JP2009227919A - Lubricant composition for internal combustion engine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lubricant composition for an internal combustion engine being excellent in fuel saving property using a friction modifier not containing sulfur, phosphorous and a metal component. <P>SOLUTION: The lubricant composition for the internal combustion engine contains a lubricant base oil comprising a mineral oil and/or a synthetic oil, [A] 0.1-5 mass% of an ester obtained by polymerizing a 8-30C straight or branched aliphatic hydroxycarboxylic acid, and [B] 0.1-5 mass% of at least one compound selected from (B-1) a mixture comprising a reaction product of a high carboxylic acid diethanolamide with molybdenum oxide and a reaction product of a high carboxylic acid monoglycerine ester with molybdenum oxide, (B-2) an aliphatic amine compound and (B-3) an ester compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lubricating oil composition for an internal combustion engine. More specifically, the present invention relates to a lubricating oil composition for an internal combustion engine that is excellent in fuel efficiency and is obtained by combining a specific additive not containing sulfur and blending a predetermined amount with a base oil.

In recent years, automobiles are equipped with an exhaust gas aftertreatment device, which is an oxidation catalyst, a NOx reduction catalyst, and a diesel particulate filter (DPF). In order to extend the life of these catalysts and filters, reduction in the amount of sulfated ash, phosphorus, and sulfur (abbreviated as SAPS: acronym for Sulfated Ash, Phosphorus and Sulfur) in engine oil is required. Low sulfur low ash oil (Low SAPS oil) has been developed (see Patent Documents 1 and 2).
However, regarding the SAPS-free engine oil, there are concerns about a decrease in wear prevention, cleanliness, oxidation stability, and the like, and in the future, severe fuel saving performance is required that is higher than that of conventional engine oil.
In order to impart fuel efficiency to engine oil, a friction modifier (FM) is blended to reduce friction under normal boundary lubrication conditions. Among FM, molybdenum dithiocarbamate (abbreviated as MoDTC), which is an organic molybdenum compound, has been reported to be most effective in reducing friction. However, the presence of sulfur element in the compound and the effect of reducing the friction of MoDTC. In order to maintain sustainability, it is necessary to use a sulfur compound in combination. For this reason, the FM which does not contain sulfur replaced with MoDTC came to be calculated | required. However, in the current situation, a conventional ester-based or amine-based FM cannot obtain a remarkable friction reducing effect.
JP 2005-146010 A Japanese Patent Laying-Open No. 2005-146011

  The present invention provides an engine oil that reduces friction in a boundary lubrication region seen in a valve system of an engine, has excellent fuel economy, and prevents sulfur poisoning of an oxidation catalyst or NOx reduction catalyst that is an exhaust gas aftertreatment device. The purpose is to provide.

As a result of diligent research on the above problems, the present inventors have found that by combining a specific additive not containing sulfur and blending a predetermined amount with the base oil, a remarkable friction reduction effect can be obtained by the synergistic action. The present invention has been completed.
That is, the present invention provides an ester 0.1 obtained by polymerizing a lubricating base oil composed of mineral oil and / or synthetic oil and [A] a linear or branched aliphatic hydroxycarboxylic acid having 8 to 30 carbon atoms. ~ 5 mass%, [B] (B-1) a reaction product of higher carboxylic acid diethanolamide and molybdenum oxide, and a mixture of a reaction product of higher carboxylic acid monoglycerin ester and molybdenum oxide, (B-2) aliphatic The present invention relates to a lubricating oil composition for internal combustion engines comprising 0.1 to 5 mass of at least one compound selected from amine compounds and (B-3) ester compounds.

