WO2021054285A1

WO2021054285A1 - Lubricating oil composition

Info

Publication number: WO2021054285A1
Application number: PCT/JP2020/034714
Authority: WO
Inventors: 啓司大木
Original assignee: 出光興産株式会社
Priority date: 2019-09-17
Filing date: 2020-09-14
Publication date: 2021-03-25
Also published as: JP7429509B2; JP2021046472A

Abstract

Provided is a lubricating oil composition comprising a base oil (A), at least one aromatic carboxylate ester derivative (B) selected from aromatic carboxylate ester derivatives (B1) represented by general formula (I) and aromatic carboxylate ester derivatives (B2) represented by general formula (II), an oxymolybdenum complex (C1) of a basic nitrogen compound, and a calcium-based detergent (D) comprising a calcium-based detergent (D1) having a base number of at least 200 mg KOH/g. A component (B) content is at least 1.5 mass%; the content of molybdenum atom originating from a component (C1) is a prescribed amount; the content of calcium atom originating from a component (D) is a prescribed amount; the sulfated ash is not more than 0.3 mass%; and the phosphorus atom content is a prescribed amount. The lubricating oil composition can reduce the friction coefficient while being able to suppress the occurrence of LSPI and providing a good high-temperature detergency.

Description

Lubricating oil composition

The present invention relates to a lubricating oil composition.

In recent years, the development of a direct-injection gasoline engine (downsizing engine) equipped with a turbocharger or other supercharger has been progressing at a rapid pace. Direct injection of a gasoline engine has the advantage of improving fuel efficiency, but has the disadvantage of generating suits such as particulate matter (PM) contained in exhaust gas, similar to diesel engines. Therefore, in addition to the exhaust gas purification catalyst, a direct injection gasoline engine equipped with an exhaust gas treatment device equipped with a gasoline particulate filter (GPF) tends to become widespread.
There is concern that the lubricating oil composition may have an adverse effect on such an exhaust gas treatment device. Specifically, when a lubricating oil composition containing a metal-based cleaning agent is used, there is a concern that the filter may be clogged by the metal content derived from the metal-based cleaning agent. As a countermeasure for that, it is required to reduce the sulfated ash content of the lubricating oil composition.

For example, Patent Document 1 discloses a lubricating oil composition for an internal combustion engine in which a calcium-based cleaning agent is blended so that the amount of sulfated ash is 0.7% by mass or less. Further, from the viewpoint of suppressing the poisoning of the exhaust gas purification catalyst, the lubricating oil composition is also required to reduce the phosphorus content.
That is, the lubricating oil composition is required to reduce not only the sulfated ash content but also the phosphorus content.

Japanese Unexamined Patent Publication No. 2000-256690

However, as a result of the examination by the present inventor, the lubricating oil composition in which the sulfated ash content and the phosphorus content are reduced is a low-speed pre-ignition (Low-Speed Pre-) during low-speed operation in a direct-injection gasoline engine equipped with a supercharger. It has been found that there is a concern of causing ignition (hereinafter referred to as "LSPI"). LSPI is a phenomenon in which ignition occurs earlier than the set ignition timing in a low-speed operation state, and abnormal combustion may occur in the engine cylinder due to the ignition. The generation of LSPI may be a factor that adversely affects the improvement of fuel efficiency or a factor that causes an engine failure. Therefore, it is considered an urgent task to provide a lubricating oil composition capable of suppressing the generation of LSPI.

Further, from the viewpoint of extending the life of the exhaust gas treatment device, it is also required to further reduce the sulfated ash content of the lubricating oil composition. However, if the sulfated ash content of the lubricating oil composition is further reduced, it becomes difficult to ensure high-temperature cleanliness.

Furthermore, the lubricating oil composition is required not only to have high temperature cleanliness but also to reduce the coefficient of friction. However, as a result of the examination by the present inventor, it has been found that it is difficult to reduce the friction coefficient while improving the high temperature cleanliness.

INDUSTRIAL APPLICABILITY The present invention is a lubricating oil composition capable of suppressing the generation of LSPI while having a low sulfuric acid ash content and a low phosphorus content, and also being able to reduce the friction coefficient while improving the high temperature cleanliness. The challenge is to provide.

In order to solve the above problems, the present inventor has diligently studied. As a result, it has been found that a lubricating oil composition containing a certain amount or more of phosphorus while reducing the phosphorus content suppresses the generation of LSPI.
As a result of further diligent studies, the present inventor has found that the lubricating oil composition containing a specific calcium-based detergent and a specific amount of a specific aromatic carboxylic acid ester derivative has a low sulfated ash content of 0.3% by mass or less. Even so, it has been found that the high temperature cleanliness is good. In addition, it has been found that a lubricating oil composition containing a specific amount of a specific molybdenum compound can effectively reduce the coefficient of friction without deteriorating high temperature cleanliness.
Based on these findings, the present inventor has made further diligent studies and completed the present invention.

That is, the present invention provides the following [1] to [10].
[1] From the base oil (A), the aromatic carboxylic acid ester derivative (B1) represented by the following general formula (I), and the aromatic carboxylic acid ester derivative (B2) represented by the following general formula (II). Calcium containing one or more selected aromatic carboxylic acid ester derivatives (B), an oxymolybdenum complex (C1) of a basic nitrogen compound, and a calcium-based cleaning agent (D1) having a base value of 200 mgKOH / g or more. A lubricating oil composition containing a system cleaning agent (D).

[In the general formula (I), x and y are integers satisfying 1 ≦ x ≦ 3 and 1 ≦ y ≦ 3, respectively. R ¹ and R ² each independently represent an alkyl group having 9 to 20 carbon atoms. When x ≧ 2, the plurality of R ^1s may be the same or different. When y ≧ 2, the plurality of R ^2s may be the same or different. ]

[In the general formula (II), m, n, о, and p are 1 ≦ m ≦ 2, 0 ≦ n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ о ≦ 3, 1 ≦ p ≦, respectively. It is an integer that satisfies 3. R ³ and R ⁴ each independently represent an alkyl group having 9 to 20 carbon atoms. If it is o ≧ 2, a plurality of R ³ may be be the same or different. When p ≧ 2, the plurality of R ^4s may be the same or different. ]
The content of the aromatic carboxylic acid ester derivative (B) is 1.5% by mass or more based on the total amount of the lubricating oil composition.
The content of molybdenum atoms derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is 0.025% by mass or more based on the total amount of the lubricating oil composition.
The content of calcium atoms derived from the calcium-based cleaning agent (D) is 0.020% by mass or more and less than 0.080% by mass based on the total amount of the lubricating oil composition.
Sulfate ash content is 0.3% by mass or less,
A lubricating oil composition having a phosphorus atom content of 0.020% by mass or more and 0.040% by mass or less based on the total amount of the lubricating oil composition.
[2] The content of calcium atoms derived from the calcium-based cleaning agent (D1) is 0.020% by mass or more and less than 0.080% by mass based on the total amount of the lubricating oil composition. The lubricating oil composition according to.
[3] The content of calcium atoms derived from the calcium-based cleaning agent (D2) having a base value of less than 200 mgKOH / g is less than 0.025% by mass based on the total amount of the lubricating oil composition. The lubricating oil composition according to 1] or [2].
[4] The content ratio of the calcium-based detergent (D2) derived from calcium atoms _{(Ca D2)} and wherein the calcium detergent (D1) derived from calcium atoms _{_{(Ca D1) [Ca D2 /}} Ca D1] is, The lubricating oil composition according to the above [3], which is less than 0.31 by mass.
[5] The above [1] to [4], wherein the content of Mo atoms derived from molybdenum dithiocarbamate (MoDTC) (C2) is less than 0.020% by mass based on the total amount of the lubricating oil composition. The lubricating oil composition according to any one.
[6] Content ratio of _{Mo atom (Mo C2} ) derived from the molybdenum dithiocarbamate (MoDTC) (C2) _{to molybdenum atom (Mo C1} ) derived from the oxymolybdenum complex (C1) of the basic nitrogen compound [ The lubricating oil composition according to the above [5], wherein Mo _C2 / Mo _{C1] is less than 1.0 in terms of mass ratio.}
[7] The lubricating oil composition according to any one of [1] to [6] above, further comprising zinc dithiophosphate (ZnDTP) (E).
[8] The lubricating oil composition according to any one of the above [1] to [7], which is used for an internal combustion engine.
[9] The lubricating oil composition according to any one of the above [1] to [7], which is used for an internal combustion engine including a gasoline particulate filter (GPF).
[10] The lubricating oil composition according to the above [9], which is used for a direct-injection internal combustion engine equipped with a supercharger.

According to the present invention, a lubricating oil capable of suppressing the generation of LSPI while having a low sulfuric acid ash content and a low phosphorus content, and also having a good high-temperature cleanliness and a reduced friction coefficient. It becomes possible to provide the composition.

In the present specification, with respect to a preferable numerical range (for example, a range such as content), the lower limit value and the upper limit value described stepwise can be combined independently. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "favorable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". be able to. Similarly, in the present specification, the numerical values of "greater than or equal to", "less than or equal to", "less than", and "exceeding" regarding the description of the numerical range are numerical values that can be arbitrarily combined.

