JP2018168344A - Lubricating oil composition for internal combustion engines - Google Patents

Abstract

To provide a lubricating oil composition for an internal combustion engine excellent in water resistance and durability upon moisture mixing.SOLUTION: Provided is a lubricating oil composition for an internal combustion engine comprising: a base oil; an overbasic calcium sulfonate (A); and an overbasic magnesium cleaning agent (B), in which the content of chlorine atoms in the component (B) is 400 mass ppm or lower based on the total quantity of the component (B).SELECTED DRAWING: None

Description

  The present invention relates to a lubricating oil composition for an internal combustion engine.

In recent years, environmental regulations on a global scale have become more and more stringent, and in particular, the situation surrounding automobiles is becoming stricter, such as fuel efficiency regulations and exhaust gas regulations. This is due to environmental issues such as global warming and resource protection from concerns over the depletion of petroleum resources. From such a recent situation, the production ratio of hybrid vehicles has been improved in order to reduce the air pollution caused by the exhaust gas of the vehicles.
Similarly, development of internal combustion engines using fuels derived from biomass, for example, alcohol fuels such as biomass methanol and biomass ethanol, has been promoted from the viewpoint of resource protection from concerns about the depletion of petroleum resources.
By the way, the same engine oil as the lubricating oil for an internal combustion engine of an automobile driven only by the conventional internal combustion engine is used as the lubricating oil of the internal combustion engine of the hybrid automobile or the above-described alcohol fuel using the alcohol fuel. Development of a lubricating oil for an internal combustion engine adapted to the use environment of the internal combustion engine of the above or an internal combustion engine using the aforementioned alcohol fuel is underway.
For example, Patent Document 1 includes that a specific lubricant base oil contains a metal detergent, a boron-containing succinimide-based ashless dispersant, and a metal salt of a phosphorus-containing acid, each with a specific content. A characteristic lubricating oil composition for internal combustion engines is disclosed.
Patent Document 2 discloses that a lubricant base oil has a specific content, a salicylate-based detergent, a succinimide-based ashless dispersant containing no boron, and a phosphorus-containing composition. A lubricating oil composition for an internal combustion engine of a hybrid vehicle characterized by containing a metal salt of an organic acid, and the lubricating oil composition for an internal combustion engine, further containing a boron-containing succinimide-based ashless component with a specific content A lubricating oil composition for an internal combustion engine of a hybrid vehicle characterized by containing a powder is disclosed.

JP 2008-144018 A JP 2008-144019 A

Incidentally, a hybrid vehicle has two power sources, an internal combustion engine (for example, an engine) and an electric motor (for example, an electric motor). And depending on the situation at the time of traveling, the vehicle is traveling using only the internal combustion engine, only the electric motor, or these simultaneously. In a conventional vehicle having only an internal combustion engine, it is necessary to always use the power of the internal combustion engine during driving. However, in a hybrid vehicle, it can be driven using electric power obtained by an electric motor without using the power of the internal combustion engine. As described above, the internal combustion engine of the hybrid vehicle has a longer stop time even when the vehicle is being used than the internal combustion engine of the conventional vehicle. Therefore, dew condensation occurs in the crank chamber, and moisture tends to be mixed into the lubricating oil for the internal combustion engine. As a result, when the lubricating oil for an internal combustion engine is used in an internal combustion engine of a hybrid vehicle, the lubricating oil is likely to deteriorate early compared to the case where it is used in a vehicle having only a conventional internal combustion engine. Yes.
Similarly, an internal combustion engine that uses an alcohol fuel such as ethanol or a biofuel such as bioethanol has a similar problem because water is easily generated or mixed in the fuel.
As described above, in hybrid vehicles, vehicles using alcohol fuel or biofuel, etc., there is a demand for internal combustion engine lubricating oil with high water resistance that is easily mixed with moisture in the internal combustion engine lubricating oil.
In addition, since the lubricating oil for internal combustion engines is required to have durability, when used in the environment described above, it is necessary to maintain a cleaning action for a long time in a state where moisture is mixed. Is also sought.

  This invention is made | formed in view of the above problem, and the subject of this invention is providing the lubricating oil composition for internal combustion engines which is excellent in water resistance and the durability at the time of moisture mixing.

As a result of intensive studies, the present inventors have found that a lubricating oil composition for an internal combustion engine containing a specific calcium-based detergent and a specific magnesium-based detergent can solve the above problems. Each embodiment of the present invention has been completed based on such knowledge. That is, according to each embodiment of the present invention, the following [1] to [4] are provided.
[1] a base oil;
An overbased calcium sulfonate (A);
Containing an overbased magnesium detergent (B),
A lubricating oil composition for internal combustion engines, wherein the chlorine atom content of component (B) is 400 ppm by mass or less based on the total amount of component (B).
[2] base oil;
An overbased calcium sulfonate (A);
A method for producing a lubricating oil composition for an internal combustion engine, comprising blending an overbased magnesium detergent (B),
The manufacturing method of the lubricating oil composition for internal combustion engines whose chlorine atom content of a component (B) is 400 mass ppm or less on the basis of the total amount of the component (B).
[3] A lubricating method using the lubricating oil composition for an internal combustion engine according to [1].
[4] A lubricating method comprising using a lubricating oil composition for an internal combustion engine obtained by the production method according to [2].
[5] An internal combustion engine using the lubricating oil composition for an internal combustion engine according to [1].
[6] An internal combustion engine using the lubricating oil composition for an internal combustion engine obtained by the production method according to [2].

  ADVANTAGE OF THE INVENTION According to this invention, the lubricating oil composition for internal combustion engines which is excellent in water resistance and the durability at the time of moisture mixing can be provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Lubricating oil composition for internal combustion engine]
An internal combustion engine lubricating oil composition (hereinafter also simply referred to as “lubricating oil composition”) according to an embodiment of the present invention includes a base oil, an overbased calcium sulfonate (A), and an overbased magnesium detergent. It is a lubricating oil composition for internal combustion engines which contains an agent (B) and whose chlorine atom content of a component (B) is 400 mass ppm or less on the basis of the total amount of the component (B).
When the chlorine atom content of the component (B) is more than 400 mass ppm based on the total amount of the component (B), the ionization tendency is increased, and the water resistance of the lubricating oil composition and the durability when mixed with water are lowered. On the other hand, the lubricating oil composition has a low ionization tendency because the chlorine atom content of the component (B) is as low as 400 mass ppm or less based on the total amount of the component (B). Durability is improved.
In addition, when containing 2 or more types of components (B), the chlorine atom content of the said component (B) represents the total amount of the chlorine atom content of those components.
Hereinafter, each component contained in the lubricating oil composition will be described.

<Base oil>
There is no restriction | limiting in particular as base oil used for the said lubricating oil composition, Arbitrary things can be suitably selected and used from the mineral oil and synthetic oil which were conventionally used as a base oil of lubricating oil.
As mineral oil, for example, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, hydrocracked, solvent dewaxed, catalytic dehydrated. Mineral oil produced by isomerizing mineral oil, wax, or GTL WAX (gas-tuly wax) refined by one or more treatments such as wax, hydrorefining, etc. A mineral oil treated by hydrorefining or a mineral oil produced by isomerizing GTL WAX is preferred. These mineral oils tend to improve the% C _P and viscosity index described later.
Synthetic oils include, for example, polybutenes; poly-α-olefins such as α-olefin homopolymers and α-olefin copolymers (for example, ethylene-α-olefin copolymers); polyol esters, dibasic acid esters, phosphorus Examples include various esters such as acid esters; various ethers such as polyphenyl ether; polyglycol; alkylbenzene; alkylnaphthalene; Of these synthetic oils, poly α-olefins and esters are preferred, and those combining these two are also suitably used as synthetic oils.
In one Embodiment of this invention, the said mineral oil may be used independently as said base oil, and may be used in combination of 2 or more type. Moreover, the said synthetic oil may be used independently and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
Further, the content of the base oil is preferably 65% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 97% by mass or less, based on the total amount of the lubricating oil composition. More preferably, it is 95 mass% or less.

The viscosity of the base oil is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 2 mm ² / s or more, more preferably 3 mm ² / s or more, and further preferably 4 mm ² / s or more. Preferably it is 30 mm < ² > / s or less, More preferably, it is 15 mm < ² > / s or less, More preferably, it is 10 mm < ² > / s or less. When the kinematic viscosity at 100 ° C. is 2 mm ² / s or more, the evaporation loss is small, and when it is 30 mm ² / s or less, the power loss due to the viscous resistance is suppressed, and the fuel efficiency improvement effect is obtained.
Although not particularly limited, kinematic viscosity at 40 ° C., is preferably ^{5 mm} 2 / s or more, more preferably ^{8 mm} 2 / s or more, more preferably 10 mm ² / s or more, and preferably 65 mm ² / It is s or less, More preferably, it is 40 mm < ² > / s or less, More preferably, it is 25 mm < ² > / s or less.
Moreover, the viscosity index of the base oil is preferably 100 or more, more preferably 110 or more, still more preferably 120 or more, and still more preferably 125 or more. A base oil having a viscosity index of 100 or more has a small change in viscosity due to a change in temperature.
When the viscosity index of the base oil is within this range, it becomes easy to improve the viscosity characteristics of the lubricating oil composition.
The kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the viscosity index are measured by the methods described in Examples described later.