  The lubricating oil composition for an internal combustion engine of the present invention is not only excellent in fuel economy, but also excellent in high-temperature cleanliness and wear resistance, reducing the concern over the effect of sulfur, phosphorus and metal on the exhaust gas aftertreatment device or It can be wiped off and can be suitably used for engines equipped with exhaust gas after-treatment devices such as gasoline engines for two-wheeled vehicles and four-wheeled vehicles, diesel engines, and gas engines. In addition, since it has excellent oxidation stability and can withstand long-term use, it is possible to prevent poisoning of the oxidation catalyst and NOx reduction catalyst, which are exhaust gas aftertreatment devices, and to prevent ash accumulation in the DPF. is there.

Hereinafter, the present invention will be described in more detail.
As the lubricating base oil used in the present invention, mineral oil, synthetic oil, or any mixture of two or more base oils selected from these can be used. For example, 1 or more types of mineral oil, 1 or more types of synthetic oil, the mixed oil of 1 or more types of mineral oil and 1 or more types of synthetic oil is mentioned.

  Specifically, as mineral oil, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing. , Oils refined by one or more treatments such as hydrorefining, or lubricating oils produced by isomerizing wax isomerized mineral oil, GTL WAX (Gas Liquid Wax) produced by Fischer-Tropsch process, etc. A base oil can be illustrated.

Although there is no restriction | limiting in particular about total aromatic content in mineral oil, Preferably it is 30 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less. When the total aromatic content of the mineral oil exceeds 30% by mass, the oxidation stability may be inferior.
The sulfur content in the mineral oil is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably 0.005% by mass or less. By reducing the sulfur content of the mineral oil, a composition having better high-temperature cleanability can be obtained.

  Synthetic oils include polybutene or hydrides thereof; poly α-olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, Or a diester such as di-2-ethylhexyl sebacate; a polyol ester such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, or pentaerythritol pelargonate; a dicarboxylic such as dibutyl maleate Examples thereof include a copolymer of an acid and an α-olefin having 2 to 30 carbon atoms, an aromatic synthetic oil such as an alkylnaphthalene, an alkylbenzene, or an aromatic ester, or a mixture of two or more of these.

The kinematic viscosity of the lubricating base oil is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 1 mm ² / s or more and 20 mm ² / s or less, preferably 2 mm ² / s or more and 10 mm ² / s or less. It is more preferable that When the kinematic viscosity at 100 ° C. of the base oil exceeds 20 mm ² / s, the low-temperature viscosity characteristics may be deteriorated. On the other hand, when the kinematic viscosity is less than 1 mm ² / s, an oil film is formed at the lubrication point. Is insufficient, the lubricity is poor and the evaporation loss of the base oil may increase.

  The viscosity index of the lubricating base oil is not particularly limited, but the value is preferably 80 or more, more preferably 100 or more, and 120 or more so that excellent viscosity characteristics can be obtained from low temperature to high temperature. Most preferably. The upper limit of the viscosity index is not particularly limited, and is about 135 to 180 such as normal paraffin, slack wax, GTL wax or the like, or isoparaffin mineral oil obtained by isomerizing these, or 150 to about 150 to about complex ester base oil. A thing of about 250 can also be used. If the viscosity index of the base oil is less than 80, the low temperature viscosity characteristics may be deteriorated.

The lubricating oil composition of the present invention is an ester obtained by polymerizing a linear or branched aliphatic hydroxycarboxylic acid having 8 to 30 carbon atoms as the [A] component (hereinafter referred to as “polyester” for convenience). ).
Here, the hydroxycarboxylic acid (also referred to as hydroxy acid) in the present invention means a carboxylic acid further having a hydroxyl group (—OH) in addition to a carboxyl group (—COOH).

  The hydroxycarboxylic acid used in the present invention is a linear or branched aliphatic hydroxycarboxylic acid having 8 to 30 carbon atoms, preferably 10 to 26 carbon atoms, more preferably 12 to 24 carbon atoms, still more preferably 14 to 22 carbon atoms. Most preferably, it is 16-20 hydroxycarboxylic acids. When the number of carbon atoms of the hydroxycarboxylic acid is less than 8, or when the number of carbon atoms of the hydroxycarboxylic acid exceeds 30, there is a possibility that a sufficient friction reducing effect cannot be obtained.

