JP2003221588A - Lubricating composition - Google Patents

Abstract

(57) [Problem] To provide a lubricating composition capable of improving the friction reducing effect and oxidative stability of an organic molybdenum compound and exhibiting the friction reducing performance for a long time. as well as,
Improved solubility of organic molybdenum compounds that are difficult to dissolve in lubricating base oils such as MoDTC, so that organic molybdenum compounds are less likely to separate and precipitate even when blended with lubricating base oils having a low aromatic content such as high VI oils. To do. SOLUTION: A lubricating base material has the following general formula (1) as a component (A). (Wherein, R ¹ represents an alkyl group having at least 4 carbon atoms, R ² represents an alkylene group having 2 to 4 carbon atoms, L represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —R
Represents a group represented by ² OH. A) a lubricating composition comprising an organic molybdenum compound as the component (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lubricating composition which can be suitably used as a lubricating oil for internal combustion engines.

[0002]

2. Description of the Related Art Currently, the circumstances surrounding automobiles are becoming stricter such as fuel consumption regulations and exhaust gas regulations. Behind this is environmental protection such as global warming, air pollution, and acid rain, and resource protection from concerns about the limited exhaustion of petroleum energy. Improving fuel efficiency is currently the most effective measure against these problems.

In order to improve the fuel efficiency of automobiles, the automobile itself is improved by reducing the weight of the automobile, improving the engine, etc., and at the same time lowering the viscosity of the engine oil to prevent friction loss in the engine, and a good friction modifier. Improvement of engine oil, such as addition of oil, is also an important factor. The engine oil acts as a lubricant between the piston and the liner, but since there is much fluid lubrication in this portion, friction loss can be reduced by lowering the viscosity of the engine oil. Therefore, in recent years, the viscosity of engine oil has been reduced, but the problems of deterioration of sealing property and increase of wear amount have newly occurred due to the reduction of viscosity of lubricating oil. In addition, engine oil plays an important role in lubrication of valve trains, bearings, etc., but since there is much mixed lubrication and boundary lubrication in this part, lowering the viscosity of engine oil causes increased wear. ing. Therefore, a friction modifier, an extreme pressure agent and the like have been added for the purpose of reducing friction loss due to a decrease in viscosity of engine oil and preventing wear.

Since the organic molybdenum compound has an excellent friction reducing action, it is added to various lubricating oils, but especially in engine oils, it is effective for fuel saving, and is essential for fuel saving oils. It has become an additive of.

[0005]

Even if fuel-saving oil exhibits excellent fuel-saving performance at the stage of new oil, it cannot be said to be excellent fuel-saving oil unless the performance can be maintained for a long period of time. Therefore,
Whether or not the friction reducing effect can be maintained even after long-term use is an important theme required for current fuel-saving oils.

On the other hand, high viscosity index base oils (high VI oils) have good low-temperature startability, have relatively low viscosity, and have little evaporation loss at high temperatures. Nitrogen oxide gas (NOx) and sulfur oxides. It is used as a base oil for fuel-saving oils because it has advantages such as being less susceptible to deterioration due to gas (SOx) and being less susceptible to oxidative deterioration. The mineral oil is composed of an aliphatic component, an alicyclic component and an aromatic component, while the high VI oil is a method such as hydrorefining of the aromatic component and the alicyclic component in the mineral oil which adversely affects the viscosity index. It is obtained by converting to an aliphatic component. Aromatic components and alicyclic components contributed to the solubility of the lubricating oil additive, but in the high VI oil, since these components are small, the lubricating oil additives that have been conventionally used, particularly oxymolybdenum dithiosulfide, have been used. Carver Mate (M
There is a problem that oDTC) is difficult to dissolve (JP-A-3-106995, etc.). On the other hand, Japanese Patent Laid-Open No. 8-
In 176579, an alkyl group asymmetric type MoD is disclosed.
It has been disclosed that TC exhibits excellent solubility even in high VI oil, but such an alkyl group asymmetric MoD
Even with TC, the solubility at low temperatures cannot be said to be sufficient, and high V
When blended with I oil and stored at low temperature for a long time, it sometimes separated and precipitated. In addition, alkyl group asymmetric type MoDTC
Is more susceptible to deterioration than the stable alkyl group symmetrical type, and it is difficult to maintain the friction reducing action for a long period of time (Japanese Patent Laid-Open No. 2000-192068).

[0007]

[Means for Solving the Problems] Therefore, the present inventors diligently studied, and by using an alkanolamine compound having a specific structure and an organic molybdenum compound in combination, the friction reducing performance of the organic molybdenum compound was further improved, The inventors have found that they have excellent oxidative stability, can exhibit their friction reducing performance for a long period of time, and can improve the solubility of organic molybdenum compounds such as MoDTC in high VI oils, etc., leading to the present invention. That is, the present invention provides a lubricating base material having the following general formula (1) as the component (A).

[0008]

[Chemical 4]

(In the formula, R ¹ represents an alkyl group having at least 4 carbon atoms, —R ² OH represents a hydroxyalkyl group having 2 to 4 carbon atoms, L represents a hydrogen atom and 1 carbon atom.
~ 4 alkyl group or a group represented by -R ² OH. ) An alkanolamine compound represented by
A lubricating composition containing an organic molybdenum compound as the component (B).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION First, the component (A) of the present invention will be described. The component (A) of the present invention is an alkanolamine compound represented by the general formula (1). In the general formula (1), R ¹ represents an alkyl group having at least 4 carbon atoms. Examples of such an alkyl group include linear alkyls such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hecisadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl; 2 Secondary butyl, secondary pentyl, secondary hexyl, secondary heptyl, secondary octyl, secondary nonyl, secondary decyl, secondary undecyl, secondary dodecyl, secondary tridecyl, secondary tetradecyl, secondary hexadecyl, secondary hexadecyl Secondary alkyl such as isobutyl, t-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, isooctyl, 2-ethylhexyl, isononyl, isodecyl, isoundecyl, isotridecyl,
Isostearyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-
Branched alkyls such as octyldecyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl-branched-isostearyl and the like can be mentioned. . Among such alkyl groups, linear alkyl having at least 4 carbon atoms is preferable, linear alkyl having 5 to 18 carbon atoms is more preferable, and linear alkyl having 6 to 16 carbon atoms is most preferable. . This is because when R ¹ is a straight-chain alkyl, the friction reducing effect of the lubricating oil composition of the present invention is greater than that of a secondary alkyl or a branched secondary alkyl.

The group represented by --R ² OH is a hydroxyalkyl group having 2 to 4 carbon atoms. 2 to 2 carbon atoms
Examples of the hydroxyalkyl group of 4 include 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 2-hydroxybutyl, 4-hydroxybutyl and the like. From the viewpoint of the friction reducing effect of the lubricating oil composition of the present invention,
Among these, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl are preferable, and 2-hydroxyethyl is most preferable.

In the general formula (1), L represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a group represented by --R ² OH. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl and t-butyl. Among these, a hydrogen atom, a 2-hydroxyethyl group, a methyl group and an ethyl group are particularly preferable from the viewpoint of the friction reducing effect of the lubricating oil composition of the present invention.