Further, as the base oil, aromatic content by ring analysis (% C _A) content of sulfur content is not more than 10 ppm by weight is preferably used in 3.0. Here, the% C _A by ring analysis shows a proportion of aromatic content calculated by ring analysis n-d-M method (percentage).
_A base oil having a% CA of 3.0 or less and a sulfur content of 10 mass ppm or less provides a lubricating oil composition having good oxidation stability and capable of suppressing an increase in acid value and sludge formation. can do. More preferably% _{C A} is 1.0 or less, further preferably 0.5 or less, also, sulfur content is more preferably at most 5 mass ppm.
Further, the base oil preferably has a paraffin content (% C _P ) by ring analysis of 70 or more, more preferably 75 or more, and still more preferably 79 or more. By setting the% _CP to 75 or more, the oxidation stability of the base oil is improved. Here, the% C _P by ring analysis shows a proportion of paraffin component calculated in ring analysis n-d-M method (percentage).
Further, the NOACK evaporation amount of the base oil is preferably 15.0% by mass or less, and more preferably 14.0% by mass or less.
The aromatic content (% C _A ), paraffin content (% C _P ), sulfur content (sulfur atom content) and NOACK evaporation by the ring analysis are each measured by the method described in the examples described later. Value.

<Component (A): Overbased calcium sulfonate>
The lubricating oil composition contains an overbased calcium sulfonate (hereinafter also simply referred to as “component (A)”) as component (A). By containing a component (A), the fall of the base number at the time of NOx gas mixing can be suppressed.

  As the component (A), for example, an alkyl aromatic sulfonic acid such as an alkyl benzene sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of preferably 300 to 1,500, more preferably 400 to 700 is preferable. Calcium salt (neutral calcium sulfonate) obtained by directly reacting with a base such as calcium oxide or hydroxide, or once substituted with calcium after being converted to an alkali metal salt such as sodium salt or potassium salt. ), And those obtained by reacting the neutral calcium sulfonate with excess calcium oxide and / or calcium hydroxide in the presence of carbon dioxide gas, boric acid or borate.

When the soap group constituting the component (A) has an alkyl group, the alkyl group preferably has 4 to 30 carbon atoms, more preferably a linear or branched alkyl group having 6 to 24 carbon atoms. And more preferably a linear or branched alkyl group having 10 to 24 carbon atoms.
Since the component (A) has a plurality of alkyl groups in the same molecule, some of the components (A) have an alkyl group having the same carbon number, and some have an alkyl group having a different carbon number. In addition, as the component (A), those described above may be used alone or in combination of two or more. Even when two or more types are used in combination as component (A), or when they are used alone, when they have a plurality of alkyl groups in the same molecule, they constitute component (A) that occupies the largest number among them. The number of carbon atoms of the alkyl group (hereinafter, also referred to as “the main carbon number of the alkyl group of component (A)”) is preferably 10 or more and 24 or less. Good oil solubility is obtained because the main carbon number of the alkyl group which a component (A) has is the said range.
As used herein, the term “oil-soluble” does not necessarily indicate that the compound or additive is completely soluble in the oil, but it dissolves and disperses in the oil during use, transportation, and storage. It means to do.

The base number (hydrochloric acid method) of component (A) is preferably 200 mgKOH / g or more, more preferably 250 mgKOH / g or more, still more preferably 300 mgKOH / g or more, and preferably 500 mgKOH / g or less, more preferably It is 450 mgKOH / g or less, More preferably, it is 400 mgKOH / g or less. When the base number (hydrochloric acid method) of component (A) is 200 mgKOH / g or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the solubility to the lubricating oil composition of a component (A) becomes favorable as it is 500 mgKOH / g or less.
The value of the base number is a value measured by the method described in Examples described later.

The content of the component (A) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.50% by mass or more, based on the total amount of the lubricating oil composition. Preferably it is 3.0 mass% or less, More preferably, it is 2.5 mass% or less, More preferably, it is 2.0 mass% or less. When the content of the component (A) is 0.05% by mass or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the ash content of a lubricating oil composition can be made low as content of the said component (A) is 3.0 mass% or less.
In the present specification, “ash” means “sulfur ash” measured by the method described in JIS K 2272: 1998, for example.
The calcium atom content derived from the component (A) is preferably 500 ppm by mass or more, more preferably 800 ppm by mass or more, still more preferably 1,000 ppm by mass or more, based on the total amount of the lubricating oil composition. Further, it is preferably 2,000 mass ppm or less, more preferably 1,800 mass ppm or less, and still more preferably 1,600 mass ppm or less. When the content is 500 mass ppm or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the ash content of a lubricating oil composition can be made low as the said content is 2,000 mass ppm or less.
In addition, as a component (A), an above described thing may be used independently, and the above-mentioned thing from which the property or structure differs may be used in combination of 2 or more types. The preferred range of the carbon number of the alkyl group of the soap group, the base number (hydrochloric acid method), the content of the component (A) in the lubricating oil composition and the calcium content derived from the component (A) is two or more components. The same applies to the total value when (A) is combined.

<Component (B): Overbased magnesium detergent>
The lubricating oil composition is an overbased magnesium detergent having a chlorine atom content of 400 mass ppm or less based on the total amount of the overbased magnesium detergent (hereinafter simply referred to as “ Component (B) ").
As described above, when the chlorine atom content of component (B) is more than 400 ppm by mass based on the total amount of component (B), the ionization tendency increases, and the water resistance of the lubricating oil composition and the durability when mixed with moisture are increased. descend. On the other hand, in the lubricating oil composition, the chlorine atom content of the component (B) is as low as 400 mass ppm or less on the basis of the total amount of the component (B), so that the ionization tendency is low, and the durability when mixed with moisture is low. improves.
From such a viewpoint, the chlorine atom content in the component (B) is preferably 350 ppm by mass or less, more preferably 300 ppm by mass or less, still more preferably 150 ppm by mass or less, based on the total amount of the component (B). More preferably, it is 100 mass ppm or less.
The lower limit of the chlorine atom content in the component (B) is not particularly limited, but is 0 mass ppm or more, preferably 50 mass ppm or more, more preferably 60 mass, based on the total amount of the component (B). ppm or more, more preferably 70 mass ppm or more.
In addition, when containing 2 or more types of components (B), the chlorine atom content of the said component (B) represents the total amount of chlorine atom content in 2 or more types of components (B).

Here, the “chlorine atom in component (B)” refers to a chlorine atom derived from a soap group in component (B).
Examples of the soap group constituting the component (B) include derivatives of alkylbenzene such as alkyl aromatic sulfonic acid (eg, alkylbenzene sulfonic acid), alkylphenol, alkyl salicylic acid and the like.
Alkylbenzene is mainly obtained by reacting chlorinated paraffin obtained by chlorinating n-paraffin refined or synthesized from crude oil with benzene using aluminum chloride (AlCl ₃ ) as a catalyst. Thereafter, alkylbenzenesulfonic acid can be obtained by sulfonating alkylbenzene.
The alkyl salicylic acid can be obtained, for example, by reacting a metal salt of an alkyl salicylic acid obtained from an alkylphenol and a metal hydroxide with hydrochloric acid.
These alkylbenzenes and derivatives thereof are appropriately purified to remove chlorine atoms, but the content of chlorine atoms varies depending on the degree of purification.
Also, for example, even when synthesizing alkylphenol from phenol, various methods such as a method of obtaining benzenesulfonic acid or chlorobenzene by alkali melting, a method of passing through a diazonium salt, a cumene method of oxidizing and decomposing cumene with oxygen, etc. The method can be selected, and the chlorine atom content in the component (B) varies depending on the process of obtaining the alkylphenol.
Therefore, since a chlorine atom is mixed in the alkylbenzene and its derivative as a raw material of the component (B), a small amount of chlorine atom is also contained in the component (B).
Therefore, the chlorine atom content in the component (B) is affected by, for example, the difference in the chlorine atom content in the alkylbenzene and its derivatives.
Also, for example, if the component (B) is an overbased magnesium sulfonate, it is removed when the alkylbenzene is sulfonated to obtain an alkyl aromatic sulfonic acid, or when the magnesium salt is formed. The chlorine atom content in component (B) also varies depending on the amount of chlorine atoms.
As described above, the chlorine atom content in the component (B) can be adjusted by selecting the chlorine atom content in the raw material used, the synthesis method of the raw material, and the synthesis method of the component (B). A component (B) having a chlorine atom content of 400 mass ppm or less based on the total amount of the detergent can be obtained.

As the component (B), as long as the chlorine atom content is satisfied, an overbased magnesium detergent used in a lubricating oil can be used, and preferably an overbased magnesium sulfonate, an overbased magnesium phenate, and an overbased magnesium detergent. One or more types of overbased magnesium detergents selected from the group consisting of basic magnesium salicylates can be mentioned, more preferably one or more types selected from the group consisting of overbased magnesium sulfonates and overbased magnesium salicylates, and more preferably Is an overbased magnesium salicylate.
By containing the said component (B) with the said component (A), the lubricating oil composition which makes low ash content and outstanding water resistance compatible can be obtained.