  The hydroxycarboxylic acid used in the present invention may be a saturated carboxylic acid or an unsaturated carboxylic acid, but is preferably a saturated carboxylic acid from the viewpoint of stability. The hydroxycarboxylic acid may be a linear carboxylic acid or a branched carboxylic acid, but is preferably a linear carboxylic acid.

  The hydroxycarboxylic acid used in the present invention is preferably a compound having one carboxyl group and one hydroxyl group.

  Moreover, although the bonding position of the hydroxyl group in the hydroxycarboxylic acid is arbitrary, for example, in the case of a hydroxycarboxylic acid having 18 carbon atoms, the hydroxyl group is preferably located at the 12th position. Further, the hydroxycarboxylic acid may be used alone, or a mixture may be used.

The polyester used as the component [A] in the present invention is an oligomer obtained by polymerizing the above hydroxycarboxylic acid. Specifically, the above hydroxycarboxylic acid can be easily obtained by condensation polymerization in the presence of an alkali catalyst.
The degree of polymerization of the polyester is preferably 2 to 15, more preferably 2 to 10, and further preferably 3 to 7. When the degree of polymerization exceeds 15, the friction reducing effect cannot be sufficiently obtained, and handling may be difficult. In addition, the polyester used in the present invention may be one having a specific degree of polymerization, or may be used by mixing ones having different degrees of polymerization.

  The content of the component [A] in the lubricating oil composition of the present invention is based on the total amount of the lubricating oil composition, and the lower limit is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.8%. 5 mass% or more, More preferably, it is 0.8 mass% or more. An upper limit is 5 mass% or less, Preferably it is 4 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2.5 mass% or less. If the content is less than 0.1% by mass, a sufficient friction reducing effect may not be obtained. If the content exceeds 5% by mass, the friction reducing effect corresponding to the content cannot be obtained, and oxidation of the lubricating oil is not possible. There is a risk of deteriorating stability.

  The lubricating oil composition of the present invention comprises (B-1) a reaction product of a higher carboxylic acid diethanolamide and molybdenum oxide and a mixture of a higher carboxylic acid monoglycerin ester and molybdenum oxide as a component [B], It contains at least one compound selected from (B-2) aliphatic amine compounds and (B-3) ester compounds.

(B-1): a reaction product of higher carboxylic acid diethanolamide and molybdenum oxide and a mixture of a reaction product of higher carboxylic acid monoglycerin ester and molybdenum oxide. The higher carboxylic acid has 6 to 30 carbon atoms. More preferred are carboxylic acids having a linear or branched, saturated or unsaturated hydrocarbon group having 8 to 24 carbon atoms, more preferably 12 to 18 carbon atoms.
A typical example of the raw material for the higher carboxylic acid is coconut oil. Specific compound names include N, N-bis (hydroxyethyl) dodecanamide, 2,3-dihydroxypropyl dodecanoate, and a reaction product of these compounds with molybdenum oxide, (B-1) It is a mixture composed of four types of compounds.

(B-2): Aliphatic amine compound As the aliphatic amine compound, a linear or branched, saturated or unsaturated hydrocarbon group having 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, particularly preferably 10 to 20 carbon atoms. And aliphatic monoamines, aliphatic polyamines, and aliphatic alkanolamines. If the carbon number is other than 6 to 30, sufficient friction reduction effect cannot be obtained.
Specifically, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, stearylamine, oleylamine, lauryldiethylamine, oleylpropylenediamine, stearyltetraethylenepentamine, dodecyldipropanolamine Lauryl diethanolamine, oleyl diethanolamine and the like. Particularly preferred is oleylamine.