[Lubricating oil composition]
The lubricating oil composition of the present embodiment contains a base oil (A), an aromatic carboxylic acid ester derivative (B), an oxymolybdenum complex (C1) of a basic nitrogen compound, and a base value of 200 mgKOH / g or more. A lubricating oil composition containing a calcium-based cleaning agent (D) containing a calcium-based cleaning agent (D1).
The aromatic carboxylic acid ester derivative (B) is an aromatic carboxylic acid ester derivative (B1) represented by the following general formula (I) and an aromatic carboxylic acid ester derivative (B2) represented by the following general formula (II). ) Is one or more selected from

[In the general formula (II), m, n, о, and p are 1 ≦ m ≦ 2, 0 ≦ n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ о ≦ 3, 1 ≦ p ≦, respectively. It is an integer that satisfies 3. R ³ and R ⁴ each independently represent an alkyl group having 9 to 20 carbon atoms. If it is o ≧ 2, a plurality of R ³ may be be the same or different. When p ≧ 2, the plurality of R ^4s may be the same or different. ]
The content of the aromatic carboxylic acid ester derivative (B) is 1.5% by mass or more based on the total amount of the lubricating oil composition.
The content of molybdenum atoms derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is 0.025% by mass or more based on the total amount of the lubricating oil composition.
The content of calcium atoms derived from the calcium-based cleaning agent (D) is 0.020% by mass or more and less than 0.080% by mass based on the total amount of the lubricating oil composition.
Sulfate ash content is 0.3% by mass or less,
A lubricating oil composition having a phosphorus atom content of 0.020% by mass or more and 0.040% by mass or less based on the total amount of the lubricating oil composition.

As a result of diligent studies by the present inventor in order to solve the above problems, LSPI may be generated if the phosphorus content in the lubricating oil composition is reduced too much, while the content of phosphorus atoms in the lubricating oil composition is high. It has been found that a lubricating oil composition having a total amount of 0.020% by mass or more and 0.040% by mass or less can suppress the generation of LSPI. That is, it has been found that securing a certain amount or more of phosphorus atom content while reducing the phosphorus content is effective in suppressing the generation of LSPI.
Further, as a result of further diligent studies by the present inventor in order to solve the above problems, a lubricating oil composition containing a specific calcium-based detergent and a specific amount of a specific aromatic carboxylic acid ester derivative has been obtained. It has been found that the high temperature cleanliness is good even with a low sulfated ash content of 3% by mass or less.
On the other hand, when molybdenum dialkyldithiocarbamate (MoDTC), which is a general-purpose friction modifier, is added to the lubricating oil composition in order to reduce the friction coefficient, the high-temperature cleanliness of the lubricating oil composition tends to deteriorate. The present inventor has come to the conclusion.
Therefore, as a result of further studies by the present inventor, the lubricating oil composition containing an oxymolybdenum complex of a basic nitrogen compound in a certain amount or more maintains a good state without deteriorating high-temperature cleanliness, and has a friction coefficient. We have come to the conclusion that it can be effectively reduced.
Based on these findings, the present inventor has made further diligent studies and completed the present invention.

In the following description, a base oil (A), an aromatic carboxylic acid ester derivative (B), an oxymolybdenum complex (C1) of a basic nitrogen compound, and a calcium-based cleaning agent having a base value of 200 mgKOH / g or more ( The calcium-based cleaning agent (D) containing D1) is also referred to as a component (A), a component (B), a component (C1), and a component (D), respectively.
Further, in the following description, the aromatic carboxylic acid ester derivative (B1) represented by the general formula (I) and the aromatic carboxylic acid ester derivative (B2) represented by the general formula (II) are used, respectively. Also referred to as a component (B1) and a component (B2).

In the lubricating oil composition of the present embodiment, the total content of the component (A), the component (B), the component (C1), and the component (D) is preferably 70% by mass or more, more preferably 75% by mass or more. , More preferably 80% by mass or more.
Further, in the lubricating oil composition of the present embodiment, the upper limit of the total content of the component (A), the component (B), the component (C1), and the component (D) may be 100% by mass. However, when the lubricating oil composition contains an additive for lubricating oil other than the component (B), the component (C1), and the component (D), the component (A), the component (B), and the component ( The upper limit of the total content of C1) and the component (D) may be adjusted in relation to the other additives for lubricating oil, preferably 95% by mass or less, more preferably 90% by mass or less, and further. It is preferably 85% by mass or less.

Hereinafter, each component contained in the lubricating oil composition of the present embodiment will be described.

<Base oil (A)>
The lubricating oil composition of this embodiment contains a base oil (A). As the base oil (A), one or more selected from mineral oils and synthetic oils conventionally used as base oils for lubricating oils can be used without particular limitation.

Examples of the mineral oil include atmospheric residual oil obtained by atmospheric distillation of crude oil such as paraffin-based crude oil, intermediate basic crude oil, and naphthen-based crude oil; reduced pressure residual oil obtained by vacuum distillation of the atmospheric residual oil; The vacuum residual oil is subjected to one or more refining treatments such as solvent removal, solvent extraction, hydrofinishing, hydrocracking, advanced hydrocracking, solvent dewaxing, contact dewaxing, and hydroisomerization dewaxing. Examples thereof include the obtained mineral oil.

Examples of the synthetic oil include polyα such as an α-olefin homopolymer and an α-olefin copolymer (for example, an α-olefin copolymer having 8 to 14 carbon atoms such as an ethylene-α-olefin copolymer). -Oolefin; Isoparaffin; Various esters such as polyol ester and dibasic acid ester; Various ethers such as polyphenyl ether; Polyalkylene glycol; Alkylbenzene; Alkylnaphthalene; Wax produced from natural gas by Fischer-Tropsch method or the like (GTL wax) , Gas To Liquids WAX), GTL-based oil obtained by isomerization, and the like can be mentioned.

As the base oil used in this embodiment, a base oil classified into Group II or III of the base oil category of API (American Petroleum Association) is preferable, and a base oil classified into Group III is more preferable.

As the base oil (A), one type selected from mineral oil may be used alone, or two or more types may be used in combination. Further, one kind selected from synthetic oils may be used alone, or two or more kinds may be used in combination. Further, one or more kinds of mineral oil and one or more kinds of synthetic oil may be used in combination.

The kinematic viscosity and viscosity index of the base oil (A) are not particularly limited, but the kinematic viscosity and viscosity index are preferably in the following ranges from the viewpoint of improving fuel efficiency and wear resistance. ..
Kinematic viscosity (hereinafter also referred to as "40 ° C. kinematic viscosity".) At 40 ° C. of the base oil (A) is ^preferably from ^{2.0mm 2 /s~100.0mm 2 / s, 5.0mm} 2 / s ~ 80 more preferably .0mm ² / ^s, still more preferably 10.0mm ² /s~60.0mm 2 / ^s, even more preferably from ^{15mm 2 / s ~ 40mm 2 /} s, 15mm 2 / s ~ 30mm 2 / s is Even more preferable.
Kinematic viscosity (hereinafter also referred to as "100 ° C. kinematic viscosity".) At 100 ° C. of the base oil (A) is ^preferably from ^{2.0mm 2 /s~20.0mm 2 / s, 3.0mm} 2 / s ~ 9 more preferably .0mm ² / ^s, more preferably from ^{^{3.5mm 2 /s~7.0mm 2 / s, 3.5mm}} 2 /s~5.0mm 2 / s and further preferably more.
The viscosity index of the base oil (A) is preferably 80 or more, more preferably 90 or more, further preferably 100 or more, and even more preferably 105 or more.
The 40 ° C. kinematic viscosity, the 100 ° C. kinematic viscosity, and the viscosity index can be measured or calculated in accordance with JIS K 2283: 2000.
When the base oil (A) is a mixed base oil containing two or more kinds of base oils, the kinematic viscosity and viscosity index of the mixed base oil are preferably within the above ranges.

In the lubricating oil composition of the present embodiment, the content of the base oil (A) is not particularly limited, but from the viewpoint of making it easier to exert the effect of the present invention, it is based on the total amount (100% by mass) of the lubricating oil composition. , 60% by mass to 90% by mass, more preferably 65% by mass to 85% by mass, still more preferably 70% by mass to 80% by mass.

<Aromatic carboxylic acid ester derivative (B)>
The lubricating oil composition of the present embodiment contains an aromatic carboxylic acid ester derivative (B). When the lubricating oil composition contains the aromatic carboxylic acid ester derivative (B), high-temperature cleanliness can be improved.
The aromatic carboxylic acid ester derivative (B) is an aromatic carboxylic acid ester derivative (B1) represented by the following general formula (I) and an aromatic carboxylic acid ester derivative (B2) represented by the following general formula (II). One or more selected from.

[In the general formula (II), m, n, о, and p are 1 ≦ m ≦ 2, 0 ≦ n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ о ≦ 3, 1 ≦ p ≦, respectively. It is an integer that satisfies 3. R ³ and R ⁴ each independently represent an alkyl group having 9 to 20 carbon atoms. If it is o ≧ 2, a plurality of R ³ may be be the same or different. When p ≧ 2, the plurality of R ^4s may be the same or different. ]

In the above general formulas (I) and (II), examples of the alkyl group having 9 to 20 carbon atoms include a hydrocarbon group such as a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group. Can be mentioned. The alkyl group having 9 to 20 carbon atoms may be a linear alkyl group or a branched alkyl group. When a low-viscosity carboxylic acid ester derivative is desired, R ¹ and R ² are preferably linear alkyl groups. The carbon number of R ¹ and R ² is preferably 10 to 20, more preferably 10 to 18, still more preferably 10 to 16, and even more preferably 10 to 14.

