JPH11140479A - Lubricant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricant composition capable of manifesting excellent friction-reducing activities and the stability thereof under a wide condition from a low temperature region to a high temperature region by adding a sulfur- containing organic molybdenum-based compound, a specific organic acid salt compound and zinc dithiophosphate together. SOLUTION: This lubricant composition is obtained by blending (A) a sulfur- containing organic molybdenum-based compound (e.g. oxymolybdenum sulfide dithiocarbamate), (B) (i) a metal salt compound of an organic acid in which the organic acid is selected from a carboxylic acid, an aliphatic sulfonic acid, an aromatic sulfonic acid, an alkylsalicyclic acid and an alkylphenol compound, and the metal is selected from the metals of groups 1A, 3A-7A, 8 and 1B-6B (with the proviso that a copper carboxylate is omitted), and (ii) an organic acid salt compound selected from an ammonium salt compound and amine salt compound of the organic acid same as that of the component (i), and (C) zinc dithiophosphate. Iron or the like is preferable as the metal of the component (i).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lubricating oil composition, and more particularly, to an organic acid salt such as a sulfur-containing organic molybdenum compound, an organic acid metal salt, an organic acid ammonium salt and an organic acid amine salt. The present invention relates to a lubricating oil composition containing a compound and zinc dithiophosphate and having an excellent friction reducing effect. The lubricating oil composition of the present invention is useful as a lubricating oil for internal combustion engines, automatic transmission oil, gear oil, hydraulic oil, plastic working oil, and the like.

[0002]

2. Description of the Related Art Reduction of friction and wear generated on sliding surfaces of moving parts of machinery, equipment, equipment, and the like is one of the fundamental problems of tribology, and a great deal of research and development has been carried out. Various types of friction modifiers have been developed to improve the quality of lubricating base oils and to be added to base oils. For example, sulfurized oxymolybdenum dithiophosphate (hereinafter abbreviated as "MoDTP") and sulfurized oxymolybdenum dithiocarbamate (hereinafter abbreviated as "MoDTC") have been proposed as metal-based friction modifiers (for example, Japanese Patent Application Laid-Open No. 54-113
See No. 604. ).

However, in recent years, the use conditions of lubricating oil have become severe with the improvement in performance of machinery and automobiles and the like. For example, for engine oil for automobiles, severe high and low temperature conditions resulting from stop and start operation are required. It is required to withstand complicated repetition and to withstand high-temperature conditions resulting from long-time high-speed continuous operation. The above MoDTP and MoDTC, etc. exhibit a corresponding friction reducing effect at low temperatures, but have a high friction reduction effect. It is clear from the results of the study of the present inventors that the effect of reducing the friction is lost, and there is a possibility that the effect may not be sufficient for high-speed operation of mechanical devices and automobiles that need to be operated at high temperatures. became.

[0004] Under such circumstances, in order to reduce the friction loss of the internal combustion engine, the effect of reducing the friction in the high temperature range is excellent, and the use of the engine for a long period of time is reduced in view of the necessity of resource saving and energy saving in environmental preservation measures. Therefore, there is a strong demand for lubricating oils having excellent durability of the friction reducing effect.

[0005]

Accordingly, the present invention provides an excellent friction reducing effect and its stability under all conditions fluctuating in the use environment of a lubricating oil, that is, under a wide range of conditions from a low temperature range to a high temperature range. An object of the present invention is to provide a lubricating oil composition that can be used.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
In view of the state of development of conventional friction reducers, as a result of intensive studies to solve the above problems, sulfur-containing organic molybdenum compounds and specific organic acid metal salts, organic salts such as ammonium salts or amine salts, etc. The present inventors have found that the aforementioned problems can be solved by using a compound and zinc dithiophosphate in combination, and have completed the present invention based on these findings.

That is, the first aspect of the present invention is to provide a lubricating base oil comprising at least one organic compound selected from the group consisting of a) a sulfur-containing organic molybdenum compound, b) the following b-1) and b-2) B-1) a metal salt of an organic acid selected from the group consisting of a carboxylic acid, an aliphatic sulfonic acid, an aromatic sulfonic acid, an alkyl salicylic acid, and an alkyl phenol compound, wherein the metal salt is a metal salt of the periodic table 1A, 3A Organic acid metal salt compounds (excluding copper carboxylate) containing a metal selected from the group consisting of metals from Groups 7A, 8 and 1B to 6B; b-2) carboxylic acids, aliphatic sulfones Ammonium salt compounds and amine salt compounds of organic acids selected from the group consisting of acids, aromatic sulfonic acids, alkylsalicylic acids and alkylphenol compounds; and c It relates lubricating oil composition characterized by being obtained by blending a zinc dithiophosphate.

A second aspect of the present invention is to provide a lubricating base oil comprising at least one kind selected from the group consisting of a) a sulfur-containing organic molybdenum compound, b) the following b-1) and b-2): Organic acid salt compound b-1) A metal salt of an organic acid selected from the group consisting of a carboxylic acid, an aliphatic sulfonic acid, an aromatic sulfonic acid, an alkyl salicylic acid, and an alkylphenol compound, wherein the metal salt is a metal salt of the periodic table 1A to Groups 7A, 8 and 1B-
Organic acid metal salt compounds containing a metal selected from the group consisting of Group 6B metals and having a total base number of less than 70 mgKOH / g (excluding copper carboxylate); b-2) carboxylic acids, aliphatic sulfones A lubricating oil composition comprising an ammonium salt compound and an amine salt compound of an organic acid selected from the group consisting of acids, aromatic sulfonic acids, alkyl salicylic acids and alkyl phenol compounds; and c) zinc dithiophosphate. Things.

Further, according to the present invention, the lubricating base oil comprises at least one organic acid selected from the group consisting of a) a sulfur-containing organic molybdenum compound, b) the following b-1) and b-2): Salt compound b-1) A metal salt of an organic acid selected from the group consisting of a carboxylic acid, an aliphatic sulfonic acid, an aromatic sulfonic acid, an alkyl salicylic acid, and an alkyl phenol compound, wherein the metal salt is a group 1A to 7A of the periodic table. , Group 8 and 1B-
Organic acid metal salt compound containing a metal selected from the group consisting of Group 6B metals (excluding copper carboxylate); b-2) carboxylic acid, aliphatic sulfonic acid, aromatic sulfonic acid, alkyl salicylic acid A lubricating oil composition comprising an ammonium salt compound and an amine salt compound of an organic acid selected from the group consisting of: an organic acid metal salt, an organic acid ammonium salt and an organic acid. A lubricating oil composition characterized by having a total base number derived from an acid amine salt compound of 5 mgKOH / g or less can be provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The lubricating base oil as a component of the lubricating oil composition of the present invention is selected depending on the use of the lubricating oil composition, but is not particularly limited as long as it exerts the effects of the present invention. Instead, those usually used as base oils for lubricating oils can be used. For example, mineral base oils,
Synthetic base oils, vegetable oil base oils and the like can be mentioned, and each of these base oils can be used alone or in combination of two or more.