(B-3): Ester compound The alcohol constituting the ester may be a monohydric alcohol or a polyhydric alcohol, and the acid may be a monobasic acid or a polybasic acid.
As the monohydric alcohol, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. Such alcohols may be linear or branched, It may be saturated or unsaturated.
As the polyhydric alcohol, those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Among these, ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and a mixture thereof are preferable.
As the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used, and the fatty acid may be linear or branched, and may be saturated or unsaturated. Among these, a saturated fatty acid having 3 to 20 carbon atoms, an unsaturated fatty acid having 3 to 22 carbon atoms, and a mixture thereof are particularly preferable, a saturated fatty acid having 4 to 18 carbon atoms, an unsaturated fatty acid having 4 to 18 carbon atoms, and these The mixture of is more preferable.
Examples of the polybasic acid include dibasic acids having 2 to 16 carbon atoms. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated.

The combination of the alcohol and the acid forming the ester is arbitrary and is not particularly limited, but an ester of a polyhydric alcohol and a monobasic acid is preferable, and an ester of glycerin and a linear fatty acid is particularly preferable.
In addition, the ester obtained when polyhydric alcohol is used as the alcohol component may be a complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified, or a portion in which some of the hydroxyl groups are not esterified and remain as hydroxyl groups. An ester may be used, but a partial ester is more preferable.

  The content of the component [B] in the lubricating oil composition of the present invention is based on the total amount of the lubricating oil composition, and the lower limit is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.8%. 5 mass% or more, More preferably, it is 0.8 mass% or more. An upper limit is 5 mass% or less, Preferably it is 4 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2.5 mass% or less. If the content is less than 0.1% by mass, a sufficient friction reducing effect may not be obtained. If the content exceeds 5% by mass, the friction reducing effect corresponding to the content cannot be obtained, and oxidation of the lubricating oil is not possible. There is a risk of deteriorating stability.

  In the lubricating oil composition of the present invention, the combined use of the [A] component and the [B] component can greatly reduce the friction in the boundary lubrication region seen in the valve system of the engine due to the synergistic action. Thus, a lubricating oil composition having excellent fuel economy can be obtained.

  In order to further improve the performance, the lubricating oil composition of the present invention may contain any additive generally used in lubricating oils depending on the purpose. Examples of such additives include metal detergents, ashless dispersants, antioxidants, antiwear agents (or extreme pressure agents), friction modifiers other than the [A] component and [B] component, and corrosion. Examples thereof include additives such as inhibitors, rust inhibitors, viscosity index improvers, pour point depressants, demulsifiers, metal deactivators, and antifoaming agents.

  Metal detergents include alkali metal sulfonates or alkaline earth metal sulfonates, alkali metal phenates or alkaline earth metal phenates, and normal salts, basic salts or overbased salts such as alkali metal salicylates or alkaline earth metal salicylates. Etc. In the present invention, one or more alkali metal or alkaline earth metal detergents selected from the group consisting of these, particularly alkaline earth metal detergents can be preferably used. In particular, a magnesium salt and / or a calcium salt is preferable, and a calcium salt is more preferably used.

  As the ashless dispersant, any ashless dispersant such as alkenyl succinimide, benzylamine, and alkenyl polyamine used in lubricating oils can be used. For example, a monosuccinimide represented by the formula (1) in which a linear or branched alkyl or alkenyl succinic anhydride having 40 to 400 carbon atoms is added to one end of a polyamine at the time of imidization, or a formula ( The bissuccinimide shown by 2) can be mentioned.