Specific examples of the aromatic carboxylic acid ester derivative (B1) represented by the general formula (I) include (nonylsalicylic acid) nonylphenyl ester, (decylsalicylic acid) decylphenyl ester, and (undecylsalicylic acid) undecylphenyl ester. , (Undecylsalicylic acid) dodecylphenyl ester, (dodecylsalicylic acid) undodecylphenyl ester, (dodecylsalicylic acid) dodecylphenyl ester, (dodecylsalicylic acid) tridodecylphenyl ester, (tridecylsalicylic acid) dodecylphenyl ester, (tridecylsalicylic acid) Tridecylphenyl ester, (tetradecylsalicylic acid) tetradecylphenyl ester, (heptadecylsalicylic acid) heptadecylphenyl ester, (hexadecylsalicylic acid) hexadecylphenyl ester, (mixed C11-C15) alkylsalicylic acid, (mixed C11-C15) Alkylphenyl ester, (mixed C11-C15) alkylsalicylic acid nonylphenyl ester, (mixed C11-C15) alkylsalicylic acid decylphenyl ester, (mixed C11-C15) alkylsalicylic acid undecylphenyl ester, (mixed C11-C15) alkylsalicylic acid dodecyl Phenyl ester, (mixed C11-C15) alkylsalicylic acid tridecylphenyl ester, (mixed C11-C15) alkylsalicylic acid tetradecylphenyl ester, (mixed C11-C15) alkylsalicylic acid heptadecylphenyl ester, (mixed C11-C15) alkylsalicylic acid Hexadecylphenyl ester and the like can be mentioned.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the aromatic carboxylic acid ester derivative (B2) represented by the general formula (II) include (nonylsalicylic acid) nonylhydroxyphenyl ester, (decylsalicylic acid) decylhydroxyphenyl ester, and (undecylsalicylic acid) undecyl. Hydroxyphenyl ester, (undesylsalicylic acid) dodecylhydroxyphenyl ester, (dodecylsalicylic acid) undecylhydroxyphenyl ester, (dodecylsalicylic acid) dodecylhydroxyphenyl ester, (dodecylsalicylic acid) tridecylhydroxyphenyl ester, (tridecylsalicylic acid) dodecylhydroxy Phenyl ester, (tridecylsalicylic acid) tridecylhydroxyphenyl ester, (tetradecylsalicylic acid) tetradecylhydroxyphenyl ester, (heptadecylsalicylic acid) heptadecylhydroxyphenyl ester, (hexadecylsalicylic acid) hexadecylhydroxyphenyl ester, (mixed C11) ~ C15) Nonyl hydroxyphenyl ester of alkyl salicylate, (Mixed C11 ~ C15) Decyl hydroxyphenyl ester of alkyl salicylate, (Mixed C11 ~ C15) Undecyl hydroxyphenyl ester of alkyl salicylate, (Mixed C11 ~ C15) Dodecyl hydroxyphenyl ester of alkyl salicylate, (Mixed C11-C15) alkylsalicylic acid tridecylhydroxyphenyl ester, (mixed C11-C15) alkylsalicylic acid tetradecylhydroxyphenyl ester, (mixed C11-C15) alkylsalicylic acid heptadecylhydroxyphenyl ester, (mixed C11-C15) alkylsalicylic acid Hexadecyl hydroxyphenyl ester, (nonyldihydroxybenzoic acid) nonylphenyl ester, (decyldihydroxybenzoic acid) decylphenyl ester, (undodecyldihydroxybenzoic acid) undodecylphenyl ester, (undesyldihydroxybenzoic acid) dodecylphenyl ester, ( Dodecyldihydroxybenzoic acid) undecylphenyl ester, (dodecyldihydroxybenzoic acid) dodecylphenyl ester, (dodecyldihydroxybenzoic acid) tridecylphenyl ester, (tridecyldihydroxybenzoic acid) dodecylphenyl ester, (tridecyldihydroxybenzoic acid) tri Decylphenyl ester, (Tetradecyldihydroxybenzoic acid ) Tetradecylphenyl ester, (heptadecyldihydroxybenzoic acid) heptaphenyl ester, (hexadecyldihydroxybenzoic acid) hexadecylphenyl ester, nonyldihydroxybenzoic acid (mixed C11-C15) alkylphenyl ester, decyldihydroxybenzoic acid (mixed C11) ~ C15) Alkylphenyl ester, undodecyldihydroxybenzoic acid (mixed C11 to C15) alkylphenyl ester, dodecyldihydroxybenzoic acid (mixed C11 to C15) alkylphenyl ester, tridecyldihydroxybenzoic acid (mixed C11 to C15) alkylphenyl ester , Tetradecyldihydroxybenzoic acid (mixed C11-C15) alkylphenyl ester, heptadecyldihydroxybenzoic acid (mixed C11-C15) alkylphenyl ester, hexadecyldihydroxybenzoic acid (mixed C11-C15) alkylphenyl ester, (nonyldihydroxybenzoic acid) Acid) Nonylhydroxyphenyl ester, (Decildihydroxybenzoic acid) Decylhydroxyphenyl ester, (Undodecyldihydroxybenzoic acid) Undodecylhydroxyphenyl ester, (Undecyldihydroxybenzoic acid) Dodecylhydroxyphenyl ester, (Dodecyldihydroxybenzoic acid) Un Decylhydroxyphenyl ester, (dodecyldihydroxybenzoic acid) dodecylhydroxyphenyl ester, (dodecyldihydroxybenzoic acid) tridecylhydroxyphenyl ester, (tridecyldihydroxybenzoic acid) dodecylhydroxyphenyl ester, (tridecyldihydroxybenzoic acid) tridecylhydroxy Phenyl ester, (tetradecyldihydroxybenzoic acid) tetradecylhydroxyphenyl ester, (heptadecyldihydroxybenzoic acid) heptadecylhydroxyphenyl ester, (hexadecyldihydroxybenzoic acid) hexadecylhydroxyphenyl ester, nonyldihydroxybenzoic acid (mixed C11- C15) Alkylhydroxyphenyl ester, decyldihydroxybenzoic acid (mixed C11-C15) alkylhydroxyphenyl ester, undodecyldihydroxybenzoic acid (mixed C11-C15) alkylhydroxyphenyl ester, dodecyldihydroxybenzoic acid (mixed C11-C15) alkylhydroxy Phenylester, tridecyldihydroxybenzoic acid Breath scent (mixed C11-C15) alkylhydroxyphenyl ester, tetradecyldihydroxybenzoic acid (mixed C11-C15) alkylhydroxyphenyl ester, heptadecyldihydroxybenzoic acid (mixed C11-C15) alkylhydroxyphenyl ester, hexadecyldihydroxybenzoic acid Acid (mixed C11 to C15) alkyl hydroxyphenyl ester and the like can be mentioned.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, in the lubricating oil composition of the present embodiment, one or more selected from the aromatic carboxylic acid ester derivative (B1) represented by the general formula (I) and the general formula (II) are represented. It may be used in combination with one or more selected from the aromatic carboxylic acid ester derivative (B2).

Among the aromatic carboxylic acid ester derivative (B1) represented by the general formula (I) and the aromatic carboxylic acid ester derivative (B2) represented by the general formula (II), decylphenyl (decylsalicylic acid) Estel, (undecylsalicylic acid) undecylphenyl ester, (dodecylsalicylic acid) dodecylphenyl ester, (tridecylsalicylic acid) tridecylphenyl ester, (tetradecylsalicylic acid) tetradecylphenyl ester, (heptadecylsalicylic acid) heptadecylphenyl ester, And one or more selected from (hexadecylsalicylic acid) hexadecylphenyl ester, preferably (decylsalicylic acid) decylphenyl ester, (undecylsalicylic acid) undecylphenyl ester, (dodecylsalicylic acid) dodecylphenyl ester, and (tridecyl). One or more selected from (salicylic acid) tridecylphenyl ester is more preferable, and (dodecyl salicylic acid) dodecylphenyl ester is further preferable.

In the lubricating oil composition of the present embodiment, the content of the aromatic carboxylic acid ester derivative (B) is 1.5% by mass or more based on the total amount of the lubricating oil composition.
If the content of the aromatic carboxylic acid ester derivative (B) is less than 1.5% by mass based on the total amount of the lubricating oil composition, it becomes difficult to ensure the high temperature cleanliness of the lubricating oil composition.
Here, the content of the aromatic carboxylic acid ester derivative (B) is determined from the viewpoint of making it easier to improve the high-temperature cleanliness of the lubricating oil composition and making the lubricating oil composition more excellent in maintaining the basic value. It is preferably 1.8% by mass or more, more preferably 2.0% by mass or more, still more preferably 3.0% by mass or more, still more preferably 4.0% by mass or more, still more preferably 5.0% by mass or more. Is.
The upper limit of the content of the aromatic carboxylic acid ester derivative (B) is usually 20% by mass or less, preferably 10% by mass or less.

<Oxymolybdenum complex of basic nitrogen compound (C1)>
The lubricating oil composition of the present embodiment contains an oxymolybdenum complex (C1) of a basic nitrogen compound. By containing the oxymolybdenum complex (C1) of the basic nitrogen compound in the lubricating oil composition, the friction coefficient can be reduced while improving the high temperature cleaning property.