The method for producing the alkanolamine compound represented by the general formula (1), which is the component (A) of the present invention, includes, for example, (a) α-olefin oxide (a fat having an epoxy group at the structural terminal in the molecule). Group compound), the following general formulas (5) to (8) HN (R ² OH) ₂ (5) HN (R ² OH) R (6) H ₂ NR ² OH (7) H ₂ NR (8) {In the general formulas (5) to (8), R represents an alkyl group having 1 to 4 carbon atoms, and -R ² OH has the same meaning as in the general formula (1). } A method of reacting an amine represented by the following formula;
(B) a method of reacting an α-olefin oxide with an amine represented by the general formula (7) or (8), and then further reacting with an alkylene oxide having 2 to 4 carbon atoms;
(C) After reacting the α-olefin oxide with an amine represented by the general formula (7) or (8), a monohalogenated alkane having 1 to 4 carbon atoms or a monohalogenated alcohol having 2 to 4 carbon atoms is further added. Method of reacting: (d) α-
A method in which olefin oxide is reacted with ammonia and then further reacted with alkylene oxide having 2 to 4 carbon atoms; (e) α-olefin oxide is reacted with ammonia, and then monohalogenated alkane having 1 to 4 carbon atoms or Examples thereof include a method of reacting a monohalogenated alcohol having 2 to 4 carbon atoms. In the above formula representing the raw material, R represents an alkyl group having 1 to 4 carbon atoms. Among these methods, in the methods (c) and (e), since a halogen compound is used as a raw material, halogen ions that cause metal corrosion easily remain in the product. Is a method that does not use
The methods (a), (b) and (d) are preferred.

The α-olefin oxide used as a starting material can be obtained by a method of oxidizing an α-olefin with a peroxide; a method of converting the α-olefin into a halohydrin compound and then ring-closing with an alkali. Among these, the method of passing through a halohydrin compound is preferably a method of oxidizing an α-olefin with a peroxide to obtain an α-olefin oxide because halogen ions that cause metal corrosion are likely to remain in the product. . Examples of the peroxide used in this case include hydrogen peroxide, peracetic acid, performic acid, t-butyl hydroperoxide, cumene hydroperoxide, and the like.

Examples of the amine used in the above methods (a) to (c) include diethanolamine and N-2.
-Hydroxypropylmonoethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, bis (2-hydroxybutyl) amine and other amines represented by the general formula (5); methylmonoethanolamine, ethylmonoethanolamine, propyl Monoethanolamine, isopropylmonoethanolamine,
Butylmonoethanolamine, isobutylmonoethanolamine, methylmonopropanolamine, methylmonoisopropanolamine, methylmonobutanolamine, methylmonoisobutanolamine, N-methyl-2
An amine represented by the general formula (6) such as hydroxybutylamine; an amine represented by the general formula (7) such as monoethanolamine, monopropanolamine, monoisopropanolamine, monobutanolamine and 2-hydroxybutylamine; methylamine, Examples thereof include amines represented by the general formula (8) such as ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, secondary butylamine, and t-butylamine.

Examples of the alkylene oxide having 2 to 4 carbon atoms used in the above method (b) or (d) include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide) and the like. be able to.

In the above methods (a) to (d), conditions for reacting with amines or ammonia represented by the general formulas (5) to (8); and reacting with alkylene oxide having 2 to 4 carbon atoms. The conditions are not particularly limited, and known reaction conditions of the epoxy compound and amine or ammonia may be used.

In the lubricating composition of the present invention, the addition amount of the component (A) is not particularly limited, but if the addition amount of the component (A) is too small, the lubricating stability of the lubricating oil composition of the present invention will be poor. Since it is sufficient, it may be difficult to exert the friction reducing performance for a long period of time, and if the addition amount of the component (A) is too large, the friction reducing effect may be insufficient. Therefore, the addition amount of the component (A) is preferably 0.01 to 5 mass% with respect to the lubricating base oil,
0.05 to 2 mass% is more preferable, and 0.1 to 1 mass%
Is most preferred.

The component (B) of the lubricating composition of the present invention is an organic molybdenum compound. Examples of the organic molybdenum compound include sulfurized oxymolybdenum dithiocarbamate (MoDTC), sulfurized oxymolybdenum dithiophosphate (MoDTP), sulfurized oxymolybdenum dithiophosphinate, sulfurized oxymolybdenum dithioxanthate, amine and pentavalent or hexavalent molybdenum. Examples thereof include a reaction product with a compound having an atom. Among these organic molybdenum compounds, the following general formula (2)

[0020]

[Chemical 5]

(In the formula, R ^{3 to} R ⁶ represent a hydrocarbon group,
X ^{1 to} X ⁴ represent a sulfur atom or an oxygen atom. ) MoDTC represented by the following general formula (3)

[0022]

[Chemical 6]

(In the formula, R ^{7 to} R ¹⁰ and X ^{5 to} X ⁸ have the same meanings as in the general formula (2)) or MoDTP represented by the following general formula (4) R ¹¹ —NH—R ¹² ( 4) (wherein R ¹¹ and R ¹² represent a hydrogen atom or a hydrocarbon group, but are not hydrogen atoms at the same time) and a compound having a pentavalent or hexavalent molybdenum atom causes friction. It is preferable because MoDTC represented by the general formula (2) is more preferable because the reduction effect and the wear reduction effect are large.

In the general formulas (2) to (4), R ^{3 to} R
¹² represents a hydrocarbon group. Examples of the hydrocarbon group represented by R ^{3 to} R ¹² include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group and a cycloalkenyl group.

Examples of the alkyl group include the alkyl groups mentioned for R ¹ and L in the general formula (1).

As the alkenyl group, for example, vinyl,
Allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like can be mentioned.

As the aryl group, for example, phenyl,
Toluyl, xylyl, cumenyl, mesityl, benzyl,
Phenethyl, styryl, cinnamil, benzhydryl,
Trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, Examples include α-naphthyl and β-naphthyl groups.

Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcyclopentenyl. Examples thereof include a heptenyl group.

Of these, an alkyl group or an alkenyl group is preferable as R ^{3 to} R ^{12, and} it has 5 to 20 carbon atoms.
Is more preferable, and a branched alkyl group having 6 to 18 carbon atoms is most preferable.

In the general formula (2) or (3),
X ^{1 to} X ⁴ and X ^{5 to} X ⁸ are each a sulfur atom or an oxygen atom, and all of X ^{1 to} X ⁴ , X ^{5 to} X ⁸ may be a sulfur atom or an oxygen atom, and four X ¹ To X ⁴ and X ^{5 to} X ⁸ may each be a sulfur atom or an oxygen atom, but in consideration of the balance between the friction reducing effect and the corrosiveness, the ratio of sulfur atom / oxygen atom in the molecule is 1/3. It is particularly preferable that it is ˜3 / 1.

Among the above organic molybdenum compounds,
Since MoDTC represented by the general formula (2) has different solubility in a lubricating base oil depending on the hydrocarbon group of R ^{3 to} R ⁶ and its combination, R ^{3 to} R ⁶ are all the same alkyl group. May be referred to as an alkyl group symmetric MoDTC, and one in which at least one alkyl group of R ^{3 to} R ⁶ is different from other alkyl groups may be referred to as an alkyl group asymmetric MoDTC.

In the lubricating composition of the present invention, the addition amount of the component (B) is not particularly limited, but if the addition amount of the component (B) is too small, the friction reducing effect is not sufficient, and if the addition amount is too large. It tends to cause sludge and corrosion. Therefore, the addition amount of the component (B) is preferably 0.001 to 3% by mass in terms of molybdenum based on the lubricating base oil when the lubricating base oil is the lubricating base oil. , 0.005 to 2 mass% is more preferable, and 0.01 to
Most preferred is 1% by weight. When the lubricious base material is a base grease, the addition amount is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and further preferably 1 to 10 mass% with respect to the base grease. %. When the addition amount of the organic molybdenum compound is relatively small (generally,
It is said that when the molybdenum content relative to the base oil is about 0.03% by mass or less), the wear resistance effect is remarkable, and when the addition amount is relatively large, the friction reducing effect is remarkable.