In formula (1) and formula (2), R ¹ , R ² and R ³ are each independently a linear or branched alkyl group or alkenyl having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms. Indicates a group. a represents an integer of 1 to 10, preferably 2 to 5, and b represents an integer of 1 to 10, preferably 2 to 5.
Alternatively, boron-modified succinimide obtained by reacting boron compound such as boric acid (orthoboric acid, metaboric acid, tetraboric acid, etc.), borate or boric acid ester with succinimide can also be used.
The method for producing the succinimide is not particularly limited. For example, an alkyl succinic acid or alkenyl succinic acid obtained by reacting a compound having an alkyl group or alkenyl group having 40 to 400 carbon atoms with maleic anhydride at 100 to 200 ° C. It is obtained by reacting an acid with a polyamine.
Examples of polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum.
Examples of phenolic antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′. -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,6-di- tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-α-dimethylamino-p -Cresol, 2,6-di-tert-butyl-4- (N, N'-dimethylaminomethylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'- Thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 2,2′-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Tridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octyl-3- (3 Preferred examples include -methyl-5-di-tert-butyl-4-hydroxyphenyl) propionate. You may use these in mixture of 2 or more types.
As the amine-based antioxidant, for example, known amine-based antioxidants generally used for lubricating oils such as aromatic amine compounds, alkyldiphenylamines, alkylnaphthylamines, phenyl-α-naphthylamines, alkylphenyl-α-naphthylamines, etc. Agents.

  As the antiwear agent (or extreme pressure agent), any antiwear agent / extreme pressure agent used in lubricating oils can be used. For example, sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used. Specifically, phosphites, thiophosphites, dithiophosphites, trithiophosphites Esters, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithiocarbamate, molybdenum dithiocarbamate, disulfide , Polysulfides, sulfurized olefins, sulfurized fats and oils, and the like. Among these, addition of a sulfur-based extreme pressure agent is preferable, and sulfurized fats and oils are particularly preferable.

In the lubricating oil composition of the present invention, a friction modifier other than the above-mentioned [A] component and [B] component can be further contained in order to improve fuel saving performance. Examples of such friction modifiers include organic molybdenum compounds and ashless friction modifiers other than the components [A] and [B].
Organic molybdenum compounds include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate, molybdenum compounds (eg, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, orthomolybdic acid, paramolybdic acid, (poly) Molybdic acid such as sulfurized molybdic acid, metal salts of these molybdic acids, molybdate such as ammonium salt, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polysulfide molybdenum, molybdenum sulfide, molybdenum sulfide Metal salts or amine salts, molybdenum halides such as molybdenum chloride) and sulfur-containing organic compounds (eg, alkyl (thio) xanthates, thiadiazoles, mercaptothiadiazoles, thiocarbonates, Lahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfide ester, etc.) or other organic compounds, or the above molybdenum sulfide, sulfurized molybdenum acid And a complex of a sulfur-containing molybdenum compound such as alkenyl succinimide.

  As the organic molybdenum compound, an organic molybdenum compound containing no sulfur as a constituent element can be used. Specific examples of organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.

  Moreover, as an ashless friction modifier other than [A] component and [B] component, the arbitrary compounds normally used as an ashless friction modifier for lubricating oil can be used, for example, C6-C30 Ashless friction adjustment of fatty acid amides, fatty acids, fatty alcohols, aliphatic ethers, etc. having at least one alkyl group or alkenyl group in the molecule, particularly a linear alkyl group or straight chain alkenyl group having 6 to 30 carbon atoms in the molecule Agents and the like. One or more compounds selected from the group consisting of nitrogen-containing compounds represented by the following general formulas (3) and (4) and acid-modified derivatives thereof, and various examples exemplified in International Publication No. 2005/037967 Ashless friction modifiers may be mentioned.

In the general formula (3), R ⁴ has a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrocarbon group having 10 to 30 carbon atoms or a functionality. A hydrocarbon group having 10 to 30 carbon atoms, more preferably an alkyl group having 12 to 20 carbon atoms, an alkenyl group or a hydrocarbon group having functionality, particularly preferably an alkenyl group having 12 to 20 carbon atoms, R ⁵ and R ⁶ each independently has a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms or hydrogen having functionality, preferably a hydrocarbon group having 1 to 10 carbon atoms, or functionality. A hydrocarbon group or hydrogen having 1 to 10 carbon atoms, more preferably a hydrocarbon group or hydrogen having 1 to 4 carbon atoms, more preferably hydrogen, and X represents oxygen or sulfur, preferably oxygen.

