenylpropyl, phenbutyl, phenpentyl, and phenylhexyl, wherein the alkyl group may be straight-chain or Branched.

Component (C-3), i.e. dithiocarbamate, can be any dithiocarbamate, but is preferably a compound shown in the following formula:

In formulas (10) and (11), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, and R ²¹ is hydrogen or A hydrocarbon group having 1 to 30 carbon atoms, preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 0 to 4, and o is an integer of 0 to 6.

Examples of hydrocarbon groups having 1 to 30 carbon atoms for ^R15 to ^R21 are alkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aryl, alkaryl and aralkyl.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl may all be straight or branched.

Specific examples of the cycloalkyl group include those having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl.

Specific examples of alkylcycloalkyl include those having 6 to 11 carbon atoms, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methyl Cyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcyclohexyl, methylethylcyclohexyl, and diethylcyclohexyl , where the alkyl group can be bonded at any position of the cycloalkyl group.

Specific examples of alkenyl groups include propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, Tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl, all can be straight or branched and the double bond position can change.

Specific examples of aryl include phenyl and naphthyl.

Examples of alkaryl groups include those having 7 to 18 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl phenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl, where the alkyl group can be straight or branched, and can be bonded at any position of the aryl group.

Specific examples of the aralkyl group include those having 7 to 12 carbon atoms, such as benzyl, phenethyl, phenylpropyl, phenbutyl, phenpentyl, and phenylhexyl, wherein the alkyl group may be straight-chain or Branched.

Component (C-4), i.e. molybdenum dithiocarbamate compound, can be any molybdenum dithiocarbamate that can be used as an additive for lubricating oil, but particularly preferably the compound shown in the following formula:

In formula (12), R ²² , R ²³ , R ²⁴ and R ²⁵ are independently hydrocarbon groups with 2 to 18 carbon atoms such as alkyl or alkaryl, and Y ¹ , Y ² , Y ³ and Y ⁴ are independently for sulfur or oxygen.

Alkyl as referred to herein includes primary, secondary and tertiary, and may be straight or branched. Specific examples of preferred alkyl groups are ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and tridecyl, all of which may be straight or branched. Specific examples of preferred alkaryl groups are butylphenyl and nonylphenyl, both of which may be straight or branched.

Specific examples of (C-4) molybdenum dithiocarbamate compounds are molybdenum sulfide diethyldithiocarbamate, molybdenum sulfide dipropyldithiocarbamate, molybdenum sulfide dibutyldithiocarbamate, Amyl dithiocarbamate molybdenum sulfide, dihexyl dithiocarbamate molybdenum sulfide, dioctyl dithiocarbamate molybdenum sulfide, didecyl dithiocarbamate molybdenum sulfide, bis(dodecyl) disulfide Molybdenum thiocarbamate sulfide, bis(tridecyl)molybdenum dithiocarbamate sulfide, bis(butylphenyl)molybdenum dithiocarbamate sulfide, bis(nonylphenyl)molybdenum dithiocarbamate sulfide, Diethyl dithiocarbamate oxymolybdenum sulfide, dipropyl dithiocarbamate oxymolybdenum sulfide, dibutyl dithiocarbamate oxymolybdenum sulfide, diamyl dithiocarbamate oxymolybdenum sulfide, dihexyl Dithiocarbamate oxymolybdenum sulfide, dioctyl dithiocarbamate oxymolybdenum sulfide, didecyl dithiocarbamate oxymolybdenum sulfide, di(dodecyl) dithiocarbamate oxymolybdenum sulfide, (Tridecyl)molybdenum sulfide dithiocarbamate, molybdenum sulfide bis(butylphenyl)dithiocarbamate, molybdenum sulfide bis(nonylphenyl)dithiocarbamate, and mixtures thereof, wherein The alkyl group can be straight chain or branched.

Any one or more of (C-4) components may be blended.