Examples of the alkyl group that the soap group such as a sulfonic acid group, a phenol group, and a salicylic acid group constituting the component (B) have include a linear alkyl group or a branched alkyl group, and a linear alkyl group having 4 to 30 carbon atoms. Group or a branched alkyl group is preferable, more preferably a linear alkyl group or a branched alkyl group having 6 to 24 carbon atoms, and still more preferably a linear alkyl group or a branched alkyl group having 10 to 24 carbon atoms. It is.
These alkyl groups may be primary alkyl groups, secondary alkyl groups, or tertiary alkyl groups.
Since the component (B) has a plurality of alkyl groups in the same molecule, some of the components (B) have alkyl groups having the same carbon number, and others have alkyl groups having different carbon numbers. And as for a component (B), the above-mentioned thing may be used independently and may be used in combination of 2 or more types, but it is the same even if it uses it in combination of 2 or more types, or it is a case where it uses independently. In the case of having a plurality of alkyl groups in the molecule, the carbon number of the alkyl group constituting the component (B) occupying the largest number among them (hereinafter also referred to as “the main carbon number of the alkyl group that the component (B) has”). Is preferably 10 or more and 24 or less. Good oil solubility is obtained because the main carbon number of the alkyl group which a component (B) has is the said range.

  As the overbased magnesium sulfonate, for example, an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound preferably having a molecular weight of 300 to 1,500, more preferably 400 to 700, Using magnesium salt (neutral magnesium sulfonate) obtained by reacting with a base such as magnesium oxide or hydroxide, or once replacing alkali metal salt such as sodium salt or potassium salt with magnesium Obtained by reacting the neutral magnesium sulfonate with excess magnesium oxide and / or magnesium hydroxide in the presence of carbon dioxide gas or boric acid or borate, or in a solvent such as a hydrocarbon solvent or alcohol To magnesium oxide, water A magnesium source such as magnesium chloride or magnesium alkoxide is mixed, and the alkyl aromatic sulfonic acid is mixed therewith, and further, the carbonation of organic monocarboxylic acid, hydrocarbon-substituted succinic anhydride or derivative thereof is promoted. And the like obtained by further introducing carbon dioxide into the mixture in which the accelerator is mixed.

  Examples of the overbased magnesium phenate include, for example, alkylphenol, alkylphenol sulfide, a Mannich reaction product of alkylphenol, directly reacted with a base such as an oxide or hydroxide of magnesium, or once a sodium salt or potassium salt. Using magnesium salt (neutral magnesium phenate) obtained by substituting magnesium with the alkali metal salt of sodium, excessive oxidation of the neutral magnesium phenate in the presence of carbon dioxide, boric acid or borate A magnesium source such as magnesium oxide, magnesium hydroxide, magnesium alkoxide or the like obtained by reacting with magnesium and / or magnesium hydroxide, or a solvent such as a hydrocarbon solvent or alcohol is mixed therewith. For a mixture in which an alkylphenol, an alkylphenol sulfide, or a Mannich reaction product of an alkylphenol is mixed and an accelerator for promoting carbonation such as an organic monocarboxylic acid, a hydrocarbon-substituted succinic anhydride, or a derivative thereof is further mixed. Further, those obtained by further introducing carbon dioxide can be mentioned.

  As the overbased magnesium salicylate, for example, alkyl salicylic acid such as dialkyl salicylic acid is directly reacted with a base such as magnesium oxide or hydroxide, or once as an alkali metal salt such as sodium salt or potassium salt. A magnesium salt of salicylic acid (neutral magnesium salicylate) obtained by substituting magnesium with magnesium, and the neutral magnesium salicylate in excess of magnesium oxide and / or water in the presence of carbon dioxide gas or boric acid or borate. A magnesium source such as magnesium oxide, magnesium hydroxide or magnesium alkoxide is mixed in a solvent obtained by reacting with magnesium oxide or a solvent such as a hydrocarbon solvent or alcohol, and the alkylsalicylic acid is mixed therewith. Further, a mixture obtained by further introducing carbon dioxide into a mixture in which an accelerator for promoting carbonation such as an organic monocarboxylic acid, a hydrocarbon-substituted succinic anhydride, or a derivative thereof is mixed can be obtained. Can be mentioned.

The base number (hydrochloric acid method) of component (B) is preferably 200 mgKOH / g or more, more preferably 250 mgKOH / g or more, still more preferably 300 mgKOH / g or more, preferably 500 mgKOH / g or less, more preferably It is 450 mgKOH / g or less, More preferably, it is 380 mgKOH / g or less, More preferably, it is 360 mgKOH / g or less. When the base number (hydrochloric acid method) of component (B) is 200 mgKOH / g or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the solubility to the lubricating oil composition of component (B) and durability of a lubricating oil composition become it favorable that it is 500 mgKOH / g or less.
The value of the base number is a value measured by the method described in Examples described later.

The content of the component (B) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and further preferably 0.30% by mass or more, based on the total amount of the lubricating oil composition. Preferably, it is 3.0 mass% or less, More preferably, it is 2.0 mass% or less, More preferably, it is 1.0 mass% or less. When the content is 0.05% by mass or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the ash content of a lubricating oil composition can be reduced as it is 3.0 mass% or less.
The chlorine atom content derived from the component (B) is preferably 2.00 ppm by mass or less, more preferably 1.50 ppm by mass or less, still more preferably 1.40 ppm by mass, based on the total amount of the lubricating oil composition. Hereinafter, it is more preferably 1.00 mass ppm or less. When the content is 2.00 mass ppm or less, the water resistance of the lubricating oil composition and the durability when mixed with moisture are improved.
Moreover, there is no restriction | limiting in particular as a lower limit of chlorine atom content derived from the said component (B), For example, it is preferable not to contain a chlorine atom, and when containing a chlorine atom, the said lubricating oil composition whole quantity reference | standard Preferably, it is 0.1 mass ppm or more.

The magnesium atom content derived from the component (B) is preferably 300 ppm by mass or more, more preferably 350 ppm by mass or more, still more preferably 400 ppm by mass or more, based on the total amount of the lubricating oil composition. Preferably it is 1,000 mass ppm or less, More preferably, it is 800 mass ppm or less, More preferably, it is 700 mass ppm or less, More preferably, it is 600 mass ppm or less. When the content is 300 mass ppm or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the ash content of a lubricating oil composition can be reduced as the said content is 1,000 mass ppm or less.
In addition, as a component (B), an above-described thing may be used independently and you may use in combination of 2 or more types mentioned above in which the property or structure differs. The chlorine atom content in the component (B) described above, the carbon number of the alkyl group of the soap group, the base number (hydrochloric acid method), the content of the component (B) in the lubricating oil composition, derived from the component (B) The preferable range of the chlorine atom content and the magnesium content derived from the component (B) is the same as the total value when two or more components (B) are combined.

<Component (C): Organic molybdenum compound>
The lubricating oil composition preferably further contains an organic molybdenum compound (hereinafter also simply referred to as “component (C)”) as component (C).
By containing the component (C), the friction reducing action of the lubricating oil composition is further improved.
The content of the component (C) can be converted as the molybdenum atom content (Mo) derived from the component (C), and the content of the component (C) in terms of molybdenum atoms is preferably based on the total amount of the lubricating oil composition. Is 30 mass ppm or more, more preferably 40 mass ppm or more, still more preferably 50 mass ppm or more, preferably 400 mass ppm or less, more preferably 300 mass ppm or less, still more preferably 200 mass ppm or less, More preferably, it is 150 mass ppm or less. When the content is 30 mass ppm or more, the friction reducing action of the lubricating oil composition is further improved. Moreover, the cleanliness of a lubricating oil composition will become favorable as the said content is 400 mass ppm or less.

  As the content of component (C), the content in terms of molybdenum atoms is preferably within the above range, but the content of component (C) is preferably based on the total amount of the lubricating oil composition. Is 0.05% by mass or more, more preferably 0.08% by mass or more, further preferably 0.10% by mass or more, preferably 1.50% by mass or less, more preferably 0.80% by mass or less. More preferably, it is 0.20 mass% or less. When the content of the component (C) is 0.05% by mass or more, the friction reducing action of the lubricating oil composition is further improved. Moreover, precipitation of molybdenum to a lubricating oil composition can be suppressed as content of a component (C) is 1.50 mass% or less.

Examples of the component (C) include organic molybdenum compounds such as molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and amine molybdate.
Among these, the component (C) preferably contains at least one selected from the group consisting of molybdenum dithiocarbamate (MoDTC) (C1) and molybdenum dithiophosphate (MoDTP) (C2) shown below, and more Preferably, molybdenum dithiocarbamate (MoDTC) (C1) is contained.

As molybdenum dithiocarbamate (C1), dinuclear molybdenum dithiocarbamate (C11) containing two molybdenum atoms in one molecule, and trinuclear molybdenum dithiocarbamate (C12) containing three molybdenum atoms in one molecule. Is mentioned.
Molybdenum dithiocarbamate (C1) may be used alone or in combination of two or more.

  The dinuclear molybdenum dithiocarbamate (C11) is preferably one or more selected from the group consisting of a compound represented by the following general formula (c11-1) and a compound represented by the general formula (c11-2) It is.

In general formulas (c11-1) and (c11-2), R ^{11 to} R ¹⁴ each independently represent a hydrocarbon group, and may be the same as or different from each other.
X ^{11 to} X ¹⁸ each 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 general formula (c11-1) are sulfur atoms.
When using the general formula (c11-2) as the component (C) is preferably ^X 11 ^{to X 14} in the general formula (c11-2) is an oxygen atom.