The organic molybdenum compound as the component (B) may be used alone or in combination of two or more kinds. When two or more organic molybdenum compounds are used, one of them is Mo represented by the general formula (2).
It is preferably DTC. As the MoDTC represented by the general formula (2), either an alkyl group symmetric type MoDTC or an alkyl group asymmetric type MoDTC may be used, but the alkyl group asymmetric type MoDTC is slightly more stable in oxidation than the alkyl group symmetric type MoDTC. There is a case where the sex is insufficient. Therefore, alkyl group asymmetric type MoDTC
In the case of using, it is preferable to use it together with the alkyl group symmetric MoDTC. In this case, the alkyl group asymmetric type Mo
The ratio of DTC and alkyl group symmetric MoDTC is preferably 1/5 to 5/1 in terms of the ratio of molybdenum amounts.

In the lubricating composition of the present invention, the ratio of the blending amount of the component (A) to the blending amount of the component (B) is preferably 1 to 20, more preferably 2 to 15 as the amount of molybdenum. 3-10 is the most preferable.

Among the lubricating oil additives, MoDTC, especially MoDTC having an alkyl group, has insufficient solubility in a lubricating base oil, and therefore, when formulated in high VI oil or the like, it can be stored at low temperature for a long time. By doing so, separation and precipitation may occur. On the other hand, in the lubricating composition of the present invention, the solubility of the organomolybdenum compound as the component (B) is significantly improved by the alkanolamine compound represented by the general formula (1) as the component (A).

Among the components (A) of the present invention, N-2
-Hydroxyalkyl monoethanolamine, N-2-
Hydroxyalkyldiethanolamine and the like are known compounds as lubricating oil additives and have a rust preventive effect (US Pat.
No. 846363, European Patent 239536, etc.), pour point depressing effect of base oil (US Pat. No. 4,123,232)
(Japanese Patent Laid-Open No. 9-10048).
5), a friction increasing effect (Japanese Patent Laid-Open No. 2001-81489), and the like. However, like the lubricating oil composition of the present invention, when used in combination with an organic molybdenum compound, the friction reducing performance of the organic molybdenum compound is further increased, the oxidation stability is excellent, and the friction reducing performance can be exhibited for a long period of time. However, the effect of improving the solubility of the organic molybdenum compound in the lubricating base oil in which the lubricating oil additive such as the high VI oil is difficult to dissolve was not disclosed.

Lubricating base materials that can be used in the present invention include base oils made of mineral oils, synthetic oils, or mixtures thereof, or base greases prepared by blending a thickener with such base oils, as well as water-based base oils. When used as a lubricating oil, water is used as the base material.

The mineral oil used as the base oil of the lubricating composition of the present invention is separated from natural crude oil, and is produced by appropriately distilling and refining it. The main component of mineral oil is hydrocarbons (mostly paraffins), and also contains 1-ring naphthenes, 2-ring naphthenes, aromatics and the like. Base oils obtained by subjecting these to purification such as hydrorefining, solvent dewaxing, solvent extraction, solvent dewaxing, catalytic dewaxing, isomerization dewaxing, hydrocracking, alkaline distillation, washing with sulfuric acid and clay treatment are also preferably used. be able to. These refining means are appropriately combined and performed, and it is also effective to repeat the same treatment in a plurality of stages.

For example, (a) a method of subjecting a distillate oil to a solvent extraction treatment, or a method of subjecting the distillate oil to a hydrogenation treatment followed by a sulfuric acid washing, and (b) a hydrotreating treatment of a distillate oil to a dewaxing treatment. Method, (c) solvent extraction treatment of distillate oil followed by hydrotreatment, (d) solvent extraction treatment of distillate oil followed by clay treatment, (e) two or three-stage distillate oil treatment A method of performing the above-mentioned hydrotreatment, or a method of performing an alkaline distillation or a sulfuric acid washing treatment thereafter, (f) a method of hydrotreating a distillate oil, or a method of performing a hydrotreatment and then an alkali distillation or a sulfuric acid washing treatment, or A method of mixing these treated oils is effective.

By performing these treatments, it is possible to remove aromatic components, sulfur content, nitrogen content, etc. in the unrefined mineral oil. It is said that mineral oil containing a large amount of aromatic components is not only low in viscosity index and oxidation stability but also susceptible to deterioration by NOx and SOx in combustion gas when used as a base oil for engine oil. Further, it is said that the oxidation stability is lower than the sulfur content and the nitrogen content in mineral oil. The base oil having a viscosity index of 100 or more is referred to as a high VI oil, while the base oil having a viscosity index of 120 or more is referred to as a VHVI oil.

According to the present technology, these impurities can be removed in a trace amount or less, but since the aromatic component has the effect of improving the solubility of the lubricating oil additive, it is used in engine oil or the like. The aromatic component in the lubricating base oil is 1 to 5
Mass% is often used. The amount of the aromatic component is determined by the ring analysis of ASTM D-3238 (nd-
m method).

The synthetic oil used as the base oil of the lubricating composition of the present invention is a chemically synthesized lubricating oil, for example, poly-α-olefin, polyisobutylene (polybutene), diester. , Polyol ester, aromatic polycarboxylic acid ester, phosphoric acid ester, silicic acid ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, alkylbenzene and the like.

Examples of poly-α-olefins include:
Examples thereof include 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, which are polymerized or oligomerized, or those which are hydrogenated. Examples of diesters include dibasic acids such as glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and alcohol diesters such as 2-ethylhexanol, octanol, decanol, dodecanol, and tridecanol. Examples of the polyol ester include neopentyl glycol, trimethylolethane, trimethylolpropane,
Glycerin, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, or polyols such as alkylene oxide adducts thereof with butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, capric acid, caproic acid, caprylic acid , Lauric acid, myristic acid, palmitic acid, stearic acid, esters with fatty acids such as oleic acid, and the like. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, and ethylene oxide / propylene oxide block or random copolymer mono- or dimethyl ether.

Each of these synthetic oils is a single substance or a mixture of homologues because it is chemically synthesized. Therefore, for example, synthetic oils such as poly-α-olefins, polyisobutylene (polybutene), diesters, polyol esters, and polyalkylene glycols include benzene, which is an impurity contained in mineral oil, and polycyclic condensed aromatic components, thiophene. Etc., sulfur content, etc., indole, carbazole, etc. nitrogen content, etc. are not included.

Among these mineral oils and synthetic oils, from the viewpoint of oxidation stability, the base oil of the lubricating composition of the present invention is a mineral oil having an aromatic content of 2% by mass or less, poly-α-olefin. , Polyisobutylene, diesters and polyol esters are preferable, and mineral oil having an aromatic content of 1% by mass or less, poly-α-olefin and polyisobutylene are more preferable. Further, in this case, the viscosity index is preferably 120 or more, more preferably 130 or more, and most preferably 135 or more. Further, from the viewpoint of fuel economy, the viscosity of the lubricating base oil is preferably 2 to 20 mm / s in terms of kinematic viscosity at 100 ° C., and 2.5 to 1
More preferably 5 mm / s, 3-10 mm /
Most preferably s.

The base grease comprises the above base oil and a thickener. Examples of the thickener include soap-based or complex soap-based thickeners, organic non-soap-based thickeners, inorganic non-soap-based thickeners, and the like. Examples of soap thickeners include lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, arachidic acid, behenic acid, zomarinic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid. Soap obtained by reacting a higher fatty acid with a base such as aluminum, barium, calcium, lithium, sodium, or potassium, and further reacting the above fatty acid with a base with acetic acid, benzoic acid, sebacic acid, azelaic acid, phosphoric acid, boric acid, or the like. Complex soap thickeners and the like.