(C-5) Dihydrocarbyl polysulfides are sulfur-based compounds commonly known as polysulfides or sulfurized olefins, represented by the following formula:

R ²⁶ -S _p -R ²⁷ (13)

In formula (13), R ²⁶ and R ²⁷ are independently a straight chain or branched chain alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkane group having 7 to 20 carbon atoms An aryl group or an aralkyl group having 7 to 20 carbon atoms, p is an integer of 2 to 6, preferably 2 to 5.

Examples of alkyl groups for R ^{and R} include n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight or branched pentyl, straight or branched Hexyl, straight or branched heptyl, straight or branched octyl, straight or branched nonyl, straight or branched decyl, straight or branched undecyl, straight or branched deca Dialkyl, straight chain or branched chain tridecyl, straight chain or branched chain tetradecyl, straight chain or branched chain pentadecyl, straight chain or branched chain hexadecyl, straight chain or branched chain decadecyl Heptadecyl, straight or branched octadecyl, straight or branched nonadecyl, and straight or branched eicosyl.

Examples of aryl groups for ^R26 and ^R27 include phenyl and naphthyl.

Examples of alkaryl groups for R ^{and R} include tolyl (including all structural isomers), ethylphenyl (including all structural isomers), straight or branched propylphenyl (including all structural isomers), isomers), straight or branched butylphenyl (including all structural isomers), straight or branched pentylphenyl (including all structural isomers), straight or branched hexylphenyl ( including all structural isomers), linear or branched heptylphenyl (including all structural isomers), linear or branched octylphenyl (including all structural isomers), linear or branched nonylphenyl phenyl (including all structural isomers), straight chain or branched decylphenyl (including all structural isomers), straight chain or branched undecylphenyl (including all structural isomers), Linear or branched dodecylphenyl (including all structural isomers), xylyl (including all structural isomers), ethylmethylphenyl (including all structural isomers), diethyl Phenyl (including all structural isomers), di(linear or branched) propylphenyl (including all structural isomers), di(linear or branched) butylphenyl (including all structural isomers) isomers), methylnaphthyl (including all structural isomers), ethylnaphthyl (including all structural isomers), straight-chain or branched propylnaphthyl (including all structural isomers), straight-chain or Branched-chain butylnaphthyl (including all structural isomers), dimethylnaphthyl (including all structural isomers), ethylmethylnaphthyl (including all structural isomers), diethylnaphthyl ( including all structural isomers), di(linear or branched) propylnaphthyl (including all structural isomers), and di(linear or branched) butylnaphthyl (including all structural isomers) .

Examples of aralkyl groups for R ²⁶ and R ²⁷ include benzyl, phenethyl (including all isomers), and phenylpropyl (including all isomers).

R ²⁶ and R ²⁷ are preferably alkyl groups having 3 to 18 carbon atoms, aryl groups having 6 to 8 carbon atoms, alkaryl groups having 7 or 8 carbon atoms derived from propylene, 1-butene or isobutene group, or an aralkyl group having 7 or 8 carbon atoms.

Specific examples of such alkyl groups include isopropyl, branched hexyl derived from propylene dimer (including all branched isomers), branched nonyl derived from propylene trimer (including all branched isomers), ), branched dodecyl derived from propylene tetramer (including all branched isomers), branched pentadecyl derived from propylene pentamer (including all branched isomers), derived from propylene Hexamer-derived branched octadecyl (including all branched isomers), sec-butyl, tert-butyl, branched octyl derived from 1-butene dimer (including all branched isomers) body), branched octyl derived from isobutene dimer (including all branched isomers), branched dodecyl derived from 1-butene trimer (including all branched isomers), branched dodecyl derived from isobutene trimer (including all branched isomers), branched hexadecyl derived from 1-butene tetramer (including all branched isomers), and Branched hexadecyl (including all branched isomers) derived from isobutene tetramer. Specific examples of this aryl group include phenyl. Specific examples of such alkaryl groups include tolyl (including all structural isomers), ethylphenyl (including all structural isomers), and xylyl (including all structural isomers). Specific examples of such aralkyl groups are benzyl and phenethyl (including all structural isomers).

For the purpose of excellent surface peeling resistance and seizure resistance, R ²⁶ and R ²⁷ are independently preferably branched chain alkyl groups with 3 to 18 carbon atoms derived from ethylene or propylene, particularly preferably organic derivatives derived from ethylene or propylene. Branched chain alkyl groups of 6 to 15 carbon atoms.