The oxymolybdenum complex (C1) of a basic nitrogen compound is a reaction product of an acidic molybdenum compound or a salt thereof and a basic nitrogen compound, and is a reaction product of the acidic molybdenum compound or a salt thereof while maintaining the reaction temperature at 120 ° C. or lower. It can be produced by contacting and reacting with a basic nitrogen compound.
Examples of the acidic molybdenum compound include molybdic acid, ammonium molybdate, alkali metal molybdate and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the basic nitrogen compound include succinate imide, carboxylic amide, hydrocarbon monoamine, hydrocarbon polyamine, Mannich hydrochloric acid, phosphon amide, thiophosphone amide, and phosphoric acid amide.
These may be used individually by 1 type, and may be used in combination of 2 or more type.
As the basic nitrogen compound, it is preferable to use succinate imide.

As the oxymolybdenum complex (C1) of the basic nitrogen compound, the reaction product of the acidic molybdenum compound or a salt thereof and the basic nitrogen compound may be used as it is, but a sulfide obtained by reacting with a smaller amount of sulfur or the sulfur compound. It is preferable to use as.
In the present invention, a sulfide obtained by reacting a reaction product of an acidic molybdenum compound and a basic nitrogen compound with a smaller amount of sulfur or a sulfur compound is also included in the oxymolybdenum complex (C1) of the basic nitrogen compound.
Here, the oxymolybdenum complex (C1) of the basic nitrogen compound is preferably a low-temperature sulfide reaction product obtained by low-temperature sulphurizing the reaction product of the acidic molybdenum compound or a salt thereof and imide succinate. From the viewpoint of low sulfur content, the sulfur content of the sulfide is preferably low, and the sulfur content is more preferably 10% or less (mass basis) of the molybdenum atom content.

Further, in the lubricating oil composition of the present embodiment, the content of molybdenum atoms derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is 0.025% by mass or more based on the total amount of the lubricating oil composition. ..
If the content of the molybdenum atom derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is less than 0.025% by mass, the friction coefficient cannot be sufficiently reduced.
Here, the content of the molybdenum atom derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is preferably 0. It is 030% by mass or more, more preferably 0.035% by mass or more, and further preferably 0.040% by mass or more.
The upper limit of the content of molybdenum atoms derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is usually 0.200% by mass or less.

In the lubricating oil composition of the present embodiment, the content of the molybdenum atom contained in the oxymolybdenum complex (C1) of the basic nitrogen compound is based on the total amount of the oxymolybdenum complex (C1) of the basic nitrogen compound, and is preferably 1. It is 0% by mass to 10.0% by mass, more preferably 2.0% by mass to 7.5% by mass, and further preferably 4.5% by mass to 6.5% by mass.
In the lubricating oil composition of the present embodiment, the content of sulfur atoms contained in the oxymolybdenum complex (C1) of the basic nitrogen compound is based on the total amount of the oxymolybdenum complex (C1) of the basic nitrogen compound, and is preferably 0. It is 01% by mass to 2.5% by mass, more preferably 0.05% by mass to 1.5% by mass, and further preferably 0.1% by mass to 0.3% by mass.
In the lubricating oil composition of the present embodiment, the content of nitrogen atoms contained in the oxymolybdenum complex (C1) of the basic nitrogen compound is based on the total amount of the oxymolybdenum complex (C1) of the basic nitrogen compound, preferably 0. It is 1% by mass to 5.0% by mass, more preferably 0.5% by mass to 2.5% by mass, and further preferably 1.0% by mass to 2.0% by mass.
In the lubricating oil composition of the present embodiment, the base value of the oxymolybdenum complex (C1) of the basic nitrogen compound is preferably 1 mgKOH / g to 200 mgKOH / g, more preferably 2 mgKOH / g to 50 mgKOH / g, and even more preferably. It is 3 mgKOH / g to 25 mgKOH / g.

<Calcium-based cleaning agent (D)>
The lubricating oil composition of the present embodiment contains a calcium-based cleaning agent (D) containing a calcium-based cleaning agent (D1) having a base value of 200 mgKOH / g or more. When the lubricating oil composition contains the calcium-based cleaning agent (D) containing the calcium-based cleaning agent (D1), the high-temperature cleanliness of the lubricating oil composition can be improved.
When the calcium-based cleaning agent (D) is not contained, sufficient high-temperature cleaning property cannot be ensured.
In the lubricating oil composition of the present embodiment, the content of calcium atoms derived from the calcium-based cleaning agent (D) is 0.020% by mass or more and less than 0.080% by mass based on the total amount of the lubricating oil composition. is there.
If the content of calcium atoms derived from the calcium-based cleaning agent (D) is less than 0.020% by mass, it is difficult to ensure high-temperature cleanliness of the lubricating oil composition. Further, when the content of calcium atoms derived from the calcium-based cleaning agent (D) is 0.080% by mass or more, the sulfated ash content of the lubricating oil composition becomes large, which causes clogging of GPF and the like.
Here, the content of calcium atoms derived from the calcium-based cleaning agent (D) is based on the total mass of the lubricating oil composition from the viewpoint of facilitating low sulfated ash content while ensuring high-temperature cleanliness of the lubricating oil composition. It is preferably 0.020% by mass to 0.070% by mass, preferably 0.030% by mass to 0.065% by mass, and more preferably 0.035% by mass to 0.055% by mass.

In the lubricating oil composition of the present embodiment, the content of the calcium-based cleaning agent (D) may be adjusted so that the content of calcium atoms derived from the calcium-based cleaning agent (D) satisfies the above range. Specifically, the content of the calcium-based cleaning agent (D) is, for example, preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass, based on the total amount of the lubricating oil composition. % Or more and 2.5% by mass or less, more preferably 0.20% by mass or more and 1.5% by mass or less.

(Calcium-based cleaning agent (D1) having a base value of 200 mgKOH / g or more)
Examples of the calcium-based cleaning agent (D1) include calcium sulfonate represented by the following general formula (D1-1), calcium salicylate represented by the following general formula (D1-2), and the following general formula (D1). Examples thereof include calcium salts such as calcium phenate represented by -3).
Among these, calcium sulfonate is preferable from the viewpoint of improving high-temperature cleanliness.
As the calcium-based cleaning agent (D1), one type may be used alone, or two or more types may be used in combination.
The calcium-based cleaning agent (D1) is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and further preferably 95% by mass to 100% by mass based on the total amount of the calcium-based cleaning agent (D). It is by mass, more preferably 100% by mass.

In the above general formula (D1-3), q is an integer of 0 or more, preferably an integer of 0 or more and 3 or less.
In the above general formulas (D1-1) to (D1-3), R is independently a hydrogen atom or a hydrocarbon group.
The hydrocarbon group that can be selected as R may have a linear structure, may have a branched chain, or may form a ring. Among these, a hydrocarbon group having a branched chain is preferable.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group and the like.
Among these, an alkyl group having a branched chain is preferable.
The number of carbon atoms of the hydrocarbon group is preferably 3 or more and 26 or less, more preferably 7 or more and 24 or less, and further preferably 10 or more and 20 or less.
In the hydrocarbon group having a branched chain, the number of carbon atoms in the branched chain is preferably 1 or more and 8 or less, more preferably 2 or more and 6 or less, and further preferably 2 or more and 5 or less.

In the lubricating oil composition of the present embodiment, the basic value of the calcium-based cleaning agent (D1) is preferably 200 mgKOH / g or more from the viewpoint of suppressing the generation of precipitates and the like while improving the high-temperature cleaning property. It is 500 mgKOH / g, more preferably 200 mgKOH / g to 480 mgKOH / g, and even more preferably 200 mgKOH / g to 460 mgKOH / g.
When the calcium-based cleaning agent (D1) is a calcium sulfonate represented by the above general formula (D1-1), the base value of the calcium-based cleaning agent (D1) is preferably from the same viewpoint as above. It is 300 mgKOH / g to 500 mgKOH / g, more preferably 350 mgKOH / g to 490 mgKOH / g, and even more preferably 400 mgKOH / g to 480 mgKOH / g.
When the calcium-based cleaning agent (D1) is a calcium salicylate represented by the above general formula (D1-2), the base value of the calcium-based cleaning agent (D1) is determined from the same viewpoint as described above. It is preferably 200 mgKOH / g to 400 mgKOH / g, more preferably 200 mgKOH / g to 300 mgKOH / g, and even more preferably 200 mgKOH / g to 250 mgKOH / g.

In the present specification, the base value of the calcium-based cleaning agent (D1) means the base value measured by the perchloric acid method in accordance with JIS K 2501: 2003.

Here, in the lubricating oil composition of the present embodiment, the content of calcium atoms derived from the calcium-based cleaning agent (D1) is 0.020% by mass or more and 0.080% by mass based on the total amount of the lubricating oil composition. Less than is preferable.
If the content of calcium atoms derived from the calcium-based cleaning agent (D1) is less than 0.020% by mass, it is difficult to ensure high-temperature cleanliness of the lubricating oil composition. Further, when the content of calcium atoms derived from the calcium-based cleaning agent (D1) is 0.080% by mass or more, the sulfated ash content of the lubricating oil composition increases, which may cause clogging of GPF and the like. is there.
Here, the content of calcium atoms derived from the calcium-based cleaning agent (D1) is based on the total mass of the lubricating oil composition from the viewpoint of facilitating low sulfated ash content while ensuring high-temperature cleanliness of the lubricating oil composition. It is preferably 0.020% by mass to 0.070% by mass, preferably 0.030% by mass to 0.065% by mass, and more preferably 0.035% by mass to 0.055% by mass.