Examples of the organic non-soap-based thickeners include terephthalate-based thickeners, urea-based thickeners, and fluorine-based compounds such as polytetrafluoroethylene and fluorinated ethylene-propylene copolymers. However, urea thickeners are preferred.

Examples of urea-based thickeners include monourea-based compounds obtained by reacting monoisocyanate and monoamine, diurea-based compounds obtained by reaction of diisocyanate and monoamine, and urea-urethane-based compounds obtained by reaction of diisocyanate, monoamine and monool. , A tetraurea-based compound obtained by reacting a diisocyanate, a diamine, and a monoisocyanate, and the like.

Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, butyl isocyanate, propyl isocyanate, hexyl isocyanate, octyl isocyanate, lauryl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate phenyl isocyanate, and tolylene isocyanate. Examples of the diisocyanate include hexamethylene diisocyanate and 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate,
Examples thereof include biphenyl diisocyanate and 3,3′-dimethyl biphenyl diisocyanate.

Examples of the monoamine include octylamine, nonylamine, decylamine, laurylamine,
Examples thereof include tridecylamine, myristylamine, palmitylamine, stearylamine, oleylamine, phenylamine, toluylamine, cyclohexylamine and the like. Examples of the diamine include ethylenediamine, propylenediamine, hexamethylenediamine, octamethylenediamine, phenylenediamine, diaminodiphenylmethane and the like.

Examples of monools include butanol, hexanol, 2-ethylhexanol, octanol, decanol, lauryl alcohol, tridecanol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, phenol, cresol and cyclohexanol. To be

Examples of the inorganic non-soap thickener include montmorillonite, bentonite, silica aerogel, boron nitride and the like.

These thickeners may be used alone,
Moreover, you may combine 2 or more types. Although the amount of the thickener is not particularly limited, it is usually preferably 3 to 40% by mass, more preferably 5 to 20% by mass based on the base grease composed of the base oil and the thickener. The consistency of the base grease comprising the above base oil and thickener is not particularly limited, but usually 10
It is about 0 to 500.

The lubricating oil composition of the present invention further contains zinc dithiophosphate as the component (C), whereby the oxidation stability and long drain property are further improved.
Zinc dithiophosphate has the following general formula (9):

[0055]

[Chemical 7]

It is represented by In the general formula (9), R is a hydrocarbon group. As R, an alkyl group or an aryl group is preferable. Among these, an alkyl group having 3 to 14 carbon atoms is preferable. Further, two or more kinds of zinc dithiophosphates having different R ⁵ and R ⁶ may be used in combination. a is 0
It is a number of 1/3, and when a = 0, it is called neutral zinc dithiophosphate, and when a = 1/3, it is called basic zinc dithiophosphate.

The amount of zinc dithiophosphate added is not particularly limited, but it is preferable to add a certain amount in order to exert a practical friction-reducing effect and antioxidant effect. On the other hand, if added too much, the cause of sludge generation. It may be. Therefore, when the lubricating base material is a lubricating base oil, the amount of phosphorus is preferably 0.001 to 3% by mass, and more preferably 0.0
05 to 2% by mass, and more preferably 0.01 to 1% by mass. When the lubricating base material is a base grease, the amount of phosphorus is preferably 0.01 to 1 with respect to the base grease.
It is 0% by mass, more preferably 0.03 to 7% by mass, and further preferably 0.05 to 5% by mass.

The lubricating oil composition agent of the present invention comprises (D1) a metal detergent, (D2) an ashless dispersant, and
(D3) Compound containing phosphorus atom, (D4) Compound containing phosphorus atom and sulfur atom, (D5) Compound containing sulfur atom and containing no metal atom, (D6) Antioxidant, (D7) Organic Metal compound, (D8) oil atom-free agent containing no metal atom, phosphorus atom and sulfur atom, (D9) rust inhibitor, (D10) viscosity index improver, (D11) metal deactivator, (D12) defoaming agent Agent, (D13) solid lubricant, etc. may be blended.

Examples of the metal detergent (D1) include metal sulfonates, metal phenates, metal salicylates,
Examples include metal phosphonates. Examples of the metal sulfonate include (mono or di) alkylbenzene sulfonic acid metal salt, (mono or di) alkylnaphthalene sulfonic acid metal salt, petroleum sulfonic acid metal salt and the like.
Examples of the metal phenate include (mono or di) alkylphenol metal salts, thiobis {(mono or di) alkylphenol} metal salts, methylenebis {(mono or di) alkylphenol} metal salts and the like. Examples of the metal salicylate include (mono or di) alkyl salicylic acid metal salt, thiobis {(mono or di) alkyl salicylic acid} metal salt, methylenebis {(mono or di)
Alkyl salicylic acid} metal salts and the like can be mentioned. The metal atom is preferably an alkali metal or an alkaline earth metal, more preferably calcium, magnesium or barium.

The above compounds are generally neutral salts, but as the metal detergent, the neutral salts are subjected to a basic treatment with a metal oxide or a metal hydroxide while blowing carbon dioxide. Basic or overbased ones are preferably used. Overbased products are usually contained in the form of carbonates. The total base number (TBN) of these basic or overbased metal detergents is generally 150-500 mg KOH.
/ G.

Most preferred of these metal detergents are neutral, basic or overbased calcium salicylates or calcium sulfonates. (D
The preferable blending amount of the component (1) is 0.
It is about 5 to 15 mass%.

Examples of the ashless dispersant (D2) include succinimide, benzylamine, succinic acid ester and boron modified products thereof. Examples of the succinimide include succinic acid having a polyalkenyl group such as polybutenyl group having a molecular weight of about 300 to 4,000, and polyethylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. Examples thereof include monoimides or bisimides, or boric acid-modified products thereof; Mannich reaction products of phenol having a polyalkenyl group, formaldehyde, and polyethylene polyamine.

The nitrogen content in the above ashless dispersant is usually about 0.5 to 2.0% by mass. Among these ashless dispersants, the preferred one is succinimide or its boron modified product. The preferable blending amount of the component (D2) is about 0.5 to 20 mass% with respect to the lubricating base material.

Examples of the compound (D3) containing a phosphorus atom include organic phosphorus compounds such as phosphine, phosphine oxide, phosphinite, phosphonite, phosphinate, phosphite, phosphonate, phosphate, and phosphoramidate. These compounds mainly improve lubricity, wear resistance, etc., but may also act as an antioxidant.

Examples of the organic phosphine represented by (R) ₃ P include tributylphosphine, trihexylphosphine, trioctylphosphine, tri (2-ethylhexyl) phosphine, trinonylphosphine, tridecylphosphine, trilaurylphosphine and trilaurylphosphine. Examples thereof include myristylphosphine, tripalmitylphosphine, tristearylphosphine, trioleylphosphine, triphenylphosphine and tricresylphosphine. Examples of the alkylidene bisphosphine represented by (R) ₂ P- (CH ₂ ) _n -P (R) ₂ include methylenebis (dibutylphosphine), methylenebis (dihexylphosphine), methylenebis (dioctylphosphine), methylenebis (di2). -Ethylhexylphosphine), methylenebis (dinonylphosphine), methylenebis (didecylphosphine), methylenebis (dilaurylphosphine), methylenebis (dimyristylphosphine), methylenebis (dipalmitylphosphine), methylenebis (distearylphosphine), methylenebis ( Dioleylphosphine), methylenebis (diphenylphosphine), methylenebis (dicresylphosphine)
Etc. Examples of the organic phosphine oxide represented by (R) ₃ P═O include tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, tri (2-ethylhexyl) phosphine oxide, trinonylphosphine oxide, and tridecylphosphine oxide. , Trilaurylphosphine oxide, trimyristylphosphine oxide,
Tripalmitylphosphine oxide, tristearylphosphine oxide, trioleylphosphine oxide,
Examples thereof include triphenylphosphine oxide and tricresylphosphine oxide.