The sulfur content of the (C-5) dihydrocarbyl polysulfide is not particularly limited. But for the purpose of peeling resistance and seizure resistance, preferred are those having a sulfur content of generally 10 to 55% by mass, preferably 20 to 50% by mass.

(C-6) Specific examples of sulfurized ester compounds include animal or vegetable fats such as tallow, lard, fish oil, rapeseed oil, or soybean oil; unsaturated fatty acids such as oleic acid, linoleic acid, or esters of unsaturated fatty acids obtained by reacting fatty acids extracted from the plant with various alcohols; and those obtained by sulfiding their mixtures.

(C-6) The sulfur content of the sulfurized ester compound is not particularly limited. However, for the purpose of peeling resistance and seizure resistance, preferred are those having a sulfur content of generally 2 to 40% by mass, preferably 5 to 35% by mass.

Any one or more compounds selected from (C-1), (C-2), (C-3), (C-4), (C-5) and (C-6) compounds can be used as the lubricant of the present invention Component (C) of the oil composition.

The lower limit content of component (C) is 0.01% (mass), preferably 0.02% (mass) based on the total amount of the lubricating oil composition in terms of sulfur, and the upper limit content is 0.3% in terms of sulfur based on the total amount of the lubricating oil composition (mass), preferably 0.2% (mass). Component (C) in an amount below the stated lower limit cannot inhibit seizing or flaking, while a component (C) exceeding the stated upper limit will impair the oxidation stability of the resulting lubricating oil composition and reduce wear resistance due to corrosive wear .

(5) Other additives

The lubricating oil compositions of the present invention may incorporate known additives to further enhance their performance as lubricating oils. Examples of such additives are (D) boron-free ashless dispersants, (E) friction modifiers, (F) antioxidants, (G) boron-based extreme pressure additives, (H) antiwear agents, (I) viscosity Index improvers, (J) rust inhibitors, (K) corrosion inhibitors, (L) pour point depressants, (M) rubber swelling agents, (N) defoamers, and (O) colorants. These additives may be used alone or in combination.

(D) Ashless dispersant without boron

Specific examples of boron-free ashless dispersants that may be blended with the lubricating oil compositions of the present invention are the ashless dispersants described for component (A) prior to modification with a boron compound. In the present invention, one or more compounds selected from such ashless dispersants may be incorporated in any amount. The content of the boron-free ashless dispersant is preferably 0.1 to 10% by mass based on the total amount of the lubricating oil composition.

(E) Friction modifier

The friction modifier that can be used in combination with the lubricating oil composition of the present invention is any compound generally used as a friction modifier in lubricating oils, including amine compounds, fatty acid esters, fatty acid amides, and fatty acid metal salts, the molecules of which Each has at least one alkyl or alkenyl group containing 6 to 30 carbon atoms, preferably a straight chain alkyl or alkenyl group containing 6 to 30 carbon atoms.

Examples of amine compounds include linear or branched (preferably linear) aliphatic monoamines having 6 to 30 carbon atoms, linear or branched (preferably linear) aliphatic polyamines having 6 to 30 carbon atoms, Amines, and alkylene oxide adducts of these aliphatic amines. Examples of fatty acid esters include esters of linear or branched (preferably linear) fatty acids having 7 to 31 carbon atoms with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of fatty acid amides include amides of linear or branched (preferably linear) fatty acids having 7 to 31 carbon atoms and aliphatic monoamines or aliphatic polyamines. Examples of fatty acid metal salts include alkaline earth metal salts (magnesium salts and calcium salts) or zinc salts of linear or branched (preferably linear) fatty acids having 7 to 31 carbon atoms.

In the present invention, any one or more compounds selected from such friction modifiers may be incorporated in any amount. The content of the friction modifier is 0.01 to 5.0% by mass, preferably 0.03 to 3.0% by mass, based on the total amount of the lubricating oil composition.