In the lubricating oil composition of the present embodiment, the content of the calcium-based cleaning agent (D1) may be adjusted so that the content of calcium atoms derived from the calcium-based cleaning agent (D1) satisfies the above range. The content of the calcium-based cleaning agent (D1) is, for example, preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 2.5, based on the total amount of the lubricating oil composition. It is mass% or less, more preferably 0.20 mass% or more and 1.5 mass% or less.

(Calcium-based cleaning agent (D2) having a base value of less than 200 mgKOH / g)
In the lubricating oil composition of the present embodiment, the content of the calcium-based cleaning agent (D2) is small among the calcium-based cleaning agents (D) from the viewpoint of facilitating the high-temperature cleanliness of the lubricating oil composition. preferable. Specifically, the content of calcium atoms derived from the calcium-based cleaning agent (D2) is preferably less than 0.025% by mass, more preferably less than 0.020% by mass, based on the total amount of the lubricating oil composition. It is more preferably less than 0.015% by mass, even more preferably less than 0.010% by mass, and even more preferably less than 0.005% by mass.

Examples of the calcium-based cleaning agent (D2) include calcium sulfonate represented by the general formula (D1-1), calcium salicylate represented by the general formula (D1-2), and the general formula (D1-3). ), And other calcium salts such as calcium phenate.
Further, the base value of the calcium-based cleaning agent (D2) may be less than 100 mgKOH / g, less than 50 mgKOH / g, or less than 30 mgKOH / g.
The base value of the calcium-based cleaning agent (D2) is usually 10 mgKOH / g or more.

Here, in the lubricating oil composition of the present embodiment, from the viewpoint of facilitating the high-temperature cleanliness of the lubricating oil composition, a calcium atom (Ca _D2 ) derived from the calcium-based cleaning agent (D2) and a calcium-based cleaning agent ( The content ratio [Ca _D2 / Ca _D1 ] with the calcium atom (Ca D1) derived from _D1 ) is preferably less than 0.31 and more preferably less than 0.25, more preferably less than 0.25 by mass ratio. It is less than 0.19, more preferably less than 0.13, and even more preferably less than 0.06.

<ZnDTP (E)>
The lubricating oil composition of the present embodiment preferably contains ZnDTP (zinc dithiophosphate) (E).
Examples of ZnDTP (E) include zinc dithiophosphate having a primary dialkyl group, zinc dithiophosphate having a secondary dialkyl group, and the like.
One type of ZnDTP (E) may be used alone, or two or more types may be used in combination.

The carbon number of the alkyl group of ZnDTP (E) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 or more and 10 or less, and more preferably 3 or more and 8 or less. In addition, zinc dithiophosphate having a secondary dialkyl group or the like may contain an alkyl group having a different number of carbon atoms.

In the lubricating oil composition of the present embodiment, the content of the phosphorus atom (EP) derived from ZnDTP (E) maintains the basic value at a certain level or higher while reducing the phosphorus atom emission amount, and the LSPI. From the viewpoint of facilitating the suppression of the occurrence of the above, it is preferably 0.020% by mass or more and 0.040% by mass or less, and more preferably 0.021% by mass or more and 0.036% by mass based on the total amount of the lubricating oil composition. It is less than or equal to, more preferably 0.022% by mass or more and 0.032% by mass or less.

In the lubricating oil composition of the present embodiment, the content of ZnDTP (E) is preferably adjusted so that the content in terms of phosphorus atom is within the above range. Specifically, the lubricating oil composition Based on the total amount (100% by mass), preferably 0.28% by mass or more and 0.57% by mass or less, more preferably 0.30% by mass or more and 0.51% by mass or less, still more preferably 0.31% by mass or more and 0. It is .45% by mass or less.

<Additives for other lubricating oils>
The lubricating oil composition of the present embodiment may contain additives for lubricating oil other than the above components as long as the effects of the present invention are not impaired.
Examples of the other additive for lubricating oil include an antioxidant, an ashless dispersant, a metal-based cleaning agent other than the calcium-based cleaning agent (D1), a pour point lowering agent, a viscosity index improver, and an anti-corrosion agent. Examples include rust agents, antifoaming agents, metal inactivating agents, anti-emulsifiers and the like.

(Antioxidant)
Examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants.
These may be used individually by 1 type, and may be used in combination of 2 or more type.
Here, as the antioxidant, it is preferable to use one or more selected from amine-based antioxidants and one or more selected from phenol-based antioxidants in combination.
Examples of the amine-based antioxidant include diphenylamine and diphenylamine-based antioxidants such as alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms; α-naphthylamine and alkyl-substituted phenyl-α-naphthylamine having 3 to 20 carbon atoms. And the like, naphthylamine-based antioxidants and the like can be mentioned.
Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and octadecyl-3- (3,5-di). Monophenolic antioxidants such as -tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6) -Diphenol-based antioxidants such as tert-butylphenol); hindered phenol-based antioxidants and the like can be mentioned.

(Ashes-free dispersant)
Examples of the ashless dispersant include boron-free succinic acid imides such as boron-free alkenyl succinate imide, boron-containing succinic acid imides such as boron-containing alkenyl succinate imide, benzylamines, and boron-containing benzylamines. Examples thereof include succinic acid esters, monovalent or divalent carboxylic acid amides typified by fatty acids or succinic acid.
These may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these, boron-free alkenyl succinate imide and boron-containing alkenyl succinate imide are preferably used, and boron-free alkenyl succinate imide and boron-containing alkenyl succinate imide are more preferably used in combination.

(Metal-based cleaning agents other than calcium-based cleaning agent (D))
Examples of the metal-based cleaning agent other than the calcium-based cleaning agent (D) include metal salicylate, metal phenate, and metal sulfonate made of a metal other than calcium.
Examples of metals other than calcium include alkali metals and alkaline earth metals. Specific examples thereof include sodium, magnesium, barium and the like, and among these, magnesium is preferably used.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Pour point depressant)
Examples of the pour point lowering agent include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Viscosity index improver)
Examples of the viscosity index improver include non-dispersive polymethacrylate, dispersed polymethacrylate, olefin-based copolymer (for example, ethylene-propylene copolymer, etc.), dispersed olefin-based copolymer, and styrene-based copolymer. (For example, a styrene-diene copolymer, a styrene-isoprene copolymer, etc.) and the like can be mentioned.
These may be used individually by 1 type, and may be used in combination of 2 or more type.
The mass average molecular weight (Mw) of these viscosity index improvers is usually 500 to 1,000,000, preferably 5,000 to 100,000, more preferably 10,000 to 50,000, but heavy. It is set appropriately according to the type of coalescence.
In the present specification, the mass average molecular weight (Mw) of each component is a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.

(anti-rust)
Examples of the rust preventive include fatty acids, alkenyl succinic acid half esters, fatty acid sequels, alkyl sulfonates, polyhydric alcohol fatty acid esters, fatty acid amines, oxidized paraffins, alkyl polyoxyethylene ethers and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Defoamer)
Examples of the defoaming agent include silicone oil, fluorosilicone oil, fluoroalkyl ether and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Metal inactivating agent)
Examples of the metal inactivating agent include benzotriazole-based compounds, tolyltriazole-based compounds, thiazizol-based compounds, imidazole-based compounds, pyrimidine-based compounds and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Anti-emulsifier)
Examples of the anti-emulsifier include anionic surfactants such as sulfate ester salt of castor oil and petroleum sulfonate; cationic surfactants such as quaternary ammonium salt and imidazolines; polyoxyalkylene polyglycol and its dicarboxylic acid. Esters; alkylene oxide adducts of alkylphenol-formaldehyde polycondensates; and the like.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the other additives for lubricating oil can be appropriately adjusted within a range that does not impair the effects of the present invention, but for each of them, based on the total amount (100% by mass) of the lubricating oil composition. Usually, it is 0.001% by mass to 15% by mass, preferably 0.005% by mass to 10% by mass, more preferably 0.01% by mass to 7% by mass, and further preferably 0.03% by mass to 5% by mass. preferable.
In the present specification, the other additives for lubricating oil are diluted and dissolved in a part of the above-mentioned base oil (A) in consideration of handleability, solubility in the base oil (A), and the like. It may be blended with other ingredients in the form of a solution. In such a case, in the present specification, the above-mentioned content of the additive as the other component means the content in terms of the active ingredient (resin content conversion) excluding the diluted oil.

<Other ingredients>
In addition to the above components, the lubricating oil composition of the present embodiment includes ester derivatives other than the aromatic carboxylic acid ester derivative (B) and molybdenum compounds other than the oxymolybdenum complex (C1) of the basic nitrogen compound ( C), a calcium-based cleaning agent (D) other than the calcium-based cleaning agent (D1) may be contained.
However, it is preferable that the content of the compound described below is small, and it is more preferable that the compound described below is not contained.

(Boric acid ester (B'))
In the lubricating oil composition of the present embodiment, from the viewpoint of ensuring high-temperature cleanliness of the lubricating oil composition, it is preferable that the content of the borate ester (B') among the ester derivatives is small. Specifically, the content of the boric acid ester (B') is preferably less than 5.0% by mass, more preferably less than 1.0% by mass, and further preferably 0. It is less than 1% by weight, more preferably less than 0.01% by weight, and even more preferably free of boric acid ester (B').
Examples of the boric acid ester (B') include borate glycerol monoolate and the like.