As the mineral base oil, a lubricating oil fraction obtained as a vacuum distillation distillate of an atmospheric distillation residue of a paraffinic, intermediate or naphthenic crude oil is subjected to solvent refining, hydrocracking, hydrotreating, Mineral oil obtained by optionally selecting and using various refining processes such as hydrorefining, catalytic dewaxing, solvent dewaxing, clay treatment, etc. Can be used as a mineral oil obtained by the above-mentioned purification step, a mineral oil obtained by isomerization of a wax component, or a mixed oil thereof.
In the solvent purification, aromatic extraction solvents such as phenol, furfural and N-methyl-2-pyrrolidone are used, while liquefied propane, MEK / toluene and the like are used as solvents for solvent dewaxing. In the catalytic dewaxing, for example, a shape-selective zeolite can be used as a catalyst. In addition, from the viewpoint of oxidation stability and the like, a hydrotreated oil composed of a saturated hydrocarbon having an aromatic hydrocarbon content of 2% by weight or less obtained by the above hydrocracking and hydrotreating can be used.

On the other hand, synthetic base oils include poly-α-olefin oligomers (for example, poly (1-hexene), poly (1-octene), poly (1-decene) and the like and mixtures thereof), polybutene, Alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, di (2
-Ethylhexyl) benzene, dinonylbenzene and the like. ), Polyphenyls (eg, biphenyl, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives thereof; dibasic acids (eg, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, Maleic acid, azelaic acid, spearic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) and various alcohols (for example, butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, diethylene glycol monoether) , Propylene glycol, etc.);
Ester of monocarboxylic acid of No. 2 with a polyol (for example, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.); others, polyoxyalkylene glycol, polyoxyalkylene glycol ester, polyoxyalkylene glycol Examples include alkylene glycol ethers, phosphoric acid esters, and silicone oils.

The vegetable oil base oils include castor oil,
Rapeseed oil, palm oil, coconut oil, coconut oil, olive oil, sunflower oil and the like can be used.

The above-mentioned various lubricating base oils can be prepared so as to have a desired viscosity and other properties according to the use of the lubricating oil composition. Can also. For example, a lubricating oil for an internal combustion engine has a kinematic viscosity at 100 ° C. of 2 mm ² / s to 30 mm.
² / s, particularly, in the range of 3mm ² / s~10mm ² / s, As the automatic transmission oil, a kinematic viscosity at ^{100 ℃ 2mm 2 / s~30mm 2 /} s, in particular, 3 mm ²
/ S to 15 mm ² / s may be adjusted by mixing the mixed base material.

Examples of the sulfur-containing organic molybdenum compound constituting the lubricating oil composition of the present invention include oxymolybdenum dithiocarbamate, oxymolybdenum dithiophosphate and oxymolybdenum dithioxanthogenate. . Sulfurized oxymolybdenum dithiocarbamate is represented by the following general formula [I], sulfided oxymolybdenum dithiophosphate is represented by a general formula [II], and sulfided oxymolybdenum dithioxanthogenate is represented by a general formula [III]. General formula [I]

[0017]

Embedded image General formula [II]

[0018]

Embedded image General formula [III]

[0019]

Embedded image In the above general formulas [I] to [III], R ¹ and R ² are a hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different. Examples of the hydrocarbon group include an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms, and 6 carbon atoms.
A cycloalkyl group having 30 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms, and the aryl group may be substituted with an alkyl group having 1 to 24 carbon atoms. Preferred hydrocarbon groups are alkyl groups having 3 to 24 carbon atoms, for example, propyl group,
Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
Examples thereof include linear or branched alkyl groups such as a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. More preferred alkyl groups are those having 3 to 20 carbon atoms in the sulfurized oxymolybdenum dithiocarbamate represented by the general formula [I], and exhibit a synergistic friction reducing effect when used in combination with an organic acid metal salt compound described below. Show. The sulfurized oxymolybdenum dithiophosphate of the general formula [II] also has 3 to 2 carbon atoms.
An alkyl group of 0 is particularly suitable from the viewpoint of a friction reducing effect. In the sulfurized oxymolybdenum dithioxanthogenate represented by the general formula [III], the alkyl group has 3 to 3 carbon atoms.
A range of 24 is preferred.

The above general formulas [I], [II] and [III]
In the formula, x is 0.5 to 2.3, and preferably 0. Accordingly, typical examples of the oxymolybdenum dithiocarbamate of the general formula [I] suitable for the lubricating oil composition of the present invention include oxymolybdenum dipropyl dithiocarbamate, oxymolybdenum diisopropyl dithiocarbamate, oxymolybdenum dibutyl dithiocarbamate, and oxymolybdenum dibutyl dithiocarbamate. Oxymolybdenum diisobutyl dithiocarbamate, oxymolybdenum dibutenyl dithiocarbamate, oxymolybdenum dipentyl dithiocarbamate, oxymolybdenum diisopentyl dithiocarbamate, oxymolybdenum dihexyl dithiocarbamate, oxymolybdenum diheptyl dithiocarbamate, oxymolybdenum dioctyl sulfide Oxymolybdenum sulfide (2-ethylhexyl) dithioca -Bamate, oxymolybdenum sulfide (2-propylpentyl) dithiocarbamate, oxymolybdenum dinonyl dithiocarbamate, oxymolybdenum sulfide (2-propylhexyl) dithiocarbamate, oxymolybdenum sulfide dodecyl dithiocarbamate, oxymolybdenum sulfide (2
-Methyldodecyl) dithiocarbamate, oxymolybdenum sulfide dihexadecyldithiocarbamate, oxymolybdenum dioctadecyldithiocarbamate, oxymolybdenum sulfide (2-methyloctadecyl) dithiocarbamate and the like. Representative examples of the oxymolybdenum dithiophosphate sulfide of the general formula [II] include oxymolybdenum dipropyl dithiophosphate, oxymolybdenum diisopropyl dithiophosphate, oxymolybdenum dibutyl dithiophosphate, oxymolybdenum diisobutyl dithiophosphate, oxymolybdenum dibutenyl dithiophosphate Phosphate, oxymolybdenum dipentyl dithiophosphate, oxymolybdenum dihexyl dithiophosphate, oxymolybdenum diheptyl dithiophosphate, oxymolybdenum dioctyl dithiophosphate, oxymolybdenum dioctyl dithiophosphate, oxymolybdenum di (2-ethylhexyl) dithiophosphate, oxymolybdenum dinonyl dithiophosphate, oxysulfide Molybdenum didecyl dithiopho Examples include sulfate, oxymolybdenum didodecyl dithiophosphate, oxymolybdenum dioctadecyl dithiophosphate, oxymolybdenum dioleyl dithiophosphate and the like, and compounds having a branched alkyl group or alkenyl group.