(F) Antioxidant

The antioxidant that can be used in combination with the lubricating oil composition of the present invention may be any conventional antioxidant commonly used as an antioxidant in lubricating oils such as phenol-based compounds or amine-based compounds.

Specific examples of antioxidants are alkylphenols such as 2,6-di-tert-butyl-4-methylphenol, bisphenols such as methylene-4,4-bisphenol (2,6-di-tert-butyl-4- methylphenol), naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, zinc dialkyldithiophosphates such as di-2-ethylhexylzincdithiophosphate, and (3,5- Di-tert-butyl-4-hydroxyphenyl) fatty acids such as propionic acid and monohydric or polyhydric alcohols such as methanol, stearyl alcohol, 1,6-hexanediol, neopentyl glycol, thiodiglycol, triethylene glycol, and pentaerythritol esters.

In the present invention, any one or more compounds selected from the above antioxidants may be incorporated in any amount. The content of the antioxidant is generally 0.01 to 5.0% by mass based on the total amount of the lubricating oil composition.

(G) Boron-based extreme pressure additives

The boron-based extreme pressure additive that may be used in combination with the lubricating oil composition of the present invention may be an alkali metal borate or a hydrate thereof. Specific examples of boron-based extreme pressure additives are lithium borate hydrate, sodium borate hydrate, potassium borate hydrate, rubidium borate hydrate, and cesium borate hydrate. Particularly preferred is potassium borate hydrate.

For example, alkali metal borates in the form of finely divided dispersants of hydrated potassium borate or hydrated sodium borate can be obtained by dissolving potassium hydroxide or sodium hydroxide and boric acid in water so that boron and alkali metal (potassium, or sodium) etc.) in an atomic ratio in the range of 2.0 to 4.5, the resulting solution is added to an oil solution containing a neutral alkaline earth metal sulfonate or succinimide based ashless dispersant, followed by vigorous stirring until an oil-in-water emulsion is obtained, The emulsion is dehydrated.

Any one or more compounds selected from the above compounds may be incorporated in any amount. However, the content of these compounds is 0.002 to 0.1% by mass in terms of boron based on the total amount of the composition.

(H) Antiwear agent

Examples of antiwear agents that may be used in combination with the lubricating oil compositions of the present invention include zinc dialkyldithiophosphates, phosphoric acid, monophosphates, diphosphates, triphosphates, combinations of phosphoric acid, monophosphates, and diphosphates. Metal or amine salts, and mixtures thereof.

Among these antiwear agents, those other than phosphoric acid are generally compounds having hydrocarbon groups of 2 to 30, preferably 3 to 20 carbon atoms.

The content of the antiwear agent is preferably 0.005 to 0.2% by mass in terms of phosphorus based on the total amount of the lubricating oil composition. A content of less than 0.005% by mass in terms of phosphorus is not effective in anti-wear, while a content of more than 0.2% by mass impairs the oxidation stability of the resulting lubricating oil composition.

(I) Viscosity Index Improver

The viscosity index improver that can be used in combination with the lubricating oil composition of the present invention may be a non-dispersible viscosity index improver such as a polymer or copolymer of one or more monomers selected from various methacrylates or their hydrogenated products and Dispersion type viscosity index improvers such as methacrylates and copolymers of various methacrylates also containing nitrogen compounds.

Other examples of viscosity index improvers are non-dispersed or dispersed ethylene-α-olefin copolymers (wherein the α-olefin may be propylene, 1-butene or 1-pentene) or hydrogenated products thereof, polyisobutylene or Hydrogenated products, styrene-diene hydrogenated copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes.

The molecular weight of these viscosity index improvers is selected taking into account their shear stability. Specifically, the number-average molecular weight of the non-dispersed or dispersed polymethacrylate is preferably from 5,000 to 150,000, more preferably from 5,000 to 35,000. The polyisobutene or its hydrogenated products have a number average molecular weight of 800 to 5 000, preferably 1 000 to 4 000. The number-average molecular weight of the ethylene-α-olefin copolymers and their hydrogenated products is from 800 to 150,000, preferably from 3,000 to 12,000.