(Molybdenum dithiocarbamate (C2))
In the lubricating oil composition of the present embodiment, the content of molybdenum dithiocarbamate (C2) is small among the molybdenum compounds (C) from the viewpoint of reducing the friction coefficient while ensuring the high temperature cleanliness of the lubricating oil composition. Is preferable. Specifically, the content of the molybdenum atom derived from molybdenum dithiocarbamate (C2) is preferably less than 0.020% by mass, more preferably less than 0.015% by mass, still more preferably, based on the total amount of the lubricating oil composition. Is less than 0.010% by mass, more preferably less than 0.005% by mass, and even more preferably free of molybdenum atoms derived from molybdenum dithiocarbamate (C2).

Examples of molybdenum dithiocarbamate (C2) include binuclear molybdenum dithiocarbamate containing two molybdenum atoms in one molecule and trinuclear molybdenum dithiocarbamate containing three molybdenum atoms in one molecule.

Examples of the dinuclear molybdenum dithiocarbamate include a compound represented by the following general formula (C2-1) and a compound represented by the following general formula (C2-2).

In the above general formulas (C2-1) and (C2-2), R ¹¹ to R ¹⁴ each independently represent a hydrocarbon group, and these may be the same or different from each other.
X ¹¹ to X ¹⁸ independently represent an oxygen atom or a sulfur atom, and may be the same as or different from each other. ^{However, at least two of X 11} to X ^{18 in} the formula (C2-1) are sulfur atoms.
The hydrocarbon group that can be selected as ^{R 11} to R ^{14 has 6 to 22 carbon atoms.}

^{Examples of the hydrocarbon group that can be selected as R 11} to R ^{14 in the} general formulas (C2-1) and (C2-2) include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an alkylaryl. Groups, arylalkyl groups and the like can be mentioned.
Examples of the alkyl group include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. ..
Examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group and the like.
Examples of the cycloalkyl group include a cyclohexyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, a methylcyclohexylmethyl group, a cyclohexylethyl group, a propylcyclohexyl group, a butylcyclohexyl group, a heptylcyclohexyl group and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a terphenyl group and the like.
Examples of the alkylaryl group include a tolyl group, a dimethylphenyl group, a butylphenyl group, a nonylphenyl group, a dimethylnaphthyl group and the like.
Examples of the arylalkyl group include a methylbenzyl group, a phenylmethyl group, a phenylethyl group, a diphenylmethyl group and the like.

Examples of the trinuclear molybdenum dithiocarbamate include compounds represented by the following general formula (C2-3).
_{_{_{_{Mo 3 S k E m L n}}}} A p Q z (C2-3)

In the general formula (C2-3), k is an integer of 1 or more, m is an integer of 0 or more, k + m is an integer of 4 to 10, and is preferably an integer of 4 to 7. n is an integer of 1 to 4, and p is an integer of 0 or more. z is an integer from 0 to 5 and includes non-stoichiometric values.
Each of E is an oxygen atom or a selenium atom independently, and can substitute sulfur in a core described later, for example.
L is an anionic ligand having an organic group containing a carbon atom independently, and the total number of carbon atoms of the organic group in each ligand is 14 or more, and each ligand may be the same. , May be different.
A is an anion other than L independently of each other.
Q is a neutral compound that donates electrons independently and exists to satisfy the empty coordination on the trinuclear molybdenum compound.

Here, in the lubricating oil composition of the present embodiment, from the viewpoint of reducing the friction coefficient while ensuring the high-temperature cleanliness of the lubricating oil composition, the Mo atom (Mo _C2 ) derived from molybdenum dithiocarbamate (C2) is used. The content ratio [Mo _C2 / Mo _C1 ] of the basic nitrogen compound to the molybdenum atom (Mo _C1 ) derived from the oxymolybdenum complex (C1) is preferably less than 1.0, more preferably 0. It is less than 5, more preferably less than 0.1, even more preferably less than 0.05, and even more preferably less than 0.01.

[Physical characteristics of lubricating oil composition]
<Kinematic viscosity and viscosity index>
40 ° C. The kinematic viscosity of the lubricating oil composition of the present embodiment is preferably not more than 5.0 mm ² / s or more 150.0 ² / s, more preferably not more than 10.0 mm ² / s or more 100.0 mm ² / s, More preferably, it is 30.0 mm ² / s or more and 60.0 mm ^{2 / s or less.} When the 40 ° C. kinematic viscosity is within the above range, it is easy to secure fuel efficiency.
The 100 ° C. kinematic viscosity of the lubricating oil composition of the present embodiment ^{is preferably 4.0 mm 2} / s or more, more preferably 5.0 mm ² / s or ^{more, further preferably 6.1 mm 2} / s or more, and 6.9 mm. ² / s or more is even more preferable, and 6.9 mm ² / s or more is even more preferable. Also, 100 ° C. kinematic viscosity of the lubricating oil composition of the present embodiment is preferably less than 22.0 mm ² / s, more preferably less than 20.0 mm ² / s, more preferably less than 16.3 mm ² / s, 12 .5mm more preferably more than ² / s, even more preferably less than 9.3 mm ² / s, even more preferably less than 8.2 mm ² / s. When the 100 ° C. kinematic viscosity is 4.0 mm ² / s or more, it is easy to secure wear resistance. Further, when the intrinsic viscosity at 100 ° C. is low, it is easy to secure fuel saving.
The viscosity index of the lubricating oil composition of the present embodiment is preferably 80 or more, more preferably 85 or more, further preferably 90 or more, and even more preferably 95 or more. When the viscosity index is 80 or more, the change in viscosity with temperature becomes small.
The 40 ° C. kinematic viscosity, the 100 ° C. kinematic viscosity, and the viscosity index can be measured or calculated in accordance with JIS K 2283: 2000, for example, using a glass capillary viscometer.

<Molybdenum atom content>
The content of molybdenum atoms in the lubricating oil composition of the present embodiment is preferably 0.025% by mass or more, more preferably 0.030, based on the total amount of the lubricating oil composition, from the viewpoint of facilitating the reduction of the coefficient of friction. It is by mass% or more, more preferably 0.035% by mass or more, and even more preferably 0.040% by mass or more.
The upper limit of the molybdenum atom content is usually 0.200% by mass or less.
The content of molybdenum atom can be measured according to JPI-5S-38-03.

<Calcium atom content>
The content of the calcium atom derived from the calcium-based cleaning agent (D) in the lubricating oil composition of the present embodiment is a lubricating oil composition from the viewpoint of maintaining good high-temperature cleaning property and low sulfated ash content. Based on the total amount, preferably 0.020% by mass to 0.070% by mass, more preferably 0.025% by mass to 0.065% by mass, still more preferably 0.030% by mass to 0.060% by mass, still more. It is preferably 0.035% by mass to 0.055% by mass.
The calcium atom content can be measured according to JPI-5S-38-03.

<Phosphorus atom content>
The content of phosphorus atoms in the lubricating oil composition of the present embodiment is 0.020% by mass or more and 0.040% by mass or less based on the total amount of the lubricating oil composition.
If the phosphorus atom content is less than 0.020% by mass, the generation of LSPI may not be suppressed. On the other hand, if it exceeds 0.040% by mass, the amount of phosphorus atoms emitted increases, and the exhaust gas purification catalyst may be poisoned.
Here, the content of the phosphorus atom in the lubricating oil composition is preferably 0, based on the total amount of the lubricating oil composition, from the viewpoint of facilitating the suppression of the generation of LSPI while reducing the phosphorus atom emission amount. It is 021% by mass or more and 0.036% by mass or less, more preferably 0.022% by mass or more and 0.032% by mass or less, and further preferably 0.022% by mass or more and 0.030% by mass or less.
The phosphorus atom content can be measured according to JPI-5S-38-03.

<Zinc atom content>
The content of zinc atoms in the lubricating oil composition of the present embodiment is preferably 0.020% by mass to 0.040% by mass based on the total amount of the lubricating oil composition from the viewpoint of improving wear resistance. , More preferably 0.022% by mass to 0.036% by mass, still more preferably 0.024% by mass to 0.032% by mass.
The zinc atom content can be measured according to JPI-5S-38-03.

<Sulfur atom content>
The content of sulfur atoms in the lubricating oil composition of the present embodiment is preferably 0.10% by mass or more and 0.25% by mass or less, and 0.15% by mass or more and 0.23 by mass or more, based on the total amount of the lubricating oil composition. More preferably, it is 0.15% by mass or more, and further preferably 0.21% by mass or less.
The sulfur atom content can be measured according to ASTM D2622.

<Boron atom content>
The content of the boron atom in the lubricating oil composition of the present embodiment is preferably 0.030% by mass or more and 0.050% by mass or less, and 0.034% by mass or more and 0.045 based on the total amount of the lubricating oil composition. More preferably, it is 0.036% by mass or more, and further preferably 0.043% by mass or less.
The content of boron atom can be measured according to JPI-5S-38-03.

<Nitrogen atom content>
The content of nitrogen atoms in the lubricating oil composition of the present embodiment is preferably 0.150% by mass or more and 0.280% by mass or less, and 0.180% by mass or more and 0.250 by mass or more, based on the total amount of the lubricating oil composition. More preferably, it is 0.200% by mass or more, and further preferably 0.230% by mass or less.
The content of nitrogen atoms can be measured according to JIS K 2609: 1998.