Representative examples of the sulfurized oxymolybdenum dithioxanthogenate represented by the general formula [III] include oxymolybdenum butyl dithioxanthogenate, oxymolybdenum pentyl dithioxanthogenate, oxymolybdenum hexyl dithioxanthogenate, Oxymolybdenum sulfide heptyl dithioxanthogenate, oxymolybdenum octyl dithioxanthogenate, oxymolybdenum (2-ethylhexyl) dithioxanthogenate, oxymolybdenum nonyl dithioxanthogenate, oxymolybdenum decyl dithioxanthogenate, sulfided Oxymolybdenum decyl dithioxanthogenate, oxymolybdenum tetradecyl dithioxanthogenate, oxymolybdenum hexadecyl dithioxanthate Sulfonate, oxymolybdenum octadecyl dithiocarbamate xanthogenate sulfide, may be mentioned compounds having a molybdenum oxysulfide nonadecyl dithio xanthogenate, sulfurized oxymolybdenum eicosyl dithio xanthogenate like or branched alkyl or alkenyl groups of these.

The above general formulas [I], [II] and [III]
The sulfur-containing organic molybdenum-based compound represented by
Each of them can be used alone, but two or more kinds may be used in combination. The amount to be added to the lubricating base oil is not limited, and it depends on the use of the lubricating oil composition and the kind of the organic molybdenum-based compound.
~ 2,000 ppm, preferably 200 ppm ~ 1,
It can be used in the range of 500 ppm. If the amount of molybdenum is less than 150 ppm, a synergistic effect with the organic acid metal salt compound cannot be obtained, and a problem that the friction reducing effect is lacking occurs. On the other hand, when the amount of molybdenum is 2,000 ppm
If the amount exceeds the above range, not only the effect corresponding to the increase in the amount is not obtained, but also there is a problem in solubility and there is a possibility of sedimentation.

Although the mechanism of action of such an organic molybdenum compound has not been fully elucidated, it is considered that the MoS _X film is formed on the sliding surface under the conditions of use of the lubricating oil to reduce the coefficient of friction. It is presumed that, therefore, the lubricating oil composition of the present invention is not limited to the above molybdenum compounds as the sulfur-containing organic molybdenum compounds, but has a friction reducing effect by forming a MoS _X film or the like. If so, other compounds can be used.

Next, the organic acid metal salt, organic acid ammonium salt, and organic acid amine salt of the organic acid salt compound used as a component of the lubricating oil composition of the present invention will be described. Organic acid metal salts include carboxylic acids, aliphatic sulfonic acids,
It is composed of an organic acid selected from the group consisting of aromatic sulfonic acids, alkyl salicylic acids and alkylphenol compounds, and a metal component selected from the group consisting of metals of Groups 1A, 3A to 7A, 8 and 1B to 6B. Also,
The organic acid ammonium salt comprises the above organic acid and an ammonium component, and the organic acid amine salt comprises the above organic acid and an amine component.

The metal component of the organic acid metal salt is represented by Periodic Table 1A,
A metal selected from the group consisting of metals of groups 3A to 7A, 8 and 1B to 6B, specifically zinc, cadmium, iron, cobalt, nickel, calcium, magnesium, barium, copper (however, organic acids Is a carboxylic acid, excluding copper.), Lithium, sodium, potassium, aluminum, titanium, manganese, vanadium or scandium. These metal components are selected because of their excellent friction characteristics at high temperatures, and zinc, cadmium, iron, cobalt, and sodium are particularly preferable.

Further, in a metal salt of an organic acid having a total base number of less than 70 mgKOH / g, particularly less than 50 mgKOH / g, in addition to the above-mentioned metal components, alkaline earth metals of the periodic table 2A, namely, magnesium, calcium and Barium is also useful from the viewpoint of the friction reducing effect.

The organic acid ammonium salt is a compound comprising each of the organic acids described below and ammonia.

The amine salt of an organic acid is a compound composed of an organic acid described later and an amine component. The amine component is a primary amine or a secondary amine containing one or two hydrogen atoms bonded to a nitrogen atom. Amines, useful amines can include monoamines or polyamines. Those having 1 to 24 carbon atoms are preferred, and specifically,
For example, methylamine, ethylamine, propylamine,
Butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, cyclopentylamine , Cyclohexylamine, cycloheptylamine and the like.

Further, alkylenediamines are also useful,
Specific examples include methylene diamine, ethylene diamine, propylene diamine, butylene diamine, pentylene diamine, and hexamethylene diamine, and polyalkylene polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and diethylene triamine. Propylene triamine, dibutylene triamine, trifluorobutyltetramine, tetrapropylenepentamine and the like can be used. The carboxylic acid has the general formula [IV]

[0030]

Embedded image (Wherein, R is an aliphatic hydrocarbon group having 1 to 30 carbon atoms or an alicyclic hydrocarbon group or an aromatic hydrocarbon group substituted with at least one chain hydrocarbon group; 4
Is an integer. ), And examples thereof include aliphatic carboxylic acids, alicyclic carboxylic acids, and aromatic carboxylic acids. Also, monocarboxylic acids, dicarboxylic acids,
Any other polycarboxylic acid may be used, and a saturated or unsaturated carboxylic acid is also used.

The aliphatic carboxylic acids include those having 4 to 3 carbon atoms.
0, especially 6 to 24 monocarboxylic acids or dicarboxylic acids are preferred, and specifically, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid) ), Decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid (tridecylic acid), tetradecanoic acid (myristic acid), pentadecanoic acid (pentadecylic acid), hexadecanoic acid (palmitic acid), heptadecanoic acid ( Margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid (nonadecylic acid), eicosanoic acid (arachidic acid),
Alkanic acids such as docosanoic acid (behenic acid) and their branched alkanoic acids, for example, 2-methylpentanoic acid, 2-
Ethylhexanoic acid, 4-propylpentanoic acid, 2-methyldecanoic acid, 3-methylhendecanoic acid, 2-methyldodecanoic acid, 2-methyltridecanoic acid, 2-methyltetradecanoic acid, 2-ethyltetradecanoic acid, 2-propyl Monocarboxylic acids such as decanoic acid, 2-ethylhexadecanoic acid and 2-methyloctadecanoic acid, hexenoic acid, octenoic acid,
Decenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid (petroserinic acid, oleic acid,
Elaidic acid, vaccenic acid, eicosenoic acid, docosenoic acid (erucic acid, brassic acid) octadecatrienyl acid (linoleic acid), hexanedioic acid (adipic acid), heptadioic acid (pimelic acid), octanedioic acid (suberin acid),
Nonanedioic acid (Azelaic acid), Decandioic acid (Sebacic acid), Undecandioic acid, Dodecandioic acid, Tridecandioic acid (Brassic acid), Tetradecandioic acid, Pentadecandioic acid, Hexadecanedioic acid (Tabscinic acid), Heptadecanediacid Examples thereof include dicarboxylic acids such as acid, octadecandioic acid, nonadecandioic acid, eicosandioic acid, and docosandioic acid.