Examples of the organic phosphite represented by (RO) ₃ P include mono, di, or tri (hereinafter, mono, di, or tri is abbreviated as mono / di / tri) butyl phosphite. Mono / di / trihexyl phosphite, mono / di / trioctyl phosphite, mono / di /
Tri (2-ethylhexyl) phosphite, mono / di /
Trinonyl phosphite, mono / di / tridecyl phosphite, mono / di / trilauryl phosphite, mono /
Di / trimyristyl phosphite, mono / di / tripalmityl phosphite, mono / di / tristearyl phosphite, mono / di / trioleyl phosphite, mono /
Examples include di / triphenyl phosphite and mono / di / tricresyl phosphite. Examples of other phosphites include pentaerythritol diphosphite, pentaerythritol tetraphosphite, and alkylidene bisphosphite.

Examples of the organic phosphate represented by (RO) ₃ P═O include mono / di / tributyl phosphate, mono / di / trihexyl phosphate, mono /
Di / trioctyl phosphate, mono / di / tri (2-
Ethylhexyl) phosphate, mono / di / trinonyl phosphate, mono / di / tridecyl phosphate, mono / di / trilauryl phosphate, mono / di / trimyristyl phosphate, mono / di / tripalmityl phosphate, mono / di / tri Stearyl phosphate, mono / di / trioleyl phosphate, mono / di / triphenyl phosphate, mono / di / tricresyl phosphate and the like can be mentioned. Further, a phosphate having a polyoxyalkylene group, for example, a phosphate of an adduct of lauryl alcohol ethylene oxide and / or propylene oxide, etc. may be mentioned.

Of these phosphates, mono- or diphosphates are called acidic phosphoric acid esters and may be used after being neutralized with a base such as alkali or amine. Examples of the alkali include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide. Examples of the amine include ammonia; methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tridecylamine, cetylamine, Alkylamines such as coconut alkylamine, soybean oil-derived alkylamine, beef tallow-derived alkylamine, oleylamine and stearylamine; monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2
-Amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ', N'-tetrakis (hydroxyethyl) ethylenediamine, N,
Alkanolamines such as N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or alkylene oxide adducts thereof; N-butyldiethanolamine, N-hexyldiethanolamine, N-
Octyldiethanolamine, N-decyldiethanolamine, N-coconut alkyldiethanolamine, N-soybean oil-derived alkyldiethanolamine, N-beef tallow-derived alkyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, N, N-
Dibutylmonoethanolamine, N, N-dihexylmonoethanolamine, N, N-dioctylmonoethanolamine, N, N-didecylmonoethanolamine,
N, N-bis (coconut alkyl) monoethanolamine,
N, N-bis (alkyl derived from soybean oil) monoethanolamine, N, N-bis (alkyl derived from beef tallow) monoethanolamine, N-dioleyl monoethanolamine, N-
Examples thereof include N-long-chain alkylalkanolamines such as distearyl monoethanolamine and their alkylene oxide adducts. Examples of phosphoramidates include those obtained by subjecting the above phosphate and the above amine to a condensation reaction. The preferable blending amount of the component (D3) is about 0.1 to 10% by mass with respect to the lubricating base material.

Examples of the compound (D4) containing a phosphorus atom and a sulfur atom include trithiophosphite, thiophosphate and the like. These compounds mainly improve lubricity, wear resistance, etc., but may also act as an antioxidant.

Examples of the organic trithiophosphite represented by (RS) ₃ P include mono / di / tributyl trithiophosphite, mono / di / trihexyl trithiophosphite, mono / di / trioctyltrithiophosphite, and mono / di / trioctyltrithiophosphite. / Di / tri (2-ethylhexyl) trithiophosphite, mono / di / trinonyltrithiophosphite, mono / di / tridecyltrithiophosphite,
Mono / di / trilauryl trithiophosphite, mono /
Di / trimyristyl trithiophosphite, mono / di /
Tripalmityl trithiophosphite, mono / di / tristearyl trithiophosphite, mono / di / trioleyl trithiophosphite, mono / di / triphenyl trithiophosphite, mono / di / tricresyl trithiophosphite, etc. To be

Examples of the organic thiophosphate represented by (RO) ₃ P = S include mono / di / tributyl thiophosphate, mono / di / trihexyl thiophosphate, mono / di / trioctyl thiophosphate, mono / di / Tri (2-ethylhexyl) thiophosphate,
Mono / di / trinonyl thiophosphate, mono / di / tridecyl thiophosphate, mono / di / trilauryl thiophosphate, mono / di / trimyristyl thiophosphate, mono / di / tripalmityl thiophosphate,
Examples include mono / di / tristearyl thiophosphate, mono / di / trioleyl thiophosphate, mono / di / triphenyl thiophosphate, mono / di / tricresyl thiophosphate, and the like. Further, dithiophosphoric acid dimer can also be used. The preferable blending amount of the component (D4) is about 0.1 to 10% by mass with respect to the lubricating base material.

Examples of the compound (D5) containing a sulfur atom and containing no metal atom include fats and oils such as sulfurized lard, sulfurized fish oil, sulfurized whale oil, sulfurized soybean oil, sulfurized pinene oil, sulfurized gypsum oil, and sulfurized fatty acid. In addition to sulfurized double bonds of the compounds derived from, simple sulfur, organic mono- or polysulfide, sulfides of polyolefin such as isobutylene, 1,
3,4-thiadiazole derivative, thiuram disulfide, dithiocarbamic acid ester and the like can be mentioned.