<Sulfate ash>
The lubricating oil composition of the present embodiment has a sulfated ash content of 0.30% by mass or less. The lubricating oil composition of the present embodiment has good high-temperature cleanliness even with such a low sulfated ash content.
In the lubricating oil composition of the present embodiment, the sulfuric acid ash content is preferably 0.29% by mass or less, more preferably 0.28% by mass or less, still more preferably 0.27% by mass or less.
Further, in the lubricating oil composition of the present embodiment, the sulfated ash content is usually 0.01% by mass or more.
The sulfated ash content of the lubricating oil composition can be measured according to JIS K2272: 1998.

<LSPI inhibitory>
The LSPI inhibitory property of the lubricating oil composition of the present embodiment can be evaluated using, for example, a 2.0 L in-line 4-cylinder engine (trade name: Ecotec engine) manufactured by GM. Specifically, it can be evaluated by the method described in Examples described later. The total number of times LSPI is generated in the method described in Examples described later is preferably 0 times.

<Base value, base value maintenance rate>
From the viewpoint of maintaining the base value of the lubricating oil composition of the present embodiment at a certain level or higher, the base value maintenance rate is preferably 0.20 or more, preferably 0.24 or more, and more preferably 0.35 or more. ..
The "base value" of the lubricating oil composition of the present embodiment can be measured by the perchloric acid method in accordance with JIS K 2501: 2003.
"Base number retention rate" of the lubricating oil composition of the present embodiment, the base number after NO _X blow test, divided by the base number of the initial value, is calculated.

<High temperature cleanliness>
High temperature detergency of the lubricating oil composition of the present embodiment, for example, by blowing a NO _X gas in the lubricating oil composition immediately after preparation was degraded processing, hot tube test against degradation treated lubricating oil composition It can be evaluated by. It can be said that this evaluation result reflects the maintainability of the high temperature cleanliness of the lubricating oil composition.
Specifically, it can be evaluated by the method described in Examples described later. Of the scores 0 to 10 of the hot tube test in the method described in Examples described later, 2.5 or more is preferable, and 3.0 or more is more preferable.

<Coefficient of friction>
The coefficient of friction of the lubricating oil composition of the present embodiment can be evaluated using, for example, an SRV tester (manufactured by Optimol). Specifically, it can be evaluated by the method described in Examples described later. The coefficient of friction in the method described in Examples described later is preferably 0.13 or less, more preferably 0.12 or less.

[Use of lubricating oil composition]
The lubricating oil composition of the present embodiment has low sulfuric acid ash content and low phosphorus content, can suppress the generation of LSPI, and has good high-temperature cleanliness, while reducing the coefficient of friction. Can be done.
Therefore, the lubricating oil composition of the present embodiment is preferably used for an internal combustion engine, more preferably used for an internal combustion engine equipped with an exhaust gas treatment device equipped with a gasoline particulate filter (GPF), and supercharged. It is more preferably used for a direct-injection internal combustion engine equipped with a machine. As the internal combustion engine, a gasoline engine is preferable, and it is more preferable to use it for a direct injection gasoline engine in which a supercharger is mounted on the gasoline engine.

[Manufacturing method of lubricating oil composition]
In this embodiment, the base oil (A), the aromatic carboxylic acid ester derivative (B1) represented by the following general formula (I), and the aromatic carboxylic acid ester derivative represented by the following general formula (II) ( One or more aromatic carboxylic acid ester derivatives (B) selected from B2), an oxymolybdenum complex (C1) of a basic nitrogen compound, and a calcium-based cleaning agent (D1) having a base value of 200 mgKOH / g or more. A method for producing a lubricating oil composition, which comprises a step of mixing with a calcium-based detergent (D) containing.

[In the general formula (II), m, n, о, and p are 1 ≦ m ≦ 2, 0 ≦ n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ о ≦ 3, 1 ≦ p ≦, respectively. It is an integer that satisfies 3. R ³ and R ⁴ each independently represent an alkyl group having 9 to 20 carbon atoms. If it is o ≧ 2, a plurality of R ³ may be be the same or different. When p ≧ 2, the plurality of R ^4s may be the same or different. ]
The blending amount of the aromatic carboxylic acid ester derivative (B) is 1.5% by mass or more based on the total amount of the lubricating oil composition.
The blending amount of the molybdenum atom derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is 0.025% by mass or more based on the total amount of the lubricating oil composition.
The amount of calcium atoms derived from the calcium-based cleaning agent (D) is 0.020% by mass or more and less than 0.080% by mass.
Sulfate ash content is 0.3% by mass or less,
Provided is a method for producing a lubricating oil composition, wherein the blending amount of phosphorus atoms is 0.020% by mass or more and 0.040% by mass or less based on the total amount of the lubricating oil composition.

The method for mixing each of the above components is not particularly limited, but for example, the base oil (A) is mixed with the aromatic carboxylic acid ester derivative (B), the oxymolybdenum complex (C1) of the basic nitrogen compound, and the base. Examples thereof include a step of adding a calcium-based cleaning agent (D) containing a calcium-based cleaning agent (D1) having a value of 200 mgKOH / g or more and then mixing the mixture.
In addition, the production method can further include a step of adding one or more selected from the above-mentioned other additives for lubricating oil and other components.
Each component may be added in the form of a solution (dispersion) by adding a diluting oil or the like. Further, after each component is added, it is preferable to include a step of stirring and uniformly dispersing by a known method.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples. In addition, each component used in Examples and Comparative Examples and various properties of the obtained lubricating oil composition were measured by the following methods. These results are shown in Tables 1 to 3.

[40 ° C. kinematic viscosity, 100 ° C. kinematic viscosity, viscosity index]
Measured and calculated using a glass capillary viscometer in accordance with JIS K2283: 2000.

[Contents of molybdenum atom, calcium atom, phosphorus atom, zinc atom, and boron atom]
The contents of molybdenum atom, calcium atom, phosphorus atom, zinc atom, and boron atom were measured according to JPI-5S-38-03.

[Sulfur atom content]
The sulfur atom content was measured according to ASTM D2622.

[Nitrogen atom content]
The content of nitrogen atoms was measured according to JIS K 2609: 1998.

[Sulfate ash]
The sulfated ash content of the lubricating oil composition was measured according to JIS K2272: 1998.

[Base value]
The base value was measured by the perchloric acid method in accordance with JIS K 2501: 2003.

[Examples 1 to 5 and Comparative Examples 1 to 14]
Each component shown below was added at the contents shown in Tables 1 to 3 and mixed sufficiently to obtain a lubricating oil composition.
Details of each component used in Examples 1 to 5 and Comparative Examples 1 to 14 are as shown below.

<Base oil (A)>
100N mineral oil (Classification in API base oil category: Group III, 40 ° C. kinematic viscosity: 20.0 mm ² / s, 100 ° C. kinematic viscosity: 4.2 mm ² / s, viscosity index: 123)

<Ester derivative>
-Aromatic carboxylic acid ester derivative (B): n-dodecyl salicylic acid-dodecylphenyl ester. It is an aromatic carboxylic acid ester derivative (B1) represented by the general formula (I), and x = 1, y = 1, R ¹ is an n-dodecyl group, and R ² is a dodecyl group.
-Boric acid ester (B'): Glycerol borate monoolate

<Molybdenum compound (C)>
-Oxymolybdenum complex of basic nitrogen compound (C1): Oxymolybdenum complex of succinate imide (sulfur-containing, Mo: 5.5% by mass, S: 0.2% by mass, N: 1.6% by mass, base value : 10 mgKOH / g, product name "OLOA17502", manufactured by Chevron Japan Co., Ltd. The base value of the oxymolybdenum complex (C1) was measured by the perchloric acid method in accordance with JIS K 2501: 2003.)
-Binuclear MoDTC (C2-1) (Mo: 10.0% by mass, S: 11.5% by mass)
-Trinuclear MoDTC (C2-3) (Mo: 5.5% by mass, S: 9.9% by mass)

<Calcium-based cleaning agent (D)>
-Calcium-based cleaning agent (D1-1): hyperbasic calcium sulfonate (base value: 421 mgKOH / g, calcium atom content: 15.8% by mass)
-Calcium-based cleaning agent (D1-2): hyperbasic calcium salicylate (base value: 221 mgKOH / g, calcium atom content: 7.9% by mass)
-Calcium-based cleaning agent (D2): Neutral calcium sulfonate (base value: 21 mgKOH / g, calcium atom content: 2.4% by mass)

<ZnDTP (E)>
ZnDTP (E1): ZnDTP having a primary alkyl group
ZnDTP (E2): ZnDTP having a secondary alkyl group

<Additives for other lubricating oils>
Viscosity index improver, pour point lowering agent, phenolic antioxidant, amine antioxidant, boron-free succinic acid imides, boron-containing succinate imides, metal deactivator, defoaming agent, etc.

In addition, the following evaluations were performed for each of the obtained lubricating oil compositions.