Among these viscosity index improvers, use of an ethylene-α-olefin copolymer or a hydrogenated product thereof contributes to a lubricating oil composition excellent in shear stability.

Any one or more compounds selected from the aforementioned viscosity index improvers may be incorporated in any amount. The content of the viscosity index improver is generally 0.1 to 40.0% by mass based on the total amount of the lubricating oil composition.

(J) Rust inhibitor

Examples of rust inhibitors include alkenyl succinic acid, alkenyl succinate, polyol ester, petroleum sulfonate, and dinonyl naphthalene sulfonate.

(K) Corrosion inhibitor

The corrosion inhibitor which may be used in combination with the lubricating oil composition of the present invention may be any compound commonly used in lubricating oils as a corrosion inhibitor. Examples of the corrosion inhibitor include benzotriazole-, tolyltriazole-, thiadiazole-, and imidazole-based compounds.

(L) pour point depressant

Examples of pour point depressants are polymethacrylate based polymers suitable for lubricating base oils.

(M) Rubber swelling agent

Examples of rubber swelling agents include aromatic compounds and sulfur-based compounds.

(N) Defoamer

Examples of antifoaming agents are silicones such as dimethylsiloxane and fluorosilicone.

In the present invention, the content of these additives can be selected arbitrarily. But generally, the content of antirust agent, corrosion inhibitor, pour point depressant and rubber swelling agent is 0.005 to 3% by mass based on the total amount of the composition. The content of the antifoaming agent is 0.0005 to 0.01% by mass based on the total amount of the composition.

(6) Viscosity of the final product

The kinematic viscosity at 100°C of the lubricating oil composition of the present invention is preferably 4 to 30 mm ² /s, more preferably 5 to 25 mm ² /s.

The lubricating oil composition of the present invention is excellent in wear resistance and seizure and spalling inhibition, resulting in a long fatigue life, and thus is suitable as lubricating oils requiring such properties, such as gear oils for automobiles, construction machinery and agricultural machinery, and automatic Or lubricating oil for manual transmissions. The lubricating oil composition of the present invention is also suitable as an industrial gear oil; a lubricating oil for gasoline engines, diesel engines, and gas engines of automobiles such as two- or four-wheeled vehicles, generators, and ships; turbine oil; and compressor oil.

best practice

The present invention is described in more detail with reference to the following examples and comparative examples, but is not limited thereto.

Examples 1 to 15 and Comparative Examples 1 to 8

Various additives shown in the table were added to the base oil (mineral oil with a kinematic viscosity of 3.8 mm ² /s at 100°C) to prepare various lubricating oil compositions (Tables 1-1, 1-2 and 1-3 Examples in and comparative examples in Tables 2-1 and 2-2). The amount of each additive is based on the total amount of the composition.

Each lubricating oil composition was evaluated by (1) antiwear test and (2) fatigue life test. The results of these evaluation tests are also shown in the tables. For comparison, commercially available lubricating oil compositions (Comparative Examples 6 to 8 in Table 2-2) were evaluated by the same test. The results are also shown in Table 2-2.

(1) Wear resistance test

The wear resistance of each composition was evaluated with an IAE gear oil tester in the following manner. Measure the weight of the gear before and after the wear test. The amount of reduction in weight was calculated as a criterion.

(run-in condition)

Oil temperature: 80℃

Speed: 2500rpm

Load: 380N

Test time: 20min

(actual test conditions)

Oil temperature: 80℃

Speed: 3 000rpm

Load: 380N

Test time: 120min

(Evaluation Standards)

When using commercially available automatic transmission oil or gear oil, the amount of wear is in the range of 0 to 100 mg. Thus, if the abrasion amount is 100 mg or less, the composition is judged to be excellent in abrasion resistance.

(2) Fatigue life test

The fatigue life of each composition was evaluated with a double cylinder type fatigue tester in the following manner.

(cylinder)

Material: SCM436

Shape: Φ68mm×10mm

Hardness: SB3000 to 340

(Test conditions)

    Peripheral speed:   Active side: 12m/s

Passive side: 10m/s

Oil temperature: 60℃

    Surface pressure:                                                

(Evaluation Standards)

The time taken until the occurrence of surface damage such as occlusal was evaluated as the fatigue life. A composition is rated as having a long fatigue life if the composition has a fatigue life of 50 hours or more.