In the general formula (c11-1), from the viewpoint of improving the solubility in the base oil, the molar ratio [sulfur atom / oxygen atom] between the sulfur atom and the oxygen atom in X ^{11 to} X ¹⁸ is preferably 1/4. It is 4/1 or less, more preferably 1/3 or more and 3/1 or less.
In the general formula (c11-2), from the same viewpoint as described above, the molar ratio [sulfur atom / oxygen atom] between the sulfur atom and the oxygen atom in X ^{11 to} X ¹⁴ is preferably 1/3 or more and 3 / 1 or less, more preferably 1.5 / 2.5 or more and 2.5 / 1.5 or less.
The carbon number of the hydrocarbon group that can be selected as R ^{11 to} R ¹⁴ is preferably 7 or more and 22 or less, more preferably 7 or more and 18 or less, still more preferably 7 or more and 14 or less, and still more preferably 8 or more and 13 or less. .

Examples of the hydrocarbon group that can be selected as R ^{11 to} R ¹⁴ in the general formulas (c11-1) and (c11-2) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Alkyl groups such as heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl; octenyl, nonenyl, decenyl, undecenyl Group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group and the like; cyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, methylcyclohexylmethyl group, cyclohexylethyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclyl Cycloalkyl group such as hexyl group; aryl group such as phenyl group, naphthyl group, anthracenyl group, biphenyl group, terphenyl group; tolyl group, dimethylphenyl group, butylphenyl group, nonylphenyl group, methylbenzyl group, dimethylnaphthyl group Alkylaryl groups such as phenylmethyl group, phenylethyl group, diphenylmethyl group and the like.

  The trinuclear molybdenum dithiocarbamate (C12) is preferably a compound represented by the following general formula (c12-1).

In general formula (c12-1), k is an integer of 1 or more, m is an integer of 0 or more, k + m is an integer of 4 or more and 10 or less, and is preferably an integer of 4 or more and 7 or less. n is an integer of 1 to 4, and p is an integer of 0 or more. z is an integer of 0 to 5, and includes a non-stoichiometric value.
Mo is a molybdenum atom and S is a sulfur atom.
Each E is independently an oxygen atom or a selenium atom, and for example, can replace sulfur in the core described later.
L is each independently an anionic ligand having an organic group containing a carbon atom, 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. And may be different.
U is an anion other than L each independently.
Q is a compound that donates a neutral electron independently, and is present to satisfy an empty coordination on the trinuclear molybdenum compound.

The total number of carbon atoms of the organic group in the anionic ligand represented by L is preferably 14 or more and 50 or less, more preferably 16 or more and 30 or less, and further preferably 18 or more and 24 or less. .
L is preferably a monoanionic ligand which is a monovalent anionic ligand, and more specifically, a ligand represented by the following general formulas (i) to (iv) is more preferable.
In the general formula (c12-1), the anionic ligand selected as L is more preferably a ligand represented by the following general formula (iv).
In the general formula (c12-1), all anionic ligands selected as L are preferably the same, and more preferably all ligands represented by the following general formula (iv).

In the general formulas (i) to (iv), X ^{31 to} X ³⁷ and Y are each independently an oxygen atom or a sulfur atom, and may be the same or different.
In the general formulas (i) to (iv), R ^{31 to} R ³⁵ are each independently an organic group, and may be the same as or different from each other.

The number of carbon atoms of each organic group that can be selected as R ³¹ , R ³² , and R ³³ is preferably 14 or more and 50 or less, more preferably 16 or more and 30 or less, and still more preferably 18 or more and 24. Or less.
The total carbon number of the two organic groups that can be selected as R ³⁴ and R ³⁵ in the general formula (iv) is preferably 14 or more and 50 or less, more preferably 16 or more and 30 or less, and still more preferably 18 The number is 24 or more.
The number of carbon atoms of each organic group that can be selected as R ³⁴ and R ³⁵ is preferably 7 or more and 30 or less, more preferably 7 or more and 20 or less, and still more preferably 8 or more and 13 or less.
Note that the organic group of R ^{34 and} the organic group of R ³⁵ may be the same or different from each other, but are preferably different from each other. Further, the carbon number of the organic group of R ³⁴ and the carbon number of the organic group of R ³⁵ may be the same or different from each other, but are preferably different from each other.

Examples of the organic group selected as R ^{31 to} R ³⁵ include hydrocarbyl groups such as alkyl groups, aryl groups, and substituted aryl groups, and alkoxy groups.
The hydrocarbyl group is a monovalent substituent formed by removing one hydrogen atom from a hydrocarbon. Examples of the substituent include the following.
1. Hydrocarbon Substituents As hydrocarbon substituents, aliphatic substituents such as alkyl groups and alkenyl groups; alicyclic substituents such as cycloalkyl groups and cycloalkenyl groups; aromatic hydrocarbon groups such as phenyl groups ( Aromatic groups); these groups substituted by aromatic groups, aliphatic groups, and alicyclic groups.
2. Substituted hydrocarbon substituent Examples of the substituted hydrocarbon substituent include the hydrocarbon substituents having a non-hydrocarbon group as a substituent. Examples of non-hydrocarbon groups include halogen groups such as chloro groups and fluoro groups, amino groups, alkoxy groups, mercapto groups, alkyl mercapto groups, nitro groups, nitroso groups, and sulfoxy groups.
Moreover, the hydrocarbyl group as an organic group selected as R ^{31 to} R ³⁵ may be independently bonded to at least one selected from other hydrocarbyl groups to form a ring.

In general formula (c12-1), the anionic ligand selected as L is preferably derived from alkylxanthate, carboxylate, dialkyldithiocarbamate, and mixtures thereof. The thing of origin is more preferable.
In general formula (c12-1), the anion that can be selected as U may be a monovalent anion or a divalent anion. Examples of the anion that can be selected as U include disulfide, hydroxide, alkoxide, amide, thiocyanate, and derivatives thereof.
In general formula (c12-1), examples of Q include water, amine, alcohol, ether, and phosphine. Q may be the same or different, but is preferably the same.

  As trinuclear molybdenum dithiocarbamate (C12), in general formula (c12-1), k is an integer of 4 to 7, n is 1 or 2, L is a monoanionic ligand, and p is an anion in U Preferred is an integer that imparts electrical neutrality to a charge-based compound, and each of m and z is 0, k is an integer of 4 to 7, and L is a monoanionic ligand More preferred is a compound wherein n is 4 and each of p, m and z is 0.

  The trinuclear molybdenum dithiocarbamate (C12) is preferably a compound having a core represented by the following formula (I) or (II), for example. Each core has a net electrical charge of +4. These cores are surrounded by anionic ligands and anions other than the anionic ligands present as needed.

Formation of the trinuclear molybdenum-sulfur compound requires selection of an appropriate anionic ligand (L) and other anions (U), for example, depending on the number of sulfur and E atoms present in the core. That is, the total anionic charge constituted by sulfur atoms, E atoms if present, L and U if present must be -4.
The trinuclear molybdenum-sulfur compound may also contain cations other than molybdenum, such as (alkyl) ammonium, amine or sodium, when the anionic charge exceeds -4. A preferred embodiment of the anionic ligand (L) and other anions (U) is a configuration having four monoanionic ligands.
Molybdenum-sulfur cores, such as the structures represented by Formulas (I) and (II) above, can be bonded to one or more polydentate ligands, ie, molybdenum atoms, to form oligomers. It can be interconnected by a ligand having more than one functional group.

As molybdenum dithiophosphate (C2), the compound represented by the following general formula (c2-1) and / or the compound represented by the following general formula (c2-2) is preferable.
In the present invention, molybdenum dithiophosphate (C2) may be used alone or in combination of two or more.

In general formulas (c2-1) and (c2-2), R ^{21 to} R ²⁴ each independently represent a hydrocarbon group, and may be the same as or different from each other.
X ^{21 to} X ²⁸ each 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 ^{21 to} X ^{28 in} the general formula (c2-1) are sulfur atoms.
In the general formula (c2-1), from the viewpoint of improving the solubility in the base oil, the molar ratio [sulfur atom / oxygen atom] of the sulfur atom and the oxygen atom in X ^{21 to} X ²⁸ is preferably 1/4. It is 4/1 or less, more preferably 1/3 or more and 3/1 or less.
Further, in the general formula (c2-2), from the same viewpoint, the molar ratio [sulfur atom / oxygen atom] of the sulfur atom and the oxygen atom in X ^{21 to} X ²⁴ is preferably 1/3 or more and 3/1. The ratio is more preferably 1.5 / 2.5 or more and 2.5 / 1.5 or less.
The carbon number of the hydrocarbon group that can be selected as R ^{21 to} R ²⁴ is preferably 1 or more and 20 or less, more preferably 5 or more and 18 or less, still more preferably 5 or more and 16 or less, and still more preferably 5 or more and 12 or less. .
In addition, as a hydrocarbon group which can be selected as R < ²¹ > -R < ²⁴ > in general formula (c2-1) and (c2-2), R in the above-mentioned general formula (c11-1) or (c11-2) the same thing can be mentioned a hydrocarbon group which may be selected as ¹¹ to R ^14.

The lubricating oil composition may contain a molybdenum compound (C3) other than molybdenum dithiocarbamate (C1) and molybdenum dithiophosphate (C2) as long as the effects of the present invention are not impaired.
Examples of such other molybdenum compounds (C3) include molybdate acid amine salts, molybdenum trioxide and / or molybdenum amine complexes formed by reacting molybdic acid with amine compounds.