[Evaluation of LSPI inhibitory properties]
A 2.0L in-line 4-cylinder engine (trade name: Ecotec engine) manufactured by GM was used. The test conditions are based on the GMW17244 test method, and the evaluation is performed under low load condition operation (rotation speed: 2,000 rpm, torque: 100 Nm, net average effective pressure: 6 bar, operation time: 30 minutes). Rotation speed: 2,000 rpm, torque: 32 Nm, net average effective pressure: 2 bar, operating time: 5 minutes) and high load condition operation (rotation speed: 2,000 rpm, torque: 350 Nm, net average effective pressure: 22 bar, The operation time (15 minutes) was repeated 9 times each, and the total number of times of LSPI generated during operation under high load conditions was measured. As for the evaluation of the LSPI inhibitory property, when the evaluation result was "A" in the following evaluation criteria, it was evaluated as a lubricating oil composition having excellent LSPI inhibitory property. The LSPI is defined as occurring when the maximum combustion pressure is 30% or more higher than the average value of the normal value and when the crank angle at the start of combustion is 5 degrees or more earlier than the normal value.
-Evaluation criteria for LSPI inhibitory properties-
A: The total number of occurrences of the LSPI is 0. B: The total number of occurrences of the LSPI is 1 or more.

[Evaluation of maintainability of high temperature cleanliness]
First, the base value (initial value) of the obtained lubricating oil composition was measured by the perchloric acid method based on JIS K 2501: 2003.
Then, the oil temperature and 0.99 ° C., the concentration: 4,000 ppm by volume of the NO _X gas 72 hours blown into the lubricating oil composition, the deteriorated processing lubricating oil composition. (By this deterioration treatment, the lubricating oil composition corresponds to the state after traveling about 16,000 km.)
A hot tube test was performed on the deteriorated lubricating oil composition under the condition of temperature: 260 ° C. Also, again JIS K 2501: by the perchloric acid method conforming to 2003, the base value of the resulting lubricating oil composition (after NO _X blow test) was measured.
Furthermore, the base number after NO _X blow test, divided by the base number of the initial value, was calculated base number retention.
When the score was 2.5 or more among the scores of 0 to 10 in the hot tube test, it was evaluated as a lubricating oil composition in which high temperature cleanliness was maintained for a long period of time.
Further, the sample after the hot tube test was visually observed, and when the evaluation result was "A" in the following evaluation criteria, it was evaluated as a lubricating oil composition having excellent maintainability of high temperature cleanliness.
-Evaluation criteria for precipitation in hot tube test-
A: No white precipitation occurred.
B: White precipitation occurred.

[Evaluation of friction coefficient reduction effect]
According to ASTM D5706, the friction coefficient when the prepared lubricating oil composition was used was measured using an SRV tester (manufactured by Optimol) under the following conditions. The average value of the friction coefficient in 10 minutes from 20 minutes after the start of the test to the end of the test was taken as the friction coefficient. When the friction coefficient was 0.13 or less, it was evaluated as a lubricating oil composition having an excellent friction coefficient reducing effect.
・ Ball: AISI52100
-Disc: AISI52100
・ Frequency: 30Hz
・ Amplitude: 3.0 mm
・ Load: 400N
・ Temperature: 120 ℃
・ Test time: 30 minutes

The evaluation results are shown in Tables 1 to 3.
In Tables 1 to 3, the content of molybdenum atoms in the lubricating oil composition is a value that reflects the content of molybdenum atoms derived from the molybdenum compound (C).
Further, in Tables 1 to 3, the content of calcium atoms in the lubricating oil composition is a value reflecting the content of calcium atoms derived from the calcium-based cleaning agent (D).
In Table 1, in Example 4, the calcium atom content derived from the calcium-based cleaning agent (D1-1) was 0.026% by mass, and the calcium atom content derived from the calcium-based cleaning agent (D2) was 0. .024% by mass.
Further, in Tables 1 to 3, the content of phosphorus atoms in the lubricating oil composition is a value reflecting the content of phosphorus atoms derived from ZnDTP (E).
Further, in Tables 1 to 3, the content of zinc atoms in the lubricating oil composition is a value reflecting the content of zinc atoms derived from ZnDTP (E).

The lubricating oil compositions of Examples 1 to 5 satisfying all the configurations of the present invention were excellent in LSPI suppression property, high temperature cleanliness property, and friction coefficient reduction effect.
On the other hand, the contents of Comparative Examples 1 and 2 which do not contain the aromatic carboxylic acid ester derivative (B) and the content of the aromatic carboxylic acid ester derivative (B) are 1.5% by mass or more based on the total amount of the lubricating oil composition. In Comparative Example 3 which did not satisfy the regulation, the result of the hot tube test was poor, and the high temperature cleanliness was inferior. Further, in Comparative Example 4 containing a boric acid ester (B') instead of the aromatic carboxylic acid ester derivative (B), white precipitation occurred in the hot tube test, resulting in inferior high-temperature cleanliness. ..
Comparative Example 5 which does not contain the oxymolybdenum complex (C1) of the basic nitrogen compound as the molybdenum compound (C), and the content of the molybdenum atom derived from the oxymolybdenum complex (C1) are 0 based on the total amount of the lubricating oil composition. In Comparative Examples 5 to 8 which did not satisfy the regulation of .025% by mass, the friction coefficient was high and the effect of reducing the friction coefficient was inferior. Further, Comparative Examples 9 to 10 containing a dinuclear MoDTC (C2-1) instead of the oxymolybdenum complex (C1) of the basic nitrogen compound, and Comparative Example 11 containing a trinuclear MoDTC (C2-3) , The result of the hot tube test was bad, and the high temperature cleanliness was inferior.
As the calcium-based cleaning agent (D), 0.050 is a calcium-based cleaning agent (D2) that does not contain a calcium-based cleaning agent (D1) having a base value of 200 mgKOH / g or more and has a base value of less than 200 mgKOH / g. In Comparative Example 12 containing% by mass, the result of the hot tube test was poor, and the high temperature cleanliness was inferior.
In Comparative Examples 13 to 14 in which the phosphorus atom content was less than 0.020% by mass based on the total amount of the lubricating oil composition, LSPI was generated, resulting in inferior LSPI suppression property.

Claims

The base oil (A) is selected from the aromatic carboxylic acid ester derivative (B1) represented by the following general formula (I) and the aromatic carboxylic acid ester derivative (B2) represented by the following general formula (II). A calcium-based cleaning agent containing one or more aromatic carboxylic acid ester derivatives (B), an oxymolybdenum complex (C1) of a basic nitrogen compound, and a calcium-based cleaning agent (D1) having a base value of 200 mgKOH / g or more. A lubricating oil composition containing (D) and

[In the general formula (I), x and y are integers satisfying 1 ≦ x ≦ 3 and 1 ≦ y ≦ 3, respectively. R 1 and R 2 each independently represent an alkyl group having 9 to 20 carbon atoms. When x ≧ 2, the plurality of R 1s may be the same or different. When y ≧ 2, the plurality of R 2s may be the same or different. ]

[In the general formula (II), m, n, о, and p are 1 ≦ m ≦ 2, 0 ≦ n ≦ 2, 2 ≦ (m + n) ≦ 4, 1 ≦ о ≦ 3, 1 ≦ p ≦, respectively. It is an integer that satisfies 3. R 3 and R 4 each independently represent an alkyl group having 9 to 20 carbon atoms. If it is o ≧ 2, a plurality of R 3 may be be the same or different. When p ≧ 2, the plurality of R 4s may be the same or different. ]
The content of the aromatic carboxylic acid ester derivative (B) is 1.5% by mass or more based on the total amount of the lubricating oil composition.
The content of molybdenum atoms derived from the oxymolybdenum complex (C1) of the basic nitrogen compound is 0.025% by mass or more based on the total amount of the lubricating oil composition.
The content of calcium atoms derived from the calcium-based cleaning agent (D) is 0.020% by mass or more and less than 0.080% by mass based on the total amount of the lubricating oil composition.
Sulfate ash content is 0.3% by mass or less,
A lubricating oil composition having a phosphorus atom content of 0.020% by mass or more and 0.040% by mass or less based on the total amount of the lubricating oil composition.
The lubrication according to claim 1, wherein the content of calcium atoms derived from the calcium-based cleaning agent (D1) is 0.020% by mass or more and less than 0.080% by mass based on the total amount of the lubricating oil composition. Oil composition.
Claim 1 or 2 in which the content of calcium atoms derived from the calcium-based cleaning agent (D2) having a base value of less than 200 mgKOH / g is less than 0.025% by mass based on the total amount of the lubricating oil composition. The lubricating oil composition according to.
The content ratio of the calcium-based detergent (D2) derived from calcium atoms (Ca D2) and wherein the calcium detergent (D1) derived from calcium atoms (Ca D1) [Ca D2 / Ca D1] is the mass ratio , The lubricating oil composition according to claim 3, which is less than 0.31.
The method according to any one of claims 1 to 4, wherein the content of Mo atoms derived from molybdenum dithiocarbamate (MoDTC) (C2) is less than 0.020% by mass based on the total amount of the lubricating oil composition. Lubricating oil composition.
Content ratio of Mo atom (Mo C2 ) derived from the molybdenum dithiocarbamate (MoDTC) (C2) to molybdenum atom (Mo C1 ) derived from the oxymolybdenum complex (C1) of the basic nitrogen compound [Mo C2 / The lubricating oil composition according to claim 5, wherein Mo C1 ] is less than 1.0 in terms of mass ratio.
The lubricating oil composition according to any one of claims 1 to 6, further comprising zinc dithiophosphate (ZnDTP) (E).
The lubricating oil composition according to any one of claims 1 to 7, which is used for an internal combustion engine.
The lubricating oil composition according to any one of claims 1 to 7, which is used for an internal combustion engine including a gasoline particulate filter (GPF).
The lubricating oil composition according to claim 9, which is used for a direct-injection internal combustion engine equipped with a supercharger.