In the general formula (4), R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrocarbon group having 10 to 30 carbon atoms or a functional group. A hydrocarbon group having 10 to 30 carbon atoms, more preferably an alkyl group having 12 to 20 carbon atoms, an alkenyl group or a hydrocarbon group having functionality, particularly preferably an alkenyl group having 12 to 20 carbon atoms, and R ^{8 to} R ¹⁰ are each independently a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms or hydrogen having functionality, preferably a hydrocarbon group having 1 to 10 carbon atoms, and functionality. A hydrocarbon group having 1 to 10 carbon atoms or hydrogen, more preferably a hydrocarbon group having 1 to 4 carbon atoms or hydrogen, and even more preferably hydrogen.

Specific examples of the nitrogen-containing compound represented by the general formula (4) include hydrazides having 1 to 30 carbon atoms or functional hydrocarbon groups having 1 to 30 carbon atoms and derivatives thereof. is there. When R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, and R ^{8 to} R ¹⁰ are hydrogen, the hydrocarbon group having 1 to 30 carbon atoms or the functionality is Any of hydrazide having a hydrocarbon group having 1 to 30 carbon atoms, R ⁷ and R ^{8 to} R ¹⁰ is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms having functionality. And when the remainder of R ^{8 to} R ¹⁰ is hydrogen, N-hydrocarbyl hydrazide having a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms having functionality (hydrocarbyl is a hydrocarbon group) Etc.).

  Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.

  Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.

  Examples of the viscosity index improver include ordinary general non-dispersed or dispersed poly (meth) acrylates, non-dispersed or dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or hydrides thereof, The styrene-diene hydrogenated copolymer may further contain a styrene-maleic anhydride copolymer, polyalkylstyrene, and the like. The weight average molecular weight of these viscosity index improvers is usually 800 to 1,000,000, preferably 100,000 to 900,000.

  As the pour point depressant, for example, a polymethacrylate polymer compatible with the lubricating base oil to be used can be used.

  Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

  Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.

Examples of the antifoaming agent include silicone oil having a kinematic viscosity at 25 ° C. of 1000 to 100,000 mm ² / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Examples thereof include hydroxybenzyl alcohol.

  When these additives are contained in the lubricating oil composition of the present invention, the content is preferably 0.01 to 20% by mass based on the total amount of the composition.

The kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is not particularly limited, but is preferably 3.8 to 21.9 mm ² / s, more preferably 4.1 to 16.3 mm ² / s, particularly preferably. Is 5.6 to 12.5 mm ² / s. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.

  Particularly preferred as the lubricating oil composition of the present invention exhibits excellent antiwear properties, high temperature cleanliness and oxidation stability, and extends the life of oxidation catalysts, NOx reduction catalysts and DPFs used in internal combustion engines. A composition that contributes to a reduced amount of SAPS. Specifically, the sulfated ash content is 0.2% by mass or less, preferably 0.15% by mass or less, the phosphorus content is less than 0.01% by mass, preferably 0, and the sulfur content is 0.1% by mass or less, preferably Is a lubricating oil composition of 0.05 mass% or less.

The lubricating oil composition for an internal combustion engine of the present invention is not only excellent in fuel economy, but also excellent in high-temperature cleanliness and wear prevention properties, reducing the concern over the influence of sulfur, phosphorus and metal on the exhaust gas aftertreatment device or It can be wiped off and can be suitably used for engines equipped with exhaust gas after-treatment devices such as gasoline engines for two-wheeled vehicles and four-wheeled vehicles, diesel engines, and gas engines. In addition, since it has excellent oxidation stability and can withstand long-term use, it is possible to prevent poisoning of the oxidation catalyst and NOx reduction catalyst, which are exhaust gas aftertreatment devices, and to prevent ash accumulation in the DPF. is there.
The lubricating oil composition of the present invention is not limited to lubricating oil for internal combustion engines, but various lubricating oils such as automatic or manual transmission oil, wet brake oil, hydraulic hydraulic oil, turbine oil, compressor oil, bearing oil, and refrigeration oil. Application to is also possible.