A component (C) may be used independently and may be used in combination of 2 or more type. In addition, as the component (C), one kind selected from the group consisting of each compound represented by each general formula may be used alone, or selected from the group consisting of each compound represented by each general formula. Two or more of them may be used in combination.
The preferred range of the total content when two or more components (C) are combined is the same as the preferred range when the component (C) is used alone.

<Other ingredients>
The lubricating oil composition for an internal combustion engine may further contain other components other than the components (A) to (C) as necessary, as long as the effects of the present invention are not impaired. Examples of other components include friction modifiers other than the component (C) that also functions as an antioxidant, such as a viscosity index improver, an antioxidant, and an organic zinc dithiophosphate, an ashless dispersant, and an ashless friction. Examples include regulators, extreme pressure agents, rust inhibitors, pour point depressants, metal deactivators, and antifoaming agents.

Examples of the viscosity index improver include, for example, non-dispersed polyalkyl (meth) acrylates, dispersed polyalkyl (meth) acrylates and other PMA-based; olefin-based copolymers (for example, ethylene-propylene copolymers), OCP type such as dispersion type olefin type copolymer; styrene type copolymer (for example, styrene-diene copolymer, styrene-isoprene copolymer, etc.) and the like.
In the present specification, “alkyl (meth) acrylate” is used to include both alkyl methacrylate and alkyl acrylate.
These viscosity index improvers preferably have a weight average molecular weight (Mw) of 5,000 or more and 1,500,000 or less, and preferably 20,000 or more, more preferably 100,000 or more in the case of a PMA system. Moreover, it is preferably 1,000,000 or less, more preferably 800,000 or less. In the case of the OCP system, it is preferably 10,000 or more, more preferably 20,000 or more, and preferably 800,000 or less, more preferably 500,000 or less.
In addition, the said weight average molecular weight (Mw) is measured by the method as described in the Example mentioned later.
The structure of the viscosity index improver may be a straight chain or a branched chain. In addition, a comb polymer having a structure having a number of trifurcated branch points with a high molecular weight side chain in the main chain, or a kind of branched polymer, and three or more chain polymers are bonded at one point. It may be a polymer having a specific structure such as a star polymer having a structure.

Further, as described above, the viscosity index improver contains a polymer having a structure having a number of trident branching points with linear side chains in the main chain (hereinafter referred to as “comb polymer”). Also good. As such a comb polymer, for example, a polymer having at least a structural unit derived from a macromonomer having a polymerizable functional group such as a methacryloyl group, an acryloyl group, an ethenyl group, a vinyl ether group, and an allyl group is preferably exemplified. Here, the structural unit corresponds to a “linear side chain”.
More specifically, various vinyl monomers such as alkyl (meth) acrylates, nitrogen atom-containing systems, halogen element-containing systems, hydroxyl group-containing systems, aliphatic hydrocarbon systems, alicyclic hydrocarbon systems, and aromatic hydrocarbon systems. Preferred is a copolymer having a side chain containing a structural unit derived from a macromonomer having the polymerizable functional group with respect to a main chain containing a structural unit derived from a monomer.

The number average molecular weight (Mn) of the macromonomer is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably. 10,000 or less.
Further, the weight average molecular weight (Mw) of the comb polymer is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 50,000 or more, from the viewpoint of improving fuel economy. Preferably it is 1,000,000 or less, More preferably, it is 800,000 or less, More preferably, it is 700,000 or less. The molecular weight distribution (Mw / Mn) is preferably 6 or less, more preferably 5.6 or less, and even more preferably 5 or less. The lower limit is not particularly limited, but is preferably 1.01 or more, more preferably 1 .05 or more, more preferably 1.10 or more, and still more preferably 1.50 or more.
In the case of containing the comb polymer, the content of the comb polymer is preferably 0.10% by mass or more, more preferably 0.50% by mass based on the total amount of the lubricating oil composition from the viewpoint of improving fuel economy. % Or more, more preferably 1.00% by mass or more, and preferably 20.00% by mass or less, more preferably 10.00% by mass or less, and further preferably 8.00% by mass or less. Here, the content of the comb polymer means the content of only the resin component composed of the comb polymer, and is, for example, a solid content content that does not include the mass of diluent oil or the like contained with the comb polymer. .

  The viscosity index improver is preferably a polyalkyl (meth) acrylate having an SSI of 30 or less. Here, SSI means a shear stability index and indicates the ability to resist degradation of the polymer (polyalkyl (meth) acrylate). The higher the SSI, the more unstable the polymer is to shear and the easier it is to degrade. The SSI indicates a decrease in viscosity due to shear derived from a polymer as a percentage, and is calculated by the following formula.

In the calculation formula, Kv ₀ is a value of 100 ° C. kinematic viscosity of a mixture obtained by adding polyalkyl (meth) acrylate to base oil. Kv ₁ is the value of the 100 ° C. kinematic viscosity after passing the mixture of the base oil plus polyalkyl (meth) acrylate through a 30 cycle high shear Bosch diesel injector according to the procedure of ASTM D6278. Kv _oil is the value of the 100 ° C. kinematic viscosity of the base oil. As the base oil, a Group II base oil having a kinematic viscosity of 100 ° C. of 5.35 mm ² / s and a viscosity index of 105 is used.
By using a polyalkyl (meth) acrylate having an SSI of 30 or less, the wear resistance of the lubricating oil composition can be further improved. The SSI is more preferably 1 or more and 25 or less. By making SSI 25 or less, the wear prevention property of the lubricating oil composition can be further enhanced.

The monomer constituting the polyalkyl (meth) acrylate is an alkyl (meth) acrylate, preferably a linear alkyl group having 1 to 18 carbon atoms or an alkyl (meth) acrylate having a branched alkyl group having 3 to 34 carbon atoms. It is.
The polystyrene-equivalent weight average molecular weight (Mw) of the polyalkyl (meth) acrylate is preferably 10,000 or more and 1,000,000 or less, more preferably 30,000 or more and 500,000 or less. By setting the weight average molecular weight of the polyalkyl (meth) acrylate within this range, the SSI value can be easily adjusted to 30 or less.
In addition, the said weight average molecular weight (Mw) is measured by the method as described in the Example mentioned later.

These viscosity index improvers may be used alone or in combination of two or more.
The content of the viscosity index improver is preferably 0.10% by mass or more, more preferably 1.00% by mass or more, and still more preferably 2.00% by mass or more, based on the total amount of the lubricating oil composition. And preferably it is 20.00 mass% or less, More preferably, it is 15.00 mass% or less, More preferably, it is 10.00 mass% or less. By setting the content in these ranges, the viscosity of the lubricating oil composition can be easily set to a desired value.
The viscosity index improver includes, for example, the above-mentioned polymer as a resin component. Normally, considering the handling property and the solubility in the base oil, the resin component containing the polymer is diluted with mineral oil or the like. Often commercially available in the form of a solution diluted with oil. The resin content concentration of the viscosity index improver is usually 10% by mass or more and 50% by mass or less based on the total amount of the viscosity index improver.
In this case, the content of the viscosity index improver is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, based on the total amount of the lubricating oil composition, as the content in terms of resin content. Preferably it is 0.20 mass% or more, Preferably it is 2.00 mass% or less, More preferably, it is 1.50 mass% or less, More preferably, it is 1.30 mass% or less.

Examples of the antioxidant include phenol-based antioxidants and amine-based antioxidants.
The phenolic antioxidant is not particularly limited, and examples thereof include 4,4′-methylenebis (2,6-di-tert-butylphenol) and 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-amyl-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, n-octyl Til-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2 ′ -Thio [diethyl-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy -, C7-C9 side chain alkyl ester.
In these, Preferably it is a bisphenol type | system | group or an ester group containing phenol type, More preferably, it is an ester group containing phenol type, More preferably, it is benzenepropanoic acid, 3,5-bis (1,1-dimethyl- ethyl). -4-Hydroxy-, C7-C9 side chain alkyl ester. Moreover, these may be used independently and may be used in combination of 2 or more type.
The content of the phenolic antioxidant is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, and further preferably 0.30% by mass or more, based on the total amount of the lubricating oil composition. And, it is preferably 3.00% by mass or less, more preferably 2.50% by mass or less, and still more preferably 2.00% by mass or less.

The amine-based antioxidant is not particularly limited, and examples thereof include diphenylamines such as diphenylamine, monoalkyldiphenylamine having an alkyl group having 3 to 20 carbon atoms, or dialkyldiphenylamine having an alkyl group having 3 to 20 carbon atoms. Naphthylamine-based compounds such as α-naphthylamine and alkyl-substituted phenyl-α-naphthylamine having 3 to 20 carbon atoms. Specifically, for example, monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamines such as dibutyldiphenylamine, dipentyldiphenylamine, dihexyldiphenylamine, diheptyldiphenylamine, dioctyldiphenylamine and dinonyldiphenylamine; tetrabutyldiphenylamine; Tetrahexyldiphenylamine; polyalkyldiphenylamines such as tetraoctyldiphenylamine and tetranonyldiphenylamine; and α-naphthylamine, phenyl-α-naphthylamine, and further butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α- Naphthylamine, heptylphenyl-α-naphth Triethanolamine, octylphenyl -α- naphthylamine, alkylated phenyl -α- naphthylamine, such as nonylphenyl -α- naphthylamine; and the like.
Of these, dialkyldiphenylamines or naphthylamines are preferable, dialkyldiphenylamines are more preferable, and 4,4′-dinonyldiphenylamine is more preferable. Moreover, these may be used independently and may be used in combination of 2 or more type.
The content of the amine-based antioxidant is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, and further preferably 0.50% by mass or more, based on the total amount of the lubricating oil composition. And, it is preferably 3.00% by mass or less, more preferably 2.50% by mass or less, and still more preferably 2.00% by mass or less.