The organic mono- or polysulfide represented by the following general formula (D5-1) R- _Sx- R (D5-1) is:
For example, dimethyl mono / di / polysulfide, diethyl mono / di / polysulfide, dipropyl mono / di /
Polysulfide, diisopropylmono / di / polysulfide, dibutylmono / di / polysulfide, diisobutylmono / di / polysulfide, ditertiarybutylmono / di / polysulfide, dipentylmono / di / polysulfide, diisopentylmono / di / polysulfide, dineopentyl Mono / di / polysulfide, ditertiary pentyl mono / di / polysulfide, dihexyl mono / di / polysulfide, diheptyl mono / di / polysulfide, dioctyl mono / di /
Polysulfide, di2-ethylhexylmono / di / polysulfide, dinonylmono / di / polysulfide, ditercharinonylmono / di / polysulfide,
Didecyl mono / di / polysulfide, diundecyl mono / di / polysulfide, didodecyl mono / di / polysulfide, ditridecyl mono / di / polysulfide, diisotridecyl mono / di / polysulfide, ditetradecyl mono / di / polysulfide, dihexadecyl mono / di / Polysulfide, distearyl mono /
Di / polysulfide, diisostearyl mono / di / polysulfide, dioleyl mono / di / polysulfide, diicosylmono / di / polysulfide, didocosylmono / di / polysulfide, ditetracosylmono /
Di / polysulfide, ditriacontyl mono / di / polysulfide, diphenyl mono / di / polysulfide, ditoluyl mono / di / polysulfide, dixylyl mono / di / polysulfide, dicumenyl mono / di /
Polysulfide, dimesityl mono / di / polysulfide, dibenzyl mono / di / polysulfide, diphenethyl mono / di / polysulfide, distyryl mono /
Di / polysulfide, dicinnamyl mono / di / polysulfide, dibenzhydryl mono / di / polysulfide, ditrityl mono / di / polysulfide, di (ethylphenyl) mono / di / polysulfide, di (propylphenyl) mono / di / polysulfide, di (butyl) Phenyl) mono / di / polysulfide, di (pentylphenyl) mono / di / polysulfide, di (hexylphenyl) mono / di / polysulfide, di (heptylphenyl) mono / di / polysulfide, di (octylphenyl) mono / di / Polysulfide, di (nonylphenyl) mono / di / polysulfide, di (decylphenyl) mono / di / polysulfide, di (undecylphenyl) mono / di / polysulfide, di (dodecylphenyl) mono / / Polysulfide, di (phenylphenyl) mono / di / polysulfide, di (benzylphenyl) mono / di / polysulfide, di (styrenated phenyl) mono / di / polysulfide, di (p-cumylphenyl) mono / di / polysulfide, di Dicyclohexylmono / di / polysulfide, dicyclohexylmono / di / polysulfide, dicycloheptylmono / di / polysulfide, dimethylcyclopentylmono / di / polysulfide, dimethylcyclohexylmono / di / polysulfide, dimethylcycloheptylmono / di / polysulfide, etc. Hydrocarbyl sulfide; di (ethylhydroxyphenyl) mono / di / polysulfide, di (propylhydroxyphenyl) mono / di / polysulfide, di (butyl) Hydroxyphenyl) mono / di / polysulfide, di (pentylhydroxyphenyl) mono / di / polysulfide, di (hexylhydroxyphenyl) mono / di / polysulfide, di (heptylhydroxyphenyl) mono / di / polysulfide, di (octylhydroxyphenyl) ) Mono / di / polysulfide, di (nonylhydroxyphenyl) mono / di / polysulfide, di (decylhydroxyphenyl) mono / di / polysulfide, di (undecylhydroxyphenyl) mono / di / polysulfide, di (dodecylhydroxyphenyl) Examples include dihydrocarbylphenol sulfide such as mono / di / polysulfide.

The 1,3,4-thiadiazole derivative has the following general formula (D5-2).

[0075]

[Chemical 8]

(In the formula, R represents a hydrocarbon group or a hydrocarbon group containing a sulfur atom). Examples of the sulfur-containing hydrocarbon group include 5-thianonyl,
2,5-dithianonyl, 3,4-dithiahexyl, 4,
5-dithiahexyl, 3,4,5-trithiaheptyl,
3,4,5,6-tetrathiaoctyl, 5-thia-2-
Heptenyl, 4-thiacyclohexyl, 1,4-dithianaphthyl, 5- (methylthio) octyl, 4- (ethylthio) -2-pentenyl, 4- (methylthio) cyclohexyl, 4-mercaptophenyl, 4- (methylthio)
Examples thereof include phenyl, 4- (hexylthio) benzyl, stearyldithio, lauryldithio, octyldithio, stearylthio, laurylthio, octylthio, N, N-dialkyldithiocarbamoyl, and the like.
A group in which four sulfur atoms are continuously bonded is particularly preferable.

Thiuram disulfide has the following general formula (D5-3).

[0078]

[Chemical 9]

(R represents a hydrocarbon group, and R ′ represents a sulfur atom, a divalent hydrocarbon group or a divalent hydrocarbon group containing a sulfur atom). As R ',-
S (-S) _n - (. Where, n is the number of 0 or 1 or more) groups represented by a methylene _{group, -S (-S) n (-CH} 2) n
-S (-S) _n- (where n is the same or different, 0 or 1
More than that. ) And the like. R is preferably a chain hydrocarbon group having 4 or more carbon atoms.

The dithiocarbamic acid ester has the following general formula (D5-4).

[0081]

[Chemical 10]

(R represents a hydrocarbon group, R ′ represents a hydrogen atom, a hydrocarbon group or a group represented by COOR ″, and R ″ represents a hydrocarbon group). The preferable blending amount of the component (D5) is about 0.1 to 15 mass% with respect to the lubricating base material.

Examples of (D6) antioxidants include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants and the like.

Examples of the phenolic antioxidant include 2,6-di-tert.-butylphenol (hereinafter, tert.-butyl is abbreviated as t-butyl),
2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t
-Butyl-4-ethylphenol, 2,4-dimethyl-
6-t-butylphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 4,4'-
Bis (2-methyl-6-t-butylphenol), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-
t-butylphenol), 4,4'-butylidene bis (3-methyl-6-t-butylphenol), 4,4 '
-Isopropylidene bis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-)
Cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol),
2,6-bis (2'-hydroxy-3'-t-butyl-
5'-methylbenzyl) -4-methylphenol, 3-
t-Butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, stearyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 3- (4-hydroxy-3) , 5-Di-t-butylphenyl) propionate oleyl, 3- (4-hydroxy-3,5-di-t-butylphenyl) dodecyl propionate, 3- (4-hydroxy-3,5-di-t) -Butylphenyl) decyl propionate, octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis {3- (4-hydroxy-3,5)
-Di-t-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy-3,5-di-t-
Butylphenyl) propionic acid glycerin monoester, ester of 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid and glycerin monooleyl ether, 3- (4-hydroxy-3,5-di) -
t-Butylphenyl) propionic acid butylene glycol ester, 3- (4-hydroxy-3,5-di-t-butylphenyl) propionic acid thiodiglycol ester, 4,4′-thiobis (3-methyl-6-t -Butylphenol), 4,4'-thiobis (2-methyl-6-
t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-
Butyl-α-dimethylamino-p-cresol, 2,6
-Di-t-butyl-4- (N, N'-dimethylaminomethylphenol), bis (3,5-di-t-butyl-4)
-Hydroxybenzyl) sulfide, Tris {(3,
5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl} isocyanurate, tris (3,5-di-t-butyl-4-hydroxyphenyl)
Isocyanurate, 1,3,5-tris (3,5-di-
t-butyl-4-hydroxybenzyl) isocyanurate, bis {2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl} sulfide, 1,3,5-tris (4-t -Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetraphthaloyl-di (2,6-dimethyl-4-t)
-Butyl-3-hydroxybenzyl sulfide), 6
-(4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine, 2,2-thio- {diethyl-bis-3--
(3,5-di-t-butyl-4-hydroxyphenyl)} propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinamide), 3,5-di -T-butyl-4-hydroxy-
Benzyl-phosphoric acid diester, bis (3-methyl-4-
Hydroxy-5-t-butylbenzyl) sulfide,
3,9-bis [1,1-dimethyl-2- {β- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-) Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis {3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid} glycol ester, etc. Can be mentioned.

As the amine-based antioxidant, for example, 1
-Naphthylamine, phenyl-1-naphthylamine, p
-Octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, phenyl-2-naphthylamine and other naphthylamine antioxidants; N, N'-diisopropyl-p-phenylenediamine , N, N'-diisobutyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl- p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-
1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine,
Phenylenediamine antioxidants such as phenylhexyl-p-phenylenediamine and phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p, p'-di-n-butyldiphenylamine, p,
p'-di-t-butyldiphenylamine, p, p'-di-t-pentyldiphenylamine, p, p'-dioctyldiphenylamine, p, p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p, p '
-Didodecyldiphenylamine, p, p'-distyryldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4-α, α-dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, dipyridylamine, etc. Diphenylamine antioxidant; phenothiazine, N-methylphenothiazine,
Examples include phenothiazine antioxidants such as N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester, and phenoselenazine.