Representative examples of aliphatic monocarboxylic acid metal salts include zinc salts such as zinc octoate, zinc nonanoate, zinc decanoate, zinc undecanoate, zinc dodecanoate, zinc tetradecanoate, zinc hexadecanoate, and zinc octadecanoate. And cadmium salts such as cadmium octanoate and cadmium octadecanoate, silver octanoate, nickel octanoate, iron octanoate and antimony octanoate. Particularly, zinc octoate, zinc octadecanoate, cadmium octoate, iron octoate, cobalt octoate and the like are preferable.

As the aliphatic dicarboxylic acid metal salt, preferred dicarboxylic acids include succinic acid, adipic acid, fumaric acid, sebacic acid and the like, and preferred metals include zinc, cadmium, cobalt, iron and nickel. These aliphatic dicarboxylic acid metal salts are preferably used.

Examples of the carboxylic acid of the metal salt of an alicyclic carboxylic acid include cyclohexane monocarboxylic acid and cyclohexane dicarboxylic acid.
Zinc, cadmium, cobalt, iron, nickel and the like are mentioned, and these alicyclic carboxylic acid metal salts are preferably used.

As the aromatic carboxylic acid, any of a carboxylic acid having a carboxyl group in a side chain as well as a carboxylic acid having a carboxyl group directly bonded to an aromatic ring can be used. The aromatic hydrocarbon group may be either a monocyclic or polycyclic fused ring, and examples thereof include benzene, naphthalene, anthracene, phenanthrene, indene, fluorene, and biphenyl.

Further, monocarboxylic acids, dicarboxylic acids or other polycarboxylic acids can be used, and specific examples thereof include benzoic acid, phthalic acid, phenylacetic acid, mandelic acid, and derivatives thereof.

Specific examples of the aromatic carboxylic acid metal salt compound include zinc, cadmium, and cobalt salts of alkyl benzoic acid, iron salts, nickel salts, zinc salts of phthalic acid, cadmium salts, cobalt salts, and iron salts. Nickel salts and the like can be exemplified. Further, ammonium salts and amine salts of the above-mentioned various carboxylic acids are also suitable. The aliphatic sulfonic acid or the aromatic sulfonic acid is composed of an aliphatic or aromatic hydrocarbon group and a sulfonic acid group, and has a general formula [V] and
[V-1]

[0038]

Embedded image

[0039]

Embedded image It is represented by In the general formulas [V] and [V-1], R,
R ′ is an aliphatic hydrocarbon group, and Ar represents an aromatic hydrocarbon group. The aliphatic sulfonic acid has a chain hydrocarbon group having 4 to 40 carbon atoms, and the aromatic sulfonic acid used is one substituted with one or two or more chain hydrocarbon groups. The chain hydrocarbon group has 4 to 4 carbon atoms.
An alkyl group of 0, particularly an alkyl group having 12 or more carbon atoms is preferable. Specifically, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, tetraxyl Groups, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octakosyl group, a nonacosyl group and a triacontyl group, a pentatriacontyl group, an octatriacontyl group and the like.

The aromatic hydrocarbon group may be a monocyclic or polycyclic condensed ring as in the case of the aromatic carboxylic acid, and examples thereof include benzene, naphthalene, anthracene, phenanthrene, indene, fluorene and biphenyl. can do.

In the lubricating oil composition of the present invention, specific examples of the aliphatic and aromatic sulfonic acid salts are further represented by the following general formula:
[VI] to [XIII]. General formula [VI]

[0042]

Embedded image General formula [VII]

[0043]

Embedded image General formula [VIII]

[0044]

Embedded image General formula [IX]

[0045]

Embedded image General formula [X]

[0046]

Embedded image General formula [XI]

[0047]

Embedded image General formula [XII]

[0048]

Embedded image General formula [XIII]

[0049]

Embedded image In the above general formulas [VI] to [XIII], R ₁ and R ₂ are alkyl groups, which may be the same or different from each other. M is selected from the group consisting of an ammonium component, an amine component and the above-mentioned metals, and includes zinc, cadmium, cobalt, copper, iron, nickel, sodium, potassium and the like. n represents the number of bonds of the alkyl group to the aromatic group, and is an integer of 1 to 5, preferably 1 to 3, and in each formula, they may be the same or different.

Specific examples of the sulfonate used in the lubricating oil composition of the present invention include monoalkylbenzenesulfonic acids, dialkylbenzenesulfonic acids, monoalkylbenzenesulfonic acids having 8 to 20 carbon atoms in the alkyl groups of R ₁ and R _2. Naphthalenesulfonic acid, zinc salts of sulfonic acids of dialkylnaphthalene, cadmium salts, cobalt salts, copper salts, iron salts, nickel salts, sodium salts, potassium salts, ammonium salts and amine salts. When the total base number of the metal sulfonic acid salt is less than 70 mgKOH / g, calcium salts, barium salts, magnesium salts and the like are also preferable. Also,
The above sulfonate may be used alone or in a mixture of two or more.

Salicylic acid is an aromatic carboxylic acid having a hydroxyl group bonded to an aromatic ring and substituted with at least one chain hydrocarbon group. The following general formula [XIV] and general formula [XIV]

[0052]

Embedded image It contains the compound represented by. In the general formula [XIV],
R is a chain hydrocarbon group, and n indicates the number of bonds of the chain hydrocarbon group to the aromatic group, and is an integer of 1 to 4.

The chain hydrocarbon group has 4 to 40 carbon atoms.
Are preferred, specifically, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl group, octadecyl group, nonadecyl group,
Examples thereof include a triacontyl group and a pentatriacontyl group.