As the antioxidant, by using a phenolic antioxidant and an amine antioxidant in combination, the phenolic antioxidant mainly acts more effectively on the initial stage of oxidation, and the amine oxidation By using it together with the inhibitor, it is possible to maintain the oxidation stability and the friction reducing effect for a longer period of time than when each of them is used alone due to a synergistic effect.
As antioxidants other than phenolic antioxidants and amine antioxidants, molybdenum amine complex antioxidants, sulfur antioxidants such as dilauryl-3,3′-thiodipropionate, and phosphites And phosphorus-based antioxidants. These can be appropriately selected from known antioxidants used as antioxidants for lubricating oils. These may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as said organic zinc dithiophosphate, For example, the compound represented by the following general formula (III) is mentioned.

In the general formula (III), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represents a hydrocarbyl group having 1 to 24 carbon atoms.
Examples of the hydrocarbyl group having 1 to 24 carbon atoms include a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 3 to 24 carbon atoms, carbon A cycloalkyl group having 5 or more and 13 or less, or a linear or branched alkylcycloalkyl group, an aryl group having 6 to 18 carbon atoms, or a linear or branched alkylaryl group, and 7 or more carbon atoms Among them, any of 19 or less arylalkyl groups is preferable, and among them, an alkyl group is preferable, and a primary or secondary alkyl group having 3 to 22 carbon atoms is more preferable.
The organic dithiophosphate is preferably zinc dialkyldithiophosphate, and more preferably zinc secondary dialkyldithiophosphate. These may be used alone or in combination of two or more.
The content of the organic zinc zinc dithiophosphate is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.50% by mass or more, even more based on the total amount of the lubricating oil composition. Preferably it is 0.80% by mass or more, preferably 20.00% by mass or less, more preferably 15.00% by mass or less, still more preferably 10.00% by mass or less, and still more preferably 5.00% by mass. % Or less.

  The organic zinc dithiophosphate also has a function as an antioxidant. Since part of the mechanism of action of the organic zinc dithiophosphate to prevent oxidation is a mechanism of action different from that of the above-mentioned antioxidant, it is preferable to use the organic zinc dithiophosphate together with the antioxidant. Specifically, the antioxidants such as the above-mentioned phenolic antioxidants and amine antioxidants are chain termination type antioxidants, but the organic zinc dithiophosphate also has a chain termination type action. However, it has an action of preventing oxidation mainly by decomposing peroxide. The chain-stopping antioxidant suppresses the formation of hydroperoxide, but has no effect on the generated hydroperoxide, so that the organic zinc dithiophosphate and the antioxidant are used in combination. Thus, a synergistic effect can be obtained, and more excellent antioxidant performance can be achieved.

Examples of the ashless dispersant include polybutenyl succinimides having a polybutenyl group having a number average molecular weight (Mn) of 900 or more and 3,500 or less (polybutenyl succinic monoimide, polybutenyl succinic acid bisimide, etc.), polybutenyl Examples thereof include derivatives such as tenenylbenzylamine, polybutenylamine, and boric acid-modified products (polybutenyl succinic acid monoimide borate). These may be used alone or in combination of two or more.
The content of the ashless dispersant is preferably 0.10% by mass or more, more preferably 1.00% by mass or more, and further preferably 2.00% by mass or more, based on the total amount of the lubricating oil composition. Preferably, it is 15.00 mass% or less, More preferably, it is 12.00 mass% or less, More preferably, it is 10.00 mass% or less.

As the ashless friction modifier, for example, an ester friction modifier such as a partial ester compound obtained by a reaction between a fatty acid and an aliphatic polyhydric alcohol is used. The fatty acid is preferably a fatty acid having a linear or branched hydrocarbon group having 6 to 30 carbon atoms, and the hydrocarbon group preferably has 8 to 24 carbon atoms, more preferably 10 to 20 carbon atoms. It is. The aliphatic polyhydric alcohol is a divalent to hexavalent alcohol, and examples thereof include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol.
These may be used alone or in combination of two or more. The content of the ashless friction modifier is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more, based on the total amount of the lubricating oil composition. Yes, and preferably 8.0% by mass or less, more preferably 5.0% by mass or less, and still more preferably 1.0% by mass or less.

  Examples of the extreme pressure agent include sulfur compounds such as sulfurized olefins, dialkyl polysulfides, diarylalkyl polysulfides, diaryl polysulfides, phosphate esters, thiophosphate esters, phosphite esters, alkyl hydrogen phosphites, phosphate ester amine salts. And phosphorus compounds such as phosphite amine salts. These may be used alone or in combination of two or more. The content of the extreme pressure agent is preferably 0.01% by mass or more and 10% by mass or less based on the total amount of the lubricating oil composition.

  Examples of the rust inhibitor include alkyl or alkenyl succinic acid derivatives such as dodecenyl succinic acid half ester, octadecenyl succinic anhydride, dodecenyl succinic acid amide, sorbitan monooleate, glycerin monooleate, pentaerythritol monooleate. A polyhydric alcohol partial ester such as rosin amine, amines such as N-oleyl sarcosine, dialkyl phosphite amine salts, and the like can be used. These may be used alone or in combination of two or more. The content of the rust inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 5.0% by mass or more, based on the total amount of the lubricating oil composition. Preferably it is 2.0 mass% or less.

  Examples of the metal deactivator include benzotriazole, triazole derivatives, benzotriazole derivatives, and thiadiazole derivatives. These metal deactivators may be used alone or in combination of two or more. The content of the metal deactivator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.10% by mass or more, based on the total amount of the lubricating oil composition. And, it is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and further preferably 1.0% by mass or less.

  Examples of the pour point depressant include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate (PMA; polyalkyl (meth)) Acrylate, etc.), polyvinyl acetate, polybutene, polyalkylstyrene and the like, and polymethacrylates are preferably used. These pour point depressants may be used alone or in combination of two or more. The content of the pour point depressant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.20% by mass or more, based on the total amount of the lubricating oil composition. And preferably it is 5.0 mass% or less, More preferably, it is 3.0 mass% or less, More preferably, it is 1.0 mass% or less.

  Examples of the antifoaming agent include dimethyl silicone and polyacrylate. These antifoaming agents may be used alone or in combination of two or more. The content of the antifoaming agent is preferably 0.0002% by mass or more, more preferably 0.0005% by mass or more, and further preferably 0.0500% by mass or more, based on the total amount of the lubricating oil composition. Is 0.15% by mass or less, more preferably 0.13% by mass or less, and still more preferably 0.10% by mass or less.

<Properties of Lubricating Oil Composition for Internal Combustion Engine>
The chlorine atom (Cl) content in the lubricating oil composition is preferably 2.00 mass ppm or less, more preferably 1.50 mass ppm or less, and even more preferably 1.40, based on the total amount of the lubricating oil composition. It is not more than ppm by mass, more preferably not more than 1.00 ppm by mass. Further, when the content is 2.00 mass ppm or less, the water resistance of the lubricating oil composition and the durability when mixed with moisture are improved.
Further, the lower limit of the chlorine atom content is not particularly limited. For example, it is preferable not to contain a chlorine atom. When the chlorine atom is contained, it is preferably 0.1 on the basis of the total amount of the lubricating oil composition. It is mass ppm or more.

  The ratio of the component (B) content, the chlorine atom (Cl) content, and the component (B) in the lubricating oil composition [component (B) / (Cl)] is preferably a mass ratio. Is 3,000 or more, more preferably 4,000 or more, still more preferably 8,000 or more, still more preferably 10,000 or more, and preferably 20,000 or less, more preferably 15,000. Hereinafter, it is more preferably 13,000 or less. When the ratio is 3,000 or more, the durability of the lubricating oil composition when mixed with moisture is further improved. In addition, when the ratio is 20,000 or less, durability of the lubricating oil composition when moisture is mixed becomes good.

  The calcium atom (Ca) content in the lubricating oil composition is preferably 500 ppm by mass or more, more preferably 800 ppm by mass or more, and even more preferably 1,000 ppm by mass or more, based on the total amount of the lubricating oil composition. In addition, it is preferably 2,000 mass ppm or less, more preferably 1,800 mass ppm or less, and still more preferably 1,500 mass ppm or less. When the content is 500 mass ppm or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the ash content of a lubricating oil composition can be reduced as the said content is 2,000 mass ppm or less.

  The magnesium atom (Mg) content in the lubricating oil composition is preferably 200 ppm by mass or more, more preferably 300 ppm by mass or more, still more preferably 400 ppm by mass or more, based on the total amount of the lubricating oil composition. Further, it is preferably 1,000 mass ppm or less, more preferably 800 mass ppm or less, and still more preferably 500 mass ppm or less. When the content is 200 ppm by mass or more, the cleanliness of the lubricating oil composition is further improved. Moreover, the ash content of a lubricating oil composition can be reduced as the said content is 1,000 mass ppm or less.