  The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Examples 1-5 and Comparative Examples 1-8]
Lubricating oil compositions having the compositions shown in Table 1 were prepared. The viscosity grades were all 5W-30 (100 ° C. kinematic viscosity: about 10 mm ² / s). The valve friction torque of these lubricating oil compositions was evaluated by the following method. The results are shown in Table 1.

In addition, 1) -7) in Table 1 is as follows.
1) Hydrorefined mineral oil (100 ° C. kinematic viscosity: 4.3 mm ² / s, sulfur content: less than 0.01% by mass, viscosity index: 124),
2) Friction modifier A: Trimer and tetramer mixture of 12-hydroxtearic acid.
3) Friction modifier B-1: N, N-bis (hydroxyethyl) dodecanamide, 2,3-dihydroxypropyl dodecanoate and a mixture composed of a reaction product of these compounds and molybdenum oxide 4) Friction modifier B-2: Oleylamine 5) Friction modifier B-3: Glycerin monooleate 6) Other additives C: SAPS free additive package (Antioxidant, ashless dispersant, ashless antiwear agent, antifoaming agent, etc.) Including)
7) Viscosity index improver D: Dispersed polymethacrylate (weight average molecular weight 400,000)

(Evaluation of valve friction torque)
Friction in the region under boundary lubrication is evaluated by extracting the valve system part of a light-load diesel engine (direct injection, displacement 1.4L, common rail fuel injection system, turbocharger installed) Torque was measured. The valve was a roller rocker type overhead camshaft (OHC), and the friction torque was measured by changing the camshaft rotation speed to 275 rpm, 375 rpm, and 425 rpm while keeping the oil temperature at 100 ° C.

As shown in Table 1, Examples 1 to 3 are compositions based on a combination of FM-A and FM- (B-1), but the friction torque was significantly reduced as compared with Comparative Example 8. In Example 2, 1.25 mass% of FM-A and 1.0 mass% of FM- (B-1) were added, but in Comparative Example 1 in which only 1.25 mass% of this FM-A was added, The friction torque reduction is not sufficient. Moreover, also in the comparative example 2 which prescribed | regulated 2.25 mass% equivalent to FM total amount of Example 2 only by FM-A, friction torque reduction is not enough. Similarly, even in Comparative Example 3 in which only FM- (B-1) is added by 1.0 mass%, the friction torque reduction level of Example 2 cannot be reached. That is, it can be seen that the friction reduction effect is synergistically exhibited by the combination of FM-A and FM- (B-1).
In Example 4, 1.25 mass% of FM-A and 0.5 mass% of FM- (B-2) were added. Comparative Example 1 and FM in which 1.25 mass% of FM-A alone was added. -Compared with Comparative Example 5 in which only 0.5% by mass of (B-2) was added, and in Comparative Example 6 in which only 1.75% by mass of FM- (B-2) was added, the friction torque showed a low value. It can be seen that even in the combination of -A and FM- (B-2), the friction reducing effect is synergistically exhibited.
In Example 5, FM-A was added at 1.25 mass% and FM- (B-3) was added at 0.5 mass%, but compared with Comparative Examples 1 and 7 in which these FMs were added individually. The friction torque has been greatly reduced.

Claims (1)

  0.1 to 5% by mass of an ester obtained by polymerizing a lubricating base oil composed of mineral oil and / or synthetic oil and [A] a linear or branched aliphatic hydroxycarboxylic acid having 8 to 30 carbon atoms, [B] (B-1) a reaction product of a higher carboxylic acid diethanolamide and molybdenum oxide and a reaction product of a higher carboxylic acid monoglycerin ester and molybdenum oxide, (B-2) an aliphatic amine compound and (B -3) A lubricating oil composition for internal combustion engines containing 0.1 to 5 mass of at least one compound selected from ester compounds.