As typical examples of the organic acid salt compound of the present invention, a typical compound of a chain hydrocarbon-substituted salicylate is as follows:
It can be represented by the following general formulas [XV] to [XX]. General formula [XV]

[0055]

Embedded image General formula [XVI]

[0056]

Embedded image General formula [XVII]

[0057]

Embedded image General formula [XVIII]

[0058]

Embedded image General formula [XIX]

[0059]

Embedded image General formula [XX]

[0060]

Embedded image In each of the general formulas [XV] to [XX], R ₁ and R ₂ are
Alkyl groups, each of which may be the same or different. M is an ammonium component, an amine component or the above-mentioned metal component, and is preferably zinc, cadmium, cobalt, copper, iron, nickel or the like. N represents the number of substitution of an alkyl group with an aromatic group, and has the general formula [XVII] and
In the formula [XVIII], an integer of 1 to 4;
X] is 1-3, and all are preferably 1-2.
In each of the general formulas, they may be the same or different. The above general formulas [XIX] and [XX] exemplify sulfided alkyl salicylates, wherein x is 1 to
2. The sulfurized alkyl salicylate can be produced, for example, by the method described in Japanese Patent Publication No. 5-80519.

As specific examples of the chain hydrocarbon-substituted salicylate used in the lubricating oil composition of the present invention, the alkyl groups of R ₁ and R ₂ in the above formulas each have 8 to ₂ carbon atoms.
0 zinc, cadmium, cobalt salts of salicylic acid,
Copper salt, iron salt, nickel salt, sodium salt, potassium salt,
Ammonium salts, amine salts and the like are particularly preferred in that they exhibit a friction reducing effect when used in combination with MoDTC or the like. Further, when the total base number is less than 70 mgKOH / g, calcium salts, barium salts, magnesium salts and the like are also preferable. Such a salicylate may be sulfurized by contact with a sulfur compound.

The oil-soluble alkylphenol compound used in the organic acid salt compound of the present invention is one substituted with at least one chain hydrocarbon group, and has the general formula [XVI] or the general formula [XXI].

[0063]

Embedded image It is represented by In the general formula [XXI], R represents 4 to 30 carbon atoms.
M is the number of bonds of a hydroxyl group to an aromatic hydrocarbon group,
It is. n is the number of bonds of the chain hydrocarbon group to the aromatic hydrocarbon group, and is an integer of 1-4, preferably 1-2.

The chain hydrocarbon group has 4 to 30 carbon atoms.
Are preferred. As the alkyl group, specifically, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
Dodecyl, tridecyl, tetradecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,
Examples thereof include a triacontyl group and a pentatriacontyl group.

The following general formulas [XXII] to [XXV] can be given as examples of typical compounds of alkylphenate salts. General formula [XXII]

[0066]

Embedded image General formula [XXIII]

[0067]

Embedded image General formula [XXIV]

[0068]

Embedded image General formula [XXV]

[0069]

Embedded image In each of the above general formulas [XXI] and [XXV], R ₁ ,
R ₂ is an alkyl group, each of which may be the same as or different from each other, and n represents the number of substitutions of the alkyl group with an aromatic group, and is an integer of 1 to 4, preferably 1 or 2,
In each of the general formulas, they may be the same or different. In each general formula, M is an ammonium component,
It is an amine component or the above-mentioned metal component, and examples thereof include zinc, cadmium, cobalt, copper, iron, nickel, sodium, and potassium. Further, x in the general formula [XVII] is 1 to
4.

Specific examples of the alkylphenate salt used in the lubricating oil composition of the present invention include a zinc salt of a phenate having 8 to 20 carbon atoms in the alkyl group of R ₁ and R ₂ .
Cadmium salt, cobalt salt, copper salt, iron salt, nickel salt,
Examples thereof include a sodium salt, a potassium salt, an ammonium salt, and an amine salt. When the total base number is less than 70 mgKOH / g, a calcium salt, a barium salt, and a magnesium salt are also preferable.

The amount of the above-mentioned organic acid salt compound can be arbitrarily determined depending on each compound and the intended use of the lubricating oil composition. A range of １００100 mmol / kg, preferably 1-80 mmol / kg is employed.
The amount of metal is preferably in the range of 100 to 1,000 ppm. In particular, by using the organic acid salt compound at a ratio of 0.5 to 30 mol, preferably 0.5 to 25 mol, per 1 mol of the sulfur-containing organic molybdenum compound, the friction reducing effect can be significantly improved. it can. They are,
Usually, it is used at a ratio of 0.01 to 5% by weight based on the total weight of the lubricating oil composition.

The zinc dithiophosphate as a component of the lubricating oil composition of the present invention will be described. As the zinc dithiophosphate, the following general formula [XXVI]

[0073]

Embedded image Can be mentioned. General formula [XXVI]
In the formula, R ₁ and R ₂ are a hydrocarbon group having 3 to 20 carbon atoms, which may be the same or different. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms;
0 alkenyl group; a cycloalkyl group having 6 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group, and the like. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl. Group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group,
Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, stearyl group, oleyl group, butylphenyl group, nonylphenyl group, etc. and their branched alkyls Groups. Preferred hydrocarbon groups are alkyl groups having 3 to 18 carbon atoms. The alkyl group may be either a primary or secondary alkyl group. Specifically, an isopropyl group,
Isobutyl group, secondary butyl group, pentyl group, hexyl group, 4-methyl-2-pentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl Group,
It is preferable to use a compound having an alkyl group such as an octadecyl group. Accordingly, typical examples of zinc dithiophosphate include, for example, zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-dibutyl thiophosphate, zinc di (n-pentyl) dithiophosphate, and di (n
-Hexyl) zinc dithiophosphate, di (4-methyl-2-)
(Pentyl) zinc dithiophosphate, zinc di-n-octyldithiophosphate, zinc di (2-ethylhexyl) dithiophosphate, zinc di-n-nonyldithiophosphate, zinc di-n-decyldithiophosphate, zinc di-n-dodecyldithiophosphate, di-n
Zinc tridecyl dithiophosphate, zinc di-n-tetradecyl dithiophosphate, zinc di-n-hexadecyl dithiophosphate, zinc di-n-octadecyl dithiophosphate, and the like. As a commercial product, Paranox 15 manufactured by Exxon Chemical Co., Ltd. has a primary alkyl group as a main component, and is appropriately mixed with another commercial product having a secondary alkyl group as a main component to form a primary alkyl group. The content of the group can also be adjusted.

The amount of zinc dithiophosphate to be added to the lubricating oil composition is 100 to 2000 ppm, preferably 200 to 1800 ppm in terms of phosphorus. In particular, for a molybdenum content of 250 ppm, a phosphorus content of 250 to 180
When used at a rate of 0 ppm, preferably 500 to 1500 ppm, a remarkable effect can be obtained in reducing friction at low temperatures. The mixing ratio (molar ratio) of (a) a sulfur-containing organic molybdenum compound, (b) an organic acid salt compound and (c) zinc dithiophosphate is as follows: (a) :( b):
(C) = 1.5 to 5.5: 1 to 30: 5 to 30, preferably (a) :( b) :( c) = 1.5 to 5.5: 1 to 1
The ratio is in the range of 30:10 to 30. By adopting such a mixing ratio of each component, it is possible to improve the friction characteristics from a low temperature range to a high temperature range without excess or deficiency.