Examples of the sulfur type antioxidant include dioctyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiol. Dipropionate, dimyristyl thiodipropionate, distearyl-β,
β'-thiodibutyrate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-stearyl (Thiopropionic acid) pentaerythritol tetraester, (3
-Oleylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid)-
4,4'-thiodi (3-methyl-5-t-butyl-4-
Phenol) ester, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, 2-
Examples thereof include benzimidazole disulfide, dilauryl sulfide and amyl thioglycolate. (D
The blending amount of the component 6) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.1 to 2% by mass with respect to the lubricating base material.

The organometallic compound (D7) improves abrasion resistance and antioxidant properties. Specifically, for example, hexanoic acid, octanoic acid, pelargonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid, linolenic acid and other fatty acids or lithium naphthenic acid. , Sodium, potassium, magnesium, calcium, barium,
Titanium, zinc, lead, tin, iron, cadmium, cobalt,
Examples thereof include nickel, manganese, strontium, titanium, vanadium, copper, antimony, bismuth and tungsten salts. The fatty acid preferably has about 12 to 18 carbon atoms.

Further, metal salts of dithiophosphoric acid, metal salts of dithiocarbamic acid, metal salts of mercaptobenzothiazole, metal salts of mercaptobenzimidazole, metal salts of benzamide thiophenol and the like can be mentioned. The metal atom is the metal atom exemplified above. In addition, sulfurized oxymolybdenum dialkyldithiocarbamate and sulfurized oxymolybdenum dithiophosphate can be preferably used. The blending amount of the component (D7) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, and most preferably 0.1 to 2% by mass with respect to the lubricating base material.

The component (D8) is an oiliness improver containing no metal atom, phosphorus atom or sulfur atom. For example, fatty acids such as hexanoic acid, octanoic acid, pelargonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, linoleic acid, linolenic acid; linseed oil, eno oil, eutica oil, olive oil,
Cocoa butter, kapok oil, white mustard oil, sesame oil, rice bran oil, safflower oil, shea nut oil, cinnamon oil, soybean oil, tea seed oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, castor oil, Sunflower oil, cottonseed oil, palm oil, wax, peanut oil, horse fat, beef tallow, beef tallow, beef tallow,
Fats and oils such as pork fat, goat fat, sheep fat, milk fat, fish oil and whale oil, or hydrogenated or partially saponified products thereof; epoxidized soybean oil, epoxidized linseed oil and other epoxidized fats and oils: butyl epoxy stearate, epoxy stearic acid Epoxidized esters such as octyl; dibasic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid; ricinoleic acid (castor oil fatty acid), 12-hydroxystearic acid A polycondensate of a hydrocarboxylic acid or an ester of a polycondensate with a fatty acid; a higher alcohol such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol; laurylamine, myristylamine, palmityl Amine, Stearyl Higher amines such as amine, oleylamine and behenylamine; higher amides such as laurylamide, myristylamide, palmitylamide, stearylamide, oleylamide, behenylamide; lauryldiethanolamide, myristyldiethanolamide, palmityldiethanolamide, stearyldiethanolamide. , Oleyldiethanolamide, behenyldiethanolamide and other diethanolamides; hexanoic acid mono /
Di / triglyceride, octanoic acid mono / di / triglyceride, decanoic acid mono / di / triglyceride, lauric acid mono / di / triglyceride, myristic acid mono / di / triglyceride, palmitic acid mono / di / triglyceride, stearic acid mono / di / Glycerides such as triglyceride, oleic acid mono / di / triglyceride, behenic acid mono / di / triglyceride; hexanoic acid polyglycerin ester, octanoic acid polyglycerin ester, decanoic acid polyglycerin ester, lauric acid polyglycerin ester, myristic acid polyglycerin ester Polyglycerin ester such as palmitic acid polyglycerin ester, stearic acid polyglycerin ester, oleic acid polyglycerin ester, behenic acid polyglycerin ester, etc .; Sorbitan esters such as sorbitan acid ester, sorbitan octanoate, sorbitan decanoate, sorbitan lauric acid, sorbitan myristic acid, sorbitan palmitate, sorbitan stearate, sorbitan oleate, and sorbitan behenate; Poly) glycerin monooctyl ether, (poly) glycerin monodecyl ether, (poly)
(Poly) glycerin ethers such as glycerin monolauryl ether, (poly) glycerin monooleyl ether, (poly) glycerin monostearyl ether; ethylene oxide, propylene oxide,
Examples thereof include those to which α-olefin oxide such as dodecane-1,2-oxide is added. The preferable blending amount of the component (D8) is 0.05 to 15 with respect to the lubricating base material.
It is about mass%.

The component (D9) is a rust preventive agent. For example,
Examples of the metal detergent include sulfonate, sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, tallow fatty acid alkali metal salt, alkaline earth metal salt or amine salt, alkenyl succinic acid or alkenyl succinic acid half ester ( The alkenyl group has a molecular weight of about 100 to 300), sorbitan monoester, pentaerythritol monoester, glycerin monoester, nonylphenol ethoxylate, lanolin fatty acid ester, lanolin fatty acid calcium salt and the like. The preferable blending amount of the component (D9) is about 0.1 to 15% by mass with respect to the lubricating base material.

The component (D10) is a viscosity index improver.
For example, poly (C1-18) alkyl methacrylate,
(C1-18) Alkyl acrylate / (C1-18)
Alkyl methacrylate copolymer, diethylaminoethyl methacrylate / (C1-18) alkyl methacrylate copolymer, ethylene / (C1-18) alkyl methacrylate copolymer, polyisobutylene, polyalkylstyrene, ethylene / propylene copolymer, styrene /
Maleic acid ester copolymer, styrene / maleic acid amide copolymer, styrene / butadiene hydrogenated copolymer,
Examples thereof include styrene / isoprene hydrogenated copolymer.
The average molecular weight is about 10,000 to 1,500,000. The preferable blending amount of the component (D10) is about 0.1 to 20 mass% with respect to the lubricating base material.

The component (D11) is a metal deactivator. For example, N, N′-salicylidene-1,2-propanediamine, alizarin, tetraalkylthiuram disulfide, benzotriazole, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, N -Dialkyldithiocarbamoyl) benzothiazole, 2,5-bis (alkyldithio) -1,3,4-thiadiazole,
2,5-bis (N, N-dialkyldithiocarbamoyl) -1,3,4-thiadiazole and the like can be mentioned.
The preferable blending amount of the component (D11) is about 0.01 to 5 mass% with respect to the lubricating base material.

The component (D12) is an antifoaming agent. Examples thereof include polydimethyl silicone, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy / propoxylate, and fatty acid ethoxy / propoxylate. The preferable blending amount of the component (D12) is about 0.001 to 1 mass% with respect to the lubricating base material.

The component (D13) is a solid lubricant. For example, graphite, molybdenum disulfide, polytetrafluoroethylene, fatty acid alkaline earth metal salts, mica, cadmium dichloride, cadmium diiodide, calcium fluoride, lead iodide, lead oxide, titanium carbide, titanium nitride, aluminum silicate , Antimony oxide, cerium fluoride, polyethylene, diamond powder, silicon nitride, boron nitride fluorocarbon, melamine isocyanurate and the like. The preferable blending amount of the component (D13) is about 0.005 to 2% by mass with respect to the lubricating base material.

The above components (D1) to (D13) are
One kind or two or more kinds can be appropriately mixed. When the lubricating composition of the present invention is used as a lubricating oil for internal combustion engines, it is preferable to incorporate at least (D1) a metal detergent.