Table 1-1 Example 1 2 3 4 5 base oil mineral oil mineral oil mineral oil mineral oil mineral oil Additive (A) boron-containing ashless dispersant boric acid modified succinimide Mass % (according to B) 0.008 0.008 0.008 0.008 0.008 (B) Alkaline earth metal detergent calcium sulfonate (300BN) calcium sulfonate (10BN) calcium salicylate (100BN) magnesium sulfonate (200BN) Mass % (as Ca or Mg) 0.02 0.02 0.02 0.02 0.02 (C) Thiadiazole A ( ^* 1) Thiadiazole B ( ^* 2) Dithiocarbamate A ( ^* 3) Dithiocarbamate ( ^* 4) Dithiocarbamate Molybdenum ( ^* 5) Dihydrocarbyl polysulfide ( ^* 6) Sulfurized fatty acid ( ^* 7) quality% 0.2 0.2 0.2 0.2 0.2 Other additives ( ^* 8) quality% 15.0 15.0 15.0 15.0 15.0 Test results Wear resistance (IAE gear test) Weight loss due to wear mg 28 11 30 twenty two 16 Fatigue life (double-cylinder type tester) fatigue life h 97 103 108 96 >120

( ^* 1) 2,5-bis(octyldithio)-1,3,4-thiadiazole

( ^* 2) 2-Hexylthio-5-mercapto-1,3,4-thiadiazole

( ^* 3) Methylenebis(diphenyldithiocarbamate)

( ^* 4) Bis(diphenyldithiocarbamoyl)disulfide

( ^* 5) A molybdenum dithiocarbamate compound represented by the following formula. Molybdenum content: 4.8% (mass)

wherein R is an alkyl group having 8 or 13 carbon atoms, and Y is oxygen or sulfur.

( ^* 6) Sulfurized polyisobutylene, sulfur content: 45% by mass

( ^* 7) Sulfurized lard, sulfur content: 30% (by mass)

( ^* 8)(D) Boron-free succinimide-based ashless dispersant

(E) Amine- and ester-based friction modifiers

(F) Amine- and phenol-based antioxidants

(H) Phosphorus-based antiwear agent

(I) polymethacrylate-based viscosity index improver

(L) Polymethacrylate based pour point depressant

Table 1-2 Example 6 7 8 9 10 base oil mineral oil mineral oil mineral oil mineral oil mineral oil Additive (A) boron-containing ashless dispersant boric acid modified succinimide Mass % (according to B) 0.008 0.008 0.008 0.008 0.008 (B) Alkaline earth metal detergent calcium sulfonate (300BN) calcium sulfonate (10BN) calcium salicylate (100BN) magnesium sulfonate (200BN) Mass % (as Ca or Mg) 0.02 0.02 0.02 0.06 0.02 (C) Thiadiazole A ( ^* 1) Thiadiazole B ( ^* 2) Dithiocarbamate A ( ^* 3) Dithiocarbamate B ( ^* 4) Dithioamino Molybdenum formate ( ^* 5) Dihydrocarbyl polysulfide ( ^* 6) Sulfurized fatty acid ( ^* 7) quality% 0.2 0.2 0.06 0.2 0.2 Other additives ( ^* 8) quality% 15.0 15.0 15.0 15.0 15.0 Test Results Wear Resistance (LAE Gear Test) Weight Loss Due to Abrasion mg 18 72 34 33 twenty two Fatigue life (double-cylinder type tester) fatigue life h 105 >120 >120 >120 >120