According to the present invention, as described above, the lubricating base oil is a) a sulfur-containing organomolybdenum compound;
Organic acid metal salt, organic acid ammonium salt, organic acid salt of organic acid amine salt and c) zinc dithiophosphate are blended, and all bases derived from organic acid metal salt, organic acid ammonium salt and organic acid amine salt The value is 5mgKOH / g
Hereinafter, in particular, a lubricating oil composition of 4 mgKOH / g or less can be provided. The total base number of the lubricating oil composition is 5 mg
In view of the fact that the frictional properties are reduced when KOH / g is exceeded,
The present invention proposes a unique lubricating oil composition having excellent friction characteristics.

The lubricating oil composition of the present invention may further comprise a viscosity index improver, an ashless dispersant, an antioxidant, an extreme pressure agent, an antiwear agent, a metal deactivator, Point depressants, corrosion inhibitors, other friction modifiers and the like can be appropriately selected and blended.

Examples of the viscosity index improver include polymethacrylates, polyisobutylenes, ethylene-propylene copolymers, styrene-butadiene hydrogenated copolymers, and the like. It is used in a proportion of from 35% by weight to 35% by weight.

Examples of the ashless dispersant include polybutenyl succinimide type, polybutenyl succinamide type,
There are benzylamine type and succinate type,
These are usually used in a proportion of 0.05% by weight to 7% by weight.

Examples of the antioxidant include amine antioxidants such as alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated phenyl-α-naphthylamine; 2,6-di-t-butylphenol;
Examples thereof include phenolic antioxidants such as' -methylenebis- (2,6-di-t-butylphenol), and zinc dithiophosphate.
It is used in a proportion of from 5% by weight to 5% by weight.

The extreme pressure agent includes, for example, dibenzyl sulfide, dibutyl disulfide and the like, and these are usually used at a ratio of 0.05% by weight to 3% by weight.

The metal deactivator includes, for example, benzotriazole, benzotriazole derivatives, thiadiazole and the like, and these are usually used at a ratio of 0.01 to 3% by weight.

Examples of the pour point depressant include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene and the like. These are usually used at a ratio of 0.1% by weight to 10% by weight.

Examples of the antiwear agent include a phosphoric acid ester, an acidic phosphoric acid ester, a phosphite, an acidic phosphite, a zinc dialkyldithiophosphate, a sulfur compound and the like. 0.0
It is used in a proportion of 1% to 5% by weight.

Other additives can be arbitrarily selected and used as long as they do not inhibit the action of the sulfur-containing organic molybdenum compound, organic acid salt compound and zinc dithiophosphate of the present invention.

The molybdenum compound and the organic acid salt compound of the present invention can be used in the form of being dissolved in a solvent such as mineral oil, and can also be used as a component of an additive package.

Preferred embodiments of the present invention include: (1) a lubricating base oil comprising: a) a sulfur-containing organic molybdenum compound; b) an aliphatic carboxylic acid having 4 to 30 carbon atoms; and at least one chain hydrocarbon. An aromatic carboxylic acid substituted with a group, an alicyclic carboxylic acid substituted with at least one chain hydrocarbon group, an aliphatic sulfonic acid having 4 to 30 carbon atoms, and at least one chain hydrocarbon group. At least one selected from the group consisting of a substituted aromatic sulfonic acid, a salicylic acid substituted with at least one chain hydrocarbon group, and a phenol compound substituted with at least one chain hydrocarbon group. A metal salt, an ammonium salt or an amine salt of an organic acid, wherein the metal salt is a metal selected from the group consisting of metals of Groups 1A, 3A to 6A, 8 and 1B to 7B of the periodic table. At least one organic acid salt selected from the group consisting of organic acid metal salt compounds, organic acid ammonium salt compounds and organic acid amine salt compounds, and c) having 3 to 3 carbon atoms
18. A lubricating oil composition comprising 18 zinc dithiophosphate.

(2) lubricating base oils include: a) a sulfur-containing organic molybdenum compound, b) dinonylnaphthalenesulfonic acid, alkylbenzenesulfonic acid, alkylsalicylic acid, aliphatic carboxylic acid,
At least one organic acid selected from the group consisting of aromatic carboxylic acids and alkylphenols, and zinc, cadmium, calcium, magnesium, barium, iron, cobalt, nickel, lithium, sodium, potassium, aluminum, titanium, manganese, vanadium and scandium And at least one organic acid salt selected from the group consisting of an organic acid metal salt, an organic acid ammonium salt and an organic acid amine salt comprising at least one metal selected from the group consisting of: and c) zinc dialkyldithiophosphate. A lubricating oil composition,

(3) lubricating base oils, a) a sulfur-containing organic molybdenum compound, b) zinc dinonylnaphthalenesulfonate, zinc alkylbenzenesulfonate, zinc aliphatic carboxylate, zinc aromatic carboxylate, zinc alkylsalicylate At least one organic acid salt selected from the group consisting of zinc alkylphenol, ammonium dinonylnaphtansulfonate, and c) a lubricating oil composition comprising zinc dialkyldithiophosphate,

(4) Based on the weight of the lubricating oil composition, based on the weight of the lubricating oil composition, a) oxymolybdenum sulfide (2-ethylhexyl) dithiocarbamate in an amount of 150 to 1,
A lubricating oil composition comprising: 500 ppm; b) 1 to 50 mmol / kg of zinc octoate; and c) 150 to 2,000 ppm of zinc di (2-ethylhexyl) dithiophosphate as a phosphorus amount.

(5) Based on the weight of the lubricating oil composition, based on the weight of the lubricating oil composition, a) oxymolybdenum sulfide (2-ethylhexyl) dithiocarbamate in an amount of 150 to 1,
500 ppm, b) 1 to 50 m of zinc alkylbenzene sulfonate
mol / kg and c) a lubricating oil composition comprising zinc di (2-ethylhexyl) dithiophosphate in an amount of 150 to 2,000 ppm in terms of phosphorus.

(6) Based on the weight of the lubricating oil composition, based on the weight of the lubricating oil composition, a) oxymolybdenum sulfide di (2-ethylhexyl) dithiocarbamate in an amount of 150 to 1,
500 ppm, b) 1 to 50 cadmium alkylbenzene sulfonate
c) a lubricating oil composition comprising 150 to 2,000 as a phosphorus amount of zinc di (2-ethylhexyl) dithiophosphate;

(7) Based on the weight of the lubricating oil composition, based on the weight of the lubricating oil composition, a) oxymolybdenum sulfide di (2-ethylhexyl) dithiocarbamate in an amount of 150 to 1,
500 ppm, b) 1 to 50 mmol / k zinc alkylsalicylate
g and c) a lubricating oil composition comprising zinc di (2-ethylhexyl) dithiophosphate in an amount of from 150 to 2,000 ppm in terms of phosphorus.