  The molybdenum atom (Mo) content in the lubricating oil composition is preferably 30 mass ppm or more, more preferably 40 mass ppm or more, and even more preferably 50 mass ppm or more, based on the total amount of the lubricating oil composition. Moreover, it is preferably 800 ppm by mass or less, more preferably 400 ppm by mass or less, further preferably 200 ppm by mass or less, and still more preferably 150 ppm by mass or less. When the content is 30 mass ppm or more, the friction reducing action of the lubricating oil composition is further improved. Moreover, the cleanliness of a lubricating oil composition will become favorable as the said content is 800 mass ppm or less.

  The sulfur atom (S) content in the lubricating oil composition is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and still more preferably 0.15, based on the total amount of the lubricating oil composition. The content is not less than ppm by mass, preferably not more than 1.00% by mass, more preferably not more than 0.50% by mass, and still more preferably not more than 0.30% by mass. When the content is 0.05% by mass or more, the friction reducing action of the lubricating oil composition is further improved.

In the lubricating oil composition, the ratio [(Ca) / (Mo)] of the calcium atom (Ca) content to the molybdenum atom (Mo) content is a mass ratio, preferably 2.00 or more. Preferably it is 2.30 or more, More preferably, it is 2.50 or more, Preferably it is 3.50 or less, More preferably, it is 3.20 or less, More preferably, it is 2.90 or less.
In the lubricating oil composition, the ratio of magnesium atom (Mg) content to molybdenum atom (Mo) content [(Mg) / (Mo)] is a mass ratio, preferably 3.50 or more, more preferably It is 4.00 or more, More preferably, it is 4.30 or more, Preferably it is 5.50 or less, More preferably, it is 5.20 or less, More preferably, it is 4.90 or less.

The base number (hydrochloric acid method) of the lubricating oil composition is preferably 4.80 mgKOH / g or more, more preferably 5.00 mgKOH / g or more, still more preferably 5.30 mgKOH / g or more, and still more preferably 5 .50 mgKOH / g or more, preferably 10.0 mgKOH / g or less, more preferably 9.00 mgKOH / g or less, still more preferably 8.00 mgKOH / g or less, still more preferably 7.00 mgKOH / g or less. is there. When the base number is 4.80 mgKOH / g or more, the cleanliness is excellent.
The value of the base number is a value measured by the method described in Examples described later.

  Further, the base number (hydrochloric acid method) of the lubricating oil composition after the water resistance test described in Examples described later is preferably 4.70 mgKOH / g or more, more preferably 4.80 mgKOH / g or more, and still more preferably. 5.00 mgKOH / g or more, more preferably 5.40 mgKOH / g or more, preferably 9.00 mgKOH / g or less, more preferably 8.00 mgKOH / g or less, still more preferably 7.00 mgKOH / g or less. More preferably, it is 6.00 mgKOH / g or less. When the base number is 4.70 mgKOH / g or more, the cleanliness when water is mixed is excellent.

  In addition, the base number maintenance rate of the lubricating oil composition evaluated by the method described in Examples described later is preferably 5.0% or more, more preferably 6.0% or more, and still more preferably 6.5%. As described above, it is more preferably 7.0% or more, still more preferably 8.0% or more. When the base number maintenance ratio is 5.0% or more, the durability of the lubricating oil composition when mixed with water is excellent.

[Method for producing lubricating oil composition for internal combustion engine]
The manufacturing method of the lubricating oil composition for internal combustion engines which is one Embodiment of this invention mix | blends base oil, an overbased calcium sulfonate (A), and an overbased magnesium detergent (B). The component (B) has a chlorine atom content of 400 ppm by mass or less based on the total amount of the component (B).
Moreover, in the said manufacturing method, you may further mix | blend components other than a component (A) and a component (B) with a base oil, Preferably, a component (C) is further mix | blended. Moreover, in the said manufacturing method, you may further mix | blend other components other than component (A)-(C) with base oil.
Each of the base oil, components (A) to (C), and other components is the same as that described for the lubricating oil composition, and the preferred embodiments thereof are also the same and are obtained by the production method. Since the lubricating oil composition is also as described above, description thereof is omitted.
In the said manufacturing method, the said components (A)-(C) and other components may be mix | blended with base oil by what kind of method, The method is not limited.

[Use of lubricating oil composition for internal combustion engine]
The lubricating oil composition can be used as a lubricating oil for internal combustion engines such as gasoline engines, diesel engines, gas engines, etc., preferably automobiles such as motorcycles and automobiles, generators, ships, etc. It is used as a lubricating oil that fills and lubricates the parts related to the internal combustion engine.
More preferably, the lubricating oil composition can be used in an internal combustion engine mounted on a vehicle employing a hybrid system described later, and more preferably an internal combustion engine mounted on a vehicle, a ship, or the like employing a hybrid system described later. And is used as a lubricating oil for lubricating between parts of the internal combustion engine.
Further, the lubricating oil composition can be used for an internal combustion engine that uses a fuel containing an alcohol fuel such as methanol or ethanol, more preferably a fuel containing an alcohol fuel such as methanol or ethanol. It is used as a lubricating oil that fills an internal combustion engine and lubricates the parts involved in the internal combustion engine.
In addition, in the fuel containing alcohol fuel, the content of the alcohol is preferably 40% by volume or more, more preferably 70% by volume or more, and still more preferably 90% by volume or more.

The lubricating oil composition for an internal combustion engine can be used more preferably for an internal combustion engine using a fuel containing biofuel and / or biodiesel fuel, and more preferably biofuel and / or biodiesel fuel. It is used as a lubricating oil that fills an internal combustion engine that uses the contained fuel and lubricates the parts involved in the internal combustion engine.
In the fuel containing biofuel and / or biodiesel fuel, the total content of the biofuel and / or biodiesel fuel is preferably 40% by volume or more, more preferably 70% by volume or more, and still more preferably 90%. Volume% or more.
Examples of the biofuel include biomethanol, bioethanol, bioethyl-tert-butyl ether, and cellulose-based ethanol.
Biodiesel fuel includes, for example, hydrotreated oil obtained by decomposing and refining raw oils and fats such as fatty acid methyl esters, plant and tallow using petroleum refining hydrotreating technology, or pyrolysis gas of biomass. Examples include fuels that are blended with synthetic oil produced by synthesizing liquid hydrocarbons from carbon monoxide and hydrogen by the Tropsch method using a catalytic reaction.

[Lubrication method using lubricating oil composition for internal combustion engine]
Therefore, as a lubricating method using the lubricating oil composition for an internal combustion engine according to an embodiment of the present invention, the lubricating oil composition is used, for example, a gasoline engine such as a motor vehicle such as a two-wheeled vehicle or a four-wheeled vehicle, a generator or a ship. An internal combustion engine such as a diesel engine or a gas engine, an internal combustion engine mounted on a vehicle or a ship that employs a hybrid system described later, or an internal combustion engine that uses a fuel containing alcohol fuel such as ethanol, And a method of lubricating between components, preferably an internal combustion engine mounted on a vehicle, a ship or the like employing a hybrid system described later, an internal combustion engine using a fuel containing alcohol fuel such as ethanol, or the bio Fill an internal combustion engine that uses fuel or the biodiesel fuel, and lubricate the parts involved in the internal combustion engine. How to, and the like.

[Internal combustion engine using lubricating oil composition for internal combustion engine]
Another embodiment of the present invention is an internal combustion engine using the lubricating oil composition, preferably an internal combustion engine (engine) using the lubricating oil composition as engine oil. Examples of the internal combustion engine include motorcycles, automobiles such as four-wheeled vehicles, generators, gasoline engines, diesel engines, gas engines and the like mounted on ships.
Another embodiment of the present invention is a hybrid system having an internal combustion engine and an electric motor using the lubricating oil composition as a power source, and preferably an engine and an electric motor using the lubricating oil composition as engine oil. It has a hybrid system. As what has the said hybrid system, a hybrid vehicle, a hybrid two-wheeled vehicle, a hybrid train, a hybrid ship etc. are mentioned, for example.
Another embodiment of the present invention is an internal combustion engine using the lubricating oil composition, wherein the internal combustion engine uses alcohol fuel. The internal combustion engine is preferably an engine using the lubricating oil composition as engine oil and using alcohol fuel. Examples of the engine using the alcohol fuel include a gasoline engine, a diesel engine, and a gas engine mounted on an automobile, a motorcycle, a train, a ship, and the like.
Another embodiment of the present invention is an internal combustion engine using the lubricating oil composition, the internal combustion engine using the biofuel or the biodiesel fuel. The internal combustion engine is preferably an engine that uses the lubricating oil composition as an engine oil and uses the biofuel or the biodiesel fuel. Examples of the engine using the biofuel or the internal combustion engine using the biodiesel fuel include a gasoline engine, a diesel engine, and a gas engine mounted on an automobile, a two-wheeled vehicle, a train, a ship, and the like.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