The lubricious composition of the present invention can be used for lubrication for all purposes. For example, industrial lubricating oil,
Turbine oil, machine oil, bearing oil, compressor oil, hydraulic oil, hydraulic oil, internal combustion engine oil, refrigeration oil, gear oil, automatic transmission oil (ATF), continuously variable continuously variable transmission oil (CVTF), transformer Examples include axle fluids and metalworking oils. or,
Sliding bearings, rolling bearings, gears, universal joints, torque limiters, constant velocity joints for automobiles (CV
J), ball joints, wheel bearings, constant velocity gears, variable speed gears, and other greases. The lubricating composition of the present invention is resistant to oxidative deterioration and exhibits excellent low-temperature stability even when the organic molybdenum compound is MoDTC. Therefore, among the above-mentioned applications, internal combustion engines such as gasoline engine oil and diesel engine oil are particularly preferable. It can be preferably used for oil.

[0097]

The present invention will be described in more detail with reference to the following examples. In the following examples,% is based on mass unless otherwise specified. In this test, the following lubricating base material and lubricating oil additive were used.

<Lubricating base material> (Base oil 1) Mineral oil high VI oil.

[0099] (Base oil 2) A synthetic oil composed of poly-α-olefin obtained by the oligomerization of 1-decene. (Base grease) Kinematic viscosity at 100 ° C is 6mm ² / s
A base grease having a consistency of 300 at 25 ° C., which is obtained by uniformly dispersing an aliphatic amine urea compound in the refined mineral oil described above.

<Component A: Alkanolamine Compound> (A-1) A mixture of N- (2-hydroxyhexadecyl) diethanolamine and (N-2-hydroxyoctadecyl) diethanolamine (molar ratio 1: 1) (A-2). N- (2-hydroxyhexadecyl) monoethanolamine and N- (2-hydroxyoctadecyl)
Mixture of monoethanolamine (molar ratio 1: 1) (A-3) N- (2-hydroxydodecyl) diethanolamine (A-4) N-methyl-N- (2-hydroxydodecyl) monoethanolamine <B component: Oil-soluble molybdenum compound> (B-1) In the general formula (2), R ^{3 to} R ⁶ are 2-ethylhexyl groups MoDTC (B-2) In the general formula (2), R ³ and R ⁴ are 2-ethylhexyl groups. MoDTC (B-3) in which R ⁵ and R ⁶ are isotridecyl groups, and R ^{7 to} R ⁸ in the general formula (3) are 2-ethylhexyl groups MoDTP (B-4) 1 mol of molybdenum trioxide and diamine Seo tridecyl amine 2 moles of reactant ^{(B-5) MoDTC R 3} ~R 6 in the general formula (2) is a butyl group <C component: zinc dithiophosphate> (C-1) general Zinc dithiophosphate in which R is a 2-ethylhexyl group in (9) (a = 0.05) (C-1) Zinc dithiophosphate in which R is a 1,3-dimethylbutyl group in general formula (9) (a = 0.0
5) <A 'component: for comparison>(A'-1) oleylamine (A'-2) coconut oil fatty acid diethanolamide (A'-3) fatty acid amide obtained by reacting coconut oil fatty acid and methyl monoethanolamine

<Evaluation with Lubricating Oil Composition> The lubricating oil compositions of Examples 1 to 28 and Comparative Examples 1 to 24 were prepared according to the formulations shown in Table 1 below, and their low temperature stability and lubricity were evaluated. evaluated. The results are shown in Tables 1 and 2.

[Evaluation Method] (Low Temperature Stability Test) Each lubricating oil composition was tested at −15 ° C. and −1.
Store at 0 ° C for 2 days, 14 days, 30 days and 90 days
The presence or absence of precipitation was visually determined after the day, and the dissolution stability at low temperature was evaluated according to the following criteria. A: No precipitation is observed even after 90 days. B: No precipitation was observed after 30 days, but precipitation was observed after 90 days. C: No precipitation was observed after 7 days, but precipitation was observed after 30 days. D: No precipitation was observed after 2 days, but precipitation was observed after 7 days. E: Precipitation was observed after 2 days. (Lubricity test) Using a SRV tester, the friction coefficient of each lubricating oil composition was measured before and after oxidative deterioration under the following conditions. Test piece Upper part: Cylindrical test piece (φ15 × 22mm, material SUJ-2) Lower part: Disc-shaped test piece (φ24 × 6.85mm, material SUJ-2) Contact condition of test piece Line contact (perpendicular to sliding direction Reciprocating) Load 200 N Amplitude 1 mm Cycle 50 Hz Measurement temperature 100 ° C. Measurement time 15 minutes (oxidation deterioration condition) Each lubricating oil composition was oxidized and deteriorated according to JIS K2514. In addition, JIS K2514
Then, the mixture was stirred at a temperature of 165.5 ° C. for 24 hours, but in this test, the mixture was stirred at a temperature of 175 ° C. for 20 hours.

[0103]

[Table 1] Table 1

[0104]

[Table 2] Table 2

<Test on Grease Composition> Each component was added to the base grease according to the formulation shown in Table 2 below, and Example 29 was used.
~ 43 and Comparative Examples 23-31 were prepared, and the lubricity of these grease compositions was evaluated before and after oxidative deterioration. The results are shown in Tables 3 and 4. [Evaluation method] (Lubricity test) Under the same conditions as the lubricity test of the lubricating oil composition, except that the measurement time was changed from 15 minutes to 2 hours.
By measuring the coefficient of friction using an SRV tester,
The lubricity of each grease composition was evaluated. (Oxidative deterioration conditions) A glass petri dish coated with the grease composition to a thickness of about 5 mm was covered with an aluminum foil and placed in a 120 ° C thermostat for 168 hours for oxidative deterioration.

[0106]

[Table 3] Table 3

[0107]

[Table 4] Table 4

[0108]

By using the alkanolamine compound having a specific structure and the organic molybdenum compound in combination,
The friction reducing effect of the organic molybdenum compound is further increased, and since the oxidation stability is excellent, the friction reducing performance can be exhibited for a long period of time. Also, MoDTC
Since the solubility of organic molybdenum compounds that are difficult to dissolve in lubricating base oils such as, for example, is improved, organic molybdenum compounds will separate and precipitate even when blended in lubricating base oils with low aromatic content such as high VI oils. It gets harder.

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Claims (4)

[Claims] 1. A lubricating base material having the following general formula (1) as the component (A): (In the formula, R ¹ represents an alkyl group having at least 4 carbon atoms, R ² represents an alkylene group having 2 to 4 carbon atoms, L represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -R.
Represents a group represented by ² OH. ) An alkanolamine compound represented by the formula (4); An organic molybdenum compound is contained as the component (B). 2. The organic molybdenum compound as the component (B) is
The following general formula (2): (In the formula, R ^{3 to} R ⁶ represent a hydrocarbon group, and X ^{1 to} X ⁴ represent a sulfur atom or an oxygen atom.), And a sulfurized oxymolybdenum dithiocarbamate represented by the following general formula (3): ] (Wherein, R ⁷ to R ¹⁰ and X ⁵ to X ⁸ are the general formula (2) as synonymous.) Sulfurized oxymolybdenum dithiocarbamate represented by or the following general formula ^{(4) R 11 -NH-R} 12 (4) (wherein R ¹¹ and R ¹² represent a hydrogen atom or a hydrocarbon group, but are not hydrogen atoms at the same time) and a compound having a pentavalent or hexavalent molybdenum atom. The lubricating composition according to claim 1, which is a reaction product of the above. 3. The lubricating composition according to claim 1, wherein the lubricating base material is a mineral oil and / or a synthetic oil having an aromatic content of 2% or less and a viscosity index of 120 or more. 4. The lubricating composition according to claim 1, further comprising zinc dithiophosphate as the component (C).