(8) The lubricating oil compositions of (1) to (7) are further added with a viscosity index improver, an ashless dispersant, an antioxidant, an extreme pressure agent, a pour point depressant, an antiwear agent, and a metal. There is provided a lubricating oil composition comprising at least one additive selected from the group consisting of deactivators.

[0094]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the performance evaluation method of the refined mineral oil, the sulfur-containing organic molybdenum-based compound and the organic acid salt compound, and the lubricating oil composition used in Examples and Comparative Examples are as follows. Lubricating base oil Refined mineral oil (100 neutral oil) (Kinematic viscosity ($ 100
° C): 4.2 mm ² / s) Raffinate sulfur-containing organic molybdenum compound obtained by extracting a lubricating oil fraction obtained by vacuum distillation of paraffinic crude oil by distillation under reduced pressure with a phenol solvent (1) MoDTC: Oxymolybdenum sulfide (2-
Ethylhexyl) dithiocarbamate (Sakura Lube 100 manufactured by Asahi Denka Kogyo Co., Ltd.) (2) MoDTP: oxymolybdenum sulfide (2-
Ethylhexyl) dithiophosphate (Sakura Lube 300 manufactured by Asahi Denka Kogyo Co., Ltd.) Organic acid salt compounds Zinc dithiophosphate ZnDTP: di (2-ethylhexyl) zinc dithiophosphate (5660 manufactured by Oroa Co., Ltd.) Lubricating oil composition performance evaluation method Total base number measurement method JIS K2501 Potentiometric titration method (base number (hydrochloric acid method))
Compliant.

Reciprocating friction tester (SRV friction tester) as a friction coefficient measuring tester
The friction coefficient was measured under the following conditions.

Friction material: steel (SUJ-2) / steel (SUJ-2), cylinder / desk Temperature: 80 ° C., 120 ° C. Load: 400 N Amplitude: 50 Hz Time: 15 min Average of the last 3 minutes of measurement for 15 minutes The value was used as the friction coefficient, and the stability of the friction coefficient was evaluated based on the fluctuation range of the friction coefficient.

Examples 1 and 2 A refined mineral oil was used as a lubricating base oil, and MoDTC was used as a sulfur-containing organic molybdenum-based compound in an amount of 500 Mo.
ppm, and zinc alkylbenzenesulfonate as an organic acid salt compound in the ratio shown in Table 1.
1,000 ppm of nDTP was added as P amount. The friction coefficient and the friction coefficient stability of the obtained lubricating oil composition were 2
The measurements were taken at 5 ° C, 80 ° C and 120 ° C, respectively. As a result, the friction coefficient was 0.03 at each temperature.
0.04, which is a good result, and the stability of the coefficient of friction was good at any temperature.

Example 3 A lubricating oil composition was prepared in the same manner as in Example 1 except that the amount of zinc dithiophosphate was reduced to 600 ppm as P. The same results as in Examples 1 and 2 were obtained except that the obtained lubricating oil composition had a friction coefficient at 25 ° C of 0.05.

Examples 4 to 9 MoDTC was added to refined mineral oil in an amount of 500 ppm of Mo, cadmium alkylbenzenesulfonate, zinc octanoate, zinc alkylsalicylate, copper alkylsalicylate,
Antimony octoate was blended in the proportions shown in Table 1, respectively, and further, zinc di (2-ethylhexyl) dithiophosphate was blended at 1,000 ppm as P amount. Of the lubricating oil compositions obtained, in Examples 8 and 9, the total base numbers derived from copper alkylsalicylate or antimony octoate were 0.03 mgKOH / g and 0.02 mK, respectively.
gKOH / g. As shown in the table, 25 ° C, 8
At both 0 ° C. and 120 ° C., the coefficient of friction was low and the coefficient of friction stability was good.

Example 10 Instead of MoDTC, MoDTP was used as the amount of Mo
In the same manner as in Example 1 except that ppm was blended,
As shown in Table 1, a lubricating oil composition excellent in friction coefficient and friction coefficient stability was obtained at any of 25 ° C., 80 ° C., and 120 ° C.

Examples 11 to 15 Refined mineral oil was prepared by adding 500 ppm of MoDTC to Mo, lithium dinonylnaphthalenesulfonate, sodium dinonylnaphthalenesulfonate, potassium dinonylnaphthalenesulfonate, zinc dinonylnaphthalenesulfonate, and aluminum oleate. 3.3m each as shown in Table 1
mol / kg, and zinc di (2-ethylhexyl) dithiophosphate as P content of 1,000
ppm was blended. A lubricating oil composition excellent in friction coefficient and friction coefficient stability was obtained at any temperature of 25 ° C, 80 ° C and 120 ° C.

Examples 16 to 30 Refined mineral oil was mixed with 500 ppm of MoDTC in the amount of Mo, and an organic acid salt compound shown in Table 2 at a ratio shown in the same table. Further, zinc di (2-ethylhexyl) dithiophosphate was added to P
1,000 ppm was added as an amount. Examples 26 to 27
, The total base number was 40.0 mgKOH / g, 6
5.0 mg KOH / g calcium dinonyl naphthalene sulfonate was used. The total base number derived from calcium dinonylnaphthalenesulfonate was 5 mgKOH / g or less. 2 of the lubricating oil composition obtained by the above example
The coefficient of friction at 5 ° C, 80 ° C and 120 ° C and its stability were all good. Tables 1 and 2 show the results.
Shown in

Examples 31 and 32 A lubricating oil composition excellent in both the coefficient of friction and its stability was prepared in the same manner as in Example 1 except that the amount of zinc dithiophosphate was changed to 200 ppm and 1,800 ppm as P. did.

Comparative Example 1 The friction characteristics of a refined mineral base oil were evaluated. As shown in Table 3, the coefficient of friction at 25 ° C., 80 ° C. and 120 ° C. was 0.1.
15 to 0.17, and the stability of the friction coefficient at 120 ° C. was also reduced.

Comparative Example 2 MoDTC and di (2-ethylhexyl) were added to a refined mineral oil.
Zinc dithiophosphate was blended in the proportions shown in Table 3. The obtained lubricating oil composition had good friction coefficient and stability at 25 ° C. and 80 ° C., but at 120 ° C., the results were all inadequate as shown in the table. Reduced the friction characteristics.

Comparative Examples 3, 6 to 8 MoDTC was used without adding zinc dithiophosphate to refined mineral oil.
Was mixed with Mo in an amount of 500 ppm and zinc alkylbenzenesulfonate, cadmium alkylbenzenesulfonate, zinc octanoate, and copper alkylsalicylate in the proportions shown in Table 3 to obtain lubricating oil compositions shown in the same table. 25
As a result, the coefficient of friction at 0 ° C. was remarkably inferior to 0.12 to 0.13.