In this specification, the measurement of each physical property of each raw material used in each Example and each Comparative Example and the lubricating oil composition of each Example and each Comparative Example is determined according to the following procedure.
<Kinematic viscosity (40 ° C. kinematic viscosity, 100 ° C. kinematic viscosity)>
It is a value measured using a glass capillary viscometer according to JIS K2283: 2000.
<Viscosity index>
It is a value measured according to JIS K2283: 2000.
<NOACK evaporation>
It is a value measured according to the method prescribed in ASTM D5800 (250 ° C., 1 hour).
<Ring analysis (% C _A and% C _P )>
Ring analysis n-d-M aromatic calculated in method (aromatic) proportion (percentage)% of fraction _{C A,} shows the percentage of paraffin component (percentage) as the% _{C P,} it was measured according to ASTM D-3238 Is.
<Base number (hydrochloric acid method)>
Based on JIS K2501: 2003, it was measured by potentiometric titration method (base number / hydrochloric acid method).
<Content of chlorine atom (Cl)>
It is a value measured according to JPI-5S-64-2002.
<Metal content: content of calcium atom (Ca), magnesium atom (Mg), molybdenum atom (Mo), phosphorus atom (P), zinc atom (Zn), and boron atom (B)>
It measured based on JPI-5S-38-2003.
<Content of sulfur atom (S)>
It is a value measured according to JIS K2541-6.
<Content of nitrogen atom (N)>
It is a value measured by a chemiluminescence method in accordance with JIS K2609: 1998.
<SSI (Shear Stability Index)>
Measured according to ASTM D6278.
<Weight average molecular weight (Mw), number average molecular weight (Mn)>
Using a gel permeation chromatograph device (manufactured by Agilent, “1260 HPLC”), the measurement was performed under the following conditions, and values measured in terms of standard polystyrene were used.
(Measurement condition)
-Column: Two "Shodex LF404" connected in sequence-Column temperature: 35 ° C
・ Developing solvent: Chloroform ・ Flow rate: 0.3 mL / min

The evaluation method of the lubricating oil composition of each example and each comparative example is as follows.
[Water resistance test]
A copper plate weighed with 130 g of sample oil and 3.3 g of distilled water was placed in a glass bottle and sealed. The glass bottle was placed in a thermostatic bath maintained at 62 ° C., and rotated at 5 rpm for 24 hours in the direction of turning upside down once during one rotation. The base number (hydrochloric acid method) of the sample oil after the operation was measured using the same method as described above. The material of the copper plate was C1100P, and the size was 51 mm (length) × 13 mm (width) × 1 mm (thickness), which was polished until a new surface appeared.
[Durability Evaluation: Water Resistance NOx Test]
100 g of sample oil after the water resistance test was put into a glass tube, and the oil temperature was adjusted to 140 ° C. Air flow rate: 100 mL / min and nitric oxide (NO) diluted with nitrogen (NO concentration: 8,000 volume ppm) and a flow rate of 100 mL / min are mixed together in the sample oil at an oil temperature of 140 ° C. Introduced and produced NOx-degraded oil over 20 hours.
The base number (hydrochloric acid method) of the NOx deteriorated oil was measured using the same method as described above.
From the obtained results, the base number maintenance rate was calculated based on the following formula.
Base number maintenance rate (%) = (base number of NOx deteriorated oil after water resistance NOx test / base number of sample oil before water resistance test) × 100

[Examples 1 to 3, Comparative Examples 1 and 2]
Each component is blended with the base oil so as to have the composition shown in Table 2 below, and after preparing a lubricating oil composition for an internal combustion engine, the compositions of the examples and comparative examples are evaluated according to the evaluation method. did. The obtained results are shown in Table 2 below.

In addition, each component shown in the following Table 2 represents the following compounds, respectively.
<Base oil>
Lubricating base oil: hydrogenated refining base oil (mineral oil), 40 ° C. kinematic viscosity 19.2 mm ² / s, 100 ° C. kinematic viscosity 4.2 mm ² / s, viscosity index 126, a sulfur content of less than 2 mass ppm, NOACK Evaporation amount 13.9 mass%, ndM ring analysis;% C _P 79.6,% C _A = 0
<Overbased calcium sulfonate: component (A)>
Overbased calcium sulfonate: base number (hydrochloric acid method) 304 mgKOH / g, calcium content 11.7% by mass, sulfur content 1.6% by mass, the alkyl group structure of the soap group is a branched alkyl group (of the alkyl group) 16 main carbons)

<Magnesium detergent: component (B) and other magnesium detergents>
(Ingredient (B))
Magnesium detergent (1): Overbased magnesium salicylate Magnesium detergent (2): Overbased magnesium sulfonate Magnesium detergent (3): Overbased magnesium sulfonate (other magnesium detergents)
Magnesium detergent (4): Overbased magnesium salicylateMagnesium detergent (5): Overbased magnesium salicylate The properties of each magnesium detergent are shown in Table 1 below.

<Organic molybdenum compound: Component (C)>
Organic molybdenum compound: “Infineum C9455B” (trade name, manufactured by Infineum), trinuclear molybdenum dithiocarbamate represented by the general formula (c12-1), molybdenum content 5.5 mass%, sulfur content 9.9 mass %

<Other ingredients>
Viscosity index improver: polyalkyl (meth) acrylate, weight average molecular weight (Mw) 380,000, SSI = 20 (1.16% by mass as a resin component based on the total amount of the lubricating oil composition)
-Zinc dialkyldithiophosphate: R ^{41 to} R ⁴⁴ in the general formula (III) are a mixture of a secondary propyl group and a secondary hexyl group [zinc content: 7.85 mass%, phosphorus content: 7.2 mass %, Sulfur content 14.4% by mass] (1.10% by mass based on the total amount of the lubricating oil composition)
Polybutenyl succinic acid monoimide borate: number average molecular weight (Mn) of polybutenyl group 1,000, nitrogen atom content 1.23 mass%, boron content 1.30 mass%, chlorine atom content 0.06 % By mass (containing 2.00% by mass based on the total amount of the lubricating oil composition)
Polybutenyl succinic acid bisimide: number average molecular weight (Mn) of polybutenyl group 1,300, nitrogen atom content 0.99 mass%, chlorine atom content 0.01 mass% or less (2 based on the total amount of the lubricating oil composition) .50% by mass)
Antifoaming agent: dimethyl silicone (containing 0.10% by mass based on the total amount of the lubricating oil composition)
-Pour point depressant: polyalkyl (meth) acrylate (containing 0.20% by mass based on the total amount of the lubricating oil composition)
・ Phenol antioxidant (0.50% by mass based on the total amount of lubricating oil composition)
・ Amine-based antioxidant (0.80% by mass based on the total amount of lubricating oil composition)
Metal deactivator: benzotriazole (containing 0.20% by mass based on the total amount of the lubricating oil composition)
・ Diluted oil (containing 0.37% by mass based on the total amount of lubricating oil composition)

  As shown in Table 3, the lubricating oil compositions of Examples 1 to 3 contain component (B) whose chlorine atom content is 400 mass ppm or less based on the total amount of component (B). It was confirmed that the value of the base number after the water resistance test was high and the base number maintenance rate after the water resistance NOx test was high for the described lubricating oil composition.

The lubricating oil composition for internal combustion engines according to an embodiment of the present invention is excellent in water resistance and durability when mixed with moisture. Therefore, it can be suitably used for an internal combustion engine mounted on a vehicle that employs a hybrid system, and more preferably, the internal combustion engine that is mounted on a vehicle, a ship, or the like that employs a hybrid system is filled with each of the internal combustion engines. It is used as a lubricating oil that lubricates between parts.
The lubricating oil composition for an internal combustion engine can also be suitably used for an internal combustion engine using a fuel containing an alcohol fuel such as methanol or ethanol, more preferably a fuel containing an alcohol fuel such as methanol or ethanol. It is used as a lubricating oil that fills an internal combustion engine that uses oil and lubricates between the parts related to the internal combustion engine.
The lubricating oil composition for an internal combustion engine can be suitably used for an internal combustion engine using a fuel containing biofuel and / or biodiesel fuel, and more preferably contains biofuel and / or biodiesel fuel. It is used as a lubricating oil that fills an internal combustion engine that uses fuel and lubricates between components of the internal combustion engine.

Claims (10)

Base oil,
An overbased calcium sulfonate (A);
Containing an overbased magnesium detergent (B),
A lubricating oil composition for internal combustion engines, wherein the chlorine atom content of component (B) is 400 ppm by mass or less based on the total amount of component (B).   The lubricating oil composition for internal combustion engines according to claim 1, wherein the component (B) is at least one selected from the group consisting of overbased magnesium sulfonate, overbased magnesium salicylate, and overbased magnesium phenate. .   The lubricating oil composition for internal combustion engines according to claim 1 or 2, wherein the base number measured by the hydrochloric acid method of component (A) is 200 mgKOH / g or more.   The lubricating oil composition for internal combustion engines according to any one of claims 1 to 3, wherein the base number measured by the hydrochloric acid method of component (B) is 200 mgKOH / g or more.   The lubricating oil composition for internal combustion engines according to any one of claims 1 to 4, wherein the component (B) has a linear alkyl group or a branched alkyl group.   Furthermore, the component (C) contains an organic molybdenum compound, and the content of the component (C) in terms of molybdenum atoms is 50 mass ppm or more and less than 400 mass ppm based on the total amount of the lubricating oil composition. The lubricating oil composition for internal combustion engines according to any one of the above.   The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 6, wherein the base number maintenance rate is 5.0% or more.   The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 7, which is used for an internal combustion engine mounted on a vehicle employing a hybrid system.   The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 8, which is used for an internal combustion engine using a fuel containing an alcohol fuel.   The ratio (component (B) / (Cl)) of the chlorine atom content (Cl) in the lubricating oil composition to the content of the component (B) in the lubricating oil composition is 3,000 by mass ratio. It is the above, The lubricating oil composition for internal combustion engines of any one of Claims 1-9.