( ^* 1)-( ^* 8) are the same as in Table 1-1

Table 1-3 Example 11 12 13 14 base oil mineral oil mineral oil mineral oil mineral oil Additive (A) boron-containing ashless dispersant boric acid modified succinimide Mass % (according to B) 0.008 0.008 0.012 0.018 (B) Alkaline earth metal detergent calcium sulfonate (300BN) calcium sulfonate (10BN) calcium salicylate (100BN) magnesium sulfonate (200BN) Mass % (as Ca or Mg) 0.02 0.02 0.02 0.06 (C) Thiadiazole A ( ^* 1) Thiadiazole B ( ^* 2) Dithiocarbamate A ( ^* 3) Dithiocarbamate B ( ^* 4) Dithioamino Molybdenum formate ( ^* 5) Dihydrocarbyl polysulfide ( ^* 6) Sulfurized fatty acid ( ^* 7) quality% 0.2 0.2 0.2 0.2 Other additives ( ^* 8) quality% 15.0 15.0 15.0 15.0 Test results Anti-wear (IAE gear test) Weight loss due to abrasion mg 41 32 6 5 Fatigue life (double-cylinder type tester) fatigue life h 87 91 84 78

( ^* 1)-( ^* 8) are the same as in Table 1-1

table 2-1 comparative example 1 2 3 4 base oil mineral oil mineral oil mineral oil mineral oil Additive (A) boron-containing ashless dispersant boric acid modified succinimide Mass % (according to B) 0.001 0.008 0.008 0.008 (B) Alkaline earth metal detergent calcium sulfonate (300BN) calcium sulfonate (10BN) calcium salicylate (100BN) magnesium sulfonate (200BN) Mass % (as Ca or Mg) 0.02 0.004 0.004 0.02 (C) Thiadiazole A ( ^* 1) Thiadiazole B ( ^* 2) Dithiocarbamate A ( ^* 3) Dithiocarbamate B ( ^* 4) Dithioamino Molybdenum formate ( ^* 5) Dihydrocarbyl polysulfide ( ^* 6) Sulfurized fatty acid ( ^* 7) quality% 0.1 0.1 0.1 Other additives ( ^* 8) quality% 15.0 15.0 15.0 15.0 Test results Anti-wear (IAE gear test) Weight loss due to abrasion mg 133 58 18 twenty one Fatigue life (double-cylinder type tester) fatigue life h >120 42 twenty two 11

( ^* 1)-( ^* 8) are the same as in Table 1-1

Table 2-2 comparative example 5 6 7 8 base oil mineral oil Commercial SP base gear oil APIGL-5 Commercial SP base gear oil APIGL-3 ATF Dexron III Additive (A) boron-containing ashless dispersant boric acid modified succinimide Mass % (according to B) 0.008 (B) Alkaline earth metal detergent calcium sulfonate (300BN) calcium sulfonate (10BN) calcium salicylate (100BN) magnesium sulfonate (200BN) Mass % (as Ca or Mg) 0.02 (C) Thiadiazole A ( ^* 1) Thiadiazole B ( ^* 2) Dithiocarbamate A ( ^* 3) Dithiocarbamate B ( ^* 4) Dithioamino Molybdenum formate ( ^* 5) Dihydrocarbyl polysulfide ( ^* 6) Sulfurized fatty acid ( ^* 7) quality% 1.0 Other additives ( ^* 8) quality% 15.0 Test results Anti-wear (IAE gear test) Weight loss due to abrasion mg 219 3 5 twenty two Fatigue life (double-cylinder type tester) fatigue life h 52 6 19 29

( ^* 1)-( ^* 8) are the same as in Table 1-1

As can be seen from the results shown in Tables 1-1, 1-2 and 1-3, the lubricating oil compositions of the present invention (Examples 1 to 14) have excellent properties such as excellent wear resistance and long fatigue life.

On the contrary, as can be seen from the results shown in Tables 2-1 and 2-2, the compositions of Comparative Examples 1 and 5 (the former containing component (A) in an amount less than the amount specified in the present invention and the latter containing Component (C)) was poor in abrasion resistance. The compositions of Comparative Examples 2, 3 and 4 whose content of component (B) or (C) was less than the specified amount of the present invention had a short fatigue life due to seizure.

The most commonly used commercially available gear oils of Comparative Examples 6 and 7 (SP base gear oil) and the commonly used commercially available automatic transmission oil of Comparative Example 8 had short fatigue life.