Comparative Examples 4, 9 to 12 As shown in Table 3, zinc oxide alkylbenzenesulfonate, zinc octanoate, copper alkyl salicylate,
Ammonium dinonylnaphthalenesulfonate and ethylenediamine dinonylnaphthalenesulfonate were blended in the proportions shown in the same table, respectively, and zinc di (2-ethylhexyl) dithiophosphate was blended at 1,000 ppm as P amount. 25
C., 80.degree. C. and 120.degree. C., no excellent friction coefficient was obtained.

Comparative Example 13 As shown in Table 3, a lubricating oil composition was prepared in the same manner as in Example 1 except that the amount of zinc di (2-ethylhexyl) dithiophosphate was reduced to 50 ppm. The coefficient of friction at 80 ° C. and 120 ° C. was improved to 0.03, but at 25 ° C., the result was remarkably inferior to 0.13.

Comparative Example 14 As shown in Table 3, the amount of MoDTC was 5
A lubricating oil composition was prepared in the same manner as in Example 1 except that the amount was reduced to 0 ppm. In particular, Comparative Example 13 showed a result that the favorable coefficient of friction at 80 ° C. was significantly inferior.

Comparative Example 15 Refined mineral oil was obtained by adding MoDTC to Mo at 500 ppm, total base number of 85.0 mgKOH / g, calcium dinonylnaphthalenesulfonate at 37.5 mmol / kg, and zinc di (2-ethylhexyl) dithiophosphate to P A lubricating oil composition having a total base number of 6 mgKOH / g derived from calcium dinonylnaphthalenesulfonate was added in an amount of 1,000 ppm. The coefficient of friction at each temperature was inferior to 0.14.

Comparative Example 16 A lubricating oil composition was obtained in the same manner as in Example 1 except that MoDTC was reduced to 100 ppm in terms of Mo content. However, the friction coefficient at 25 ° C. was inferior to 0.15.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

From the results of the above Examples and Comparative Examples, M
Periodic Table 1A of oDTC or MoDTP and alkylbenzenesulfonic acid, octanoic acid, octadecanoic acid, dinonylnaphthalenesulfonic acid and alkylsalicylic acid
The combined use of metal salts, ammonium salts, and amine salts of groups 7A, 8 and 1B to 6B, and zinc dithiophosphate remarkably improves the friction reduction effect in the low temperature range of 25 ° C, 80 ° C, and 120 ° C. And its stability is shown to be excellent.

[0116]

According to the present invention, the combined use of a sulfur-containing organic molybdenum compound, the above-specified organic acid salt compound and zinc dithiophosphate has an excellent friction reducing effect even at a wide range of temperatures from low to high, and It is possible to provide a lubricating oil composition that is also excellent in the durability of the friction reducing effect.

[Procedure amendment]

[Submission date] October 29, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

[0018]

Embedded image General formula [III]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0083

[Correction method] Change

[Correction contents]

Examples of the antiwear agent include a phosphoric ester, an acidic phosphoric ester, a phosphite, an acidic phosphite, a sulfur compound and the like.
These are usually used at a ratio of 0.01% by weight to 5% by weight.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C10M 139/00 C10M 139/00 Z // C10N 10:02 10:04 10:06 10:10 10:12 10:16 20: 00 30:06 30:08 40:25

Claims (5)

[Claims] 1. A lubricating base oil comprising: a) a sulfur-containing organic molybdenum compound; b) at least one organic acid salt compound selected from the group consisting of the following b-1) and b-2): b-1) A metal salt of an organic acid selected from the group consisting of a carboxylic acid, an aliphatic sulfonic acid, an aromatic sulfonic acid, an alkyl salicylic acid, and an alkylphenol compound, wherein the metal salt is a metal of the periodic table 1A, 3A to 7A, 8 or An organic acid metal salt compound containing a metal selected from the group consisting of Group 1B to 6B metals (excluding copper carboxylate), b-2) carboxylic acid, aliphatic sulfonic acid, aromatic sulfonic acid, An ammonium salt compound and an amine salt compound of an organic acid selected from the group consisting of alkyl salicylic acid and alkyl phenol compound, and c) zinc dithiophosphate. The lubricating oil composition characterized by comprising. 2. The lubricating oil composition according to claim 1, wherein the metal of the organic acid metal salt is zinc, cadmium, iron, cobalt, nickel, copper, lithium, sodium, potassium, aluminum, titanium, manganese, vanadium or scandium. Stuff. 3. A lubricating base oil comprising: a) a sulfur-containing organic molybdenum compound; b) at least one organic acid salt compound selected from the group consisting of the following b-1) and b-2): b-1 A) a metal salt of an organic acid selected from the group consisting of carboxylic acids, aliphatic sulfonic acids, aromatic sulfonic acids, alkyl salicylic acids, and alkylphenol compounds, wherein the metal salts are groups 1A to 7A, 8 and 1B of the periodic table; ~
Organic acid metal salt compounds containing a metal selected from the group consisting of Group 6B metals and having a total base number of less than 70 mgKOH / g (excluding copper carboxylate); b-2) carboxylic acids, aliphatic sulfones A lubricating oil composition comprising an ammonium salt compound and an amine salt compound of an organic acid selected from the group consisting of acids, aromatic sulfonic acids, alkylsalicylic acids and alkylphenol compounds, and c) zinc dithiophosphate. 4. The metal of the organic acid metal salt compound is zinc,
The lubricating oil composition according to claim 3, which is cadmium, iron, cobalt, nickel, calcium, magnesium, barium, copper, lithium, sodium, potassium, aluminum, titanium, manganese, vanadium or scandium. 5. A lubricating base oil comprising: a) a sulfur-containing organic molybdenum compound; b) at least one organic acid salt compound selected from the group consisting of the following b-1) and b-2): b-1) A metal salt of an organic acid selected from the group consisting of a carboxylic acid, an aliphatic sulfonic acid, an aromatic sulfonic acid, an alkyl salicylic acid, and an alkyl phenol compound, wherein the metal salt is a metal of Group 1A to Group 7A, Group 8 and Group 1B to Periodic Table.
Organic acid metal salt compound containing a metal selected from the group consisting of Group 6B metals (excluding copper carboxylate); b-2) carboxylic acid, aliphatic sulfonic acid, aromatic sulfonic acid, alkyl salicylic acid A lubricating oil composition comprising an ammonium salt compound and an amine salt compound of an organic acid selected from the group consisting of: an organic acid metal salt, an organic acid ammonium salt and an organic acid. A lubricating oil composition having a total base number derived from an acid amine salt compound of 5 mgKOH / g or less.