Industrial Applicability

As previously stated, the lubricating oil composition of the present invention is excellent in anti-wear properties and can prolong fatigue life by inhibiting seizure or surface spalling. Thus, the lubricating oil composition is suitable as a lubricating oil requiring such properties, such as gear oils for automobiles, construction machinery and agricultural machinery, and lubricating oils for automatic or manual transmissions. The lubricating oil composition of the present invention is also suitable as an industrial gear oil; a lubricating oil for gasoline engines, diesel engines, and gas engines of automobiles such as two- or four-wheeled vehicles, generators, and ships; turbine oil; and compressor oil.

Claims (16)

1. automatic transmission lubricating oil composition comprises that lubricating base oil, (A) are that the boracic ashless dispersant, (B) of 0.004 to 0.05% (quality) is that 0.01% (quality) or higher base number are 0 to 500mgKOH/g alkaline-earth metal-based washing agent and (C) are the sulfenyl additive of 0.01 to 0.3% (quality) by sulphur content based on the total amount of composition based on the total amount of composition by alkaline-earth metal content by boron content based on the total amount of composition.

2. the lubricating oil composition of claim 1, wherein component (A) is the succinimide of boron compound modification.

3. the lubricating oil composition of claim 1, wherein component (B) is alkaline earth metals calcium or alkaline-earth metal magnesium.

4. the lubricating oil composition of claim 1, wherein component (B) is sulfonate or salicylate.

5. the lubricating oil composition of claim 1, wherein component (C) is for being selected from (C-1) thiazole compound, (C-2) thiadiazole compound, (C-3) dithio amino formate compounds, (C-4) molybdenum dithiocarbamate compounds, (C-5) dialkyl polysulfide and (C-6) at least a compound of sulfuration ester compound.

6. the lubricating oil composition of claim 1, wherein this lubricating oil composition is used for automobile-used transmission mechanism.

7. gear and manual gear shifting lubricating oil composition, comprise lubricating base oil, (A) total amount based on composition is the boracic ashless dispersant of 0.004 to 0.05% (quality) by boron content, (B) total amount based on composition is that 0.01% (quality) or higher base number are 0 to 500mgKOH/g alkaline-earth metal-based washing agent by alkaline-earth metal content, (C) total amount based on composition is the sulfenyl additive of 0.01 to 0.3% (quality) by sulphur content, and condition is that the total amount that described composition does not contain based on composition is the primary alkyl zinc dithiophosphate of 0.015 to 0.15 quality % by zinc content.

8. the lubricating oil composition of claim 7, wherein component (A) is the succinimide of boron compound modification.

9. the lubricating oil composition of claim 7, wherein component (B) is alkaline earth metals calcium or alkaline-earth metal magnesium.

10. the lubricating oil composition of claim 7, wherein component (B) is sulfonate or salicylate.

11. the lubricating oil composition of claim 7, wherein component (C) is at least a compound that is selected from (C-1) thiazole compound, (C-2) thiadiazole compound, (C-3) dithio amino formate compounds, (C-4) molybdenum dithiocarbamate compounds, (C-5) dialkyl polysulfide and (C-6) vulcanizes ester compound.

12. the lubricating oil composition of claim 7, wherein this lubricating oil composition is used for automobile-used transmission mechanism.

13. an automatic transmission lubricating oil composition, comprise lubricating base oil, (A) based on the total amount of composition be by boron content 0.004 to 0.05% (quality) boracic ashless dispersant, (B) based on the total amount of composition by alkaline-earth metal content be 0.01% (quality) or higher base number be 0 to 500mgKOH/g alkaline-earth metal-based washing agent and (C) based on the total amount of composition by sulphur content be 0.01 weight % to 0.3 quality % be selected from (C-1) thiazole compound and (C-2) at least a compound of thiadiazole compound.

14. the lubricating oil composition of claim 13, wherein component (A) is the succinimide of boron compound modification.

15. the lubricating oil composition of claim 13, wherein component (B) is alkaline earth metals calcium or alkaline-earth metal magnesium.

16. the lubricating oil composition of claim 13, wherein component (B) is sulfonate or salicylate.