DE112017001595T5 - Lubricating oil composition - Google Patents

Abstract

This invention relates to a lubricating oil composition containing a base oil, (A) a benzotriazole derivative having a specific structure, (B) an epoxy compound, and (C) an ashless friction modifier, wherein the ashless friction modifier (C) is in an amount of 0, 20 mass% or more, based on the total amount of the lubricant oil composition.

Description

Technical area

This invention relates to a lubricant oil composition.

background

At the present time, regulation for global environmental protection is becoming more stringent, and in particular, circumstances on automobiles are becoming much stricter in fuel economy regulations, exhaust gas regulations, etc. The background of the circumstances includes environmental problems such as global warming and resource conservation caused by concerns about the emptying of the environment oil Ressoursen. It is considered that fuel economy has been saved due to the above factors. For the saving of fuel consumption in automobiles, an improvement in an engine oil such as a reduction in the viscosity of an engine oil and the addition of an advantageous friction modifier are important for preventing the friction loss in an engine, in addition to improving an automobile itself such as a reduction in the weight of an automobile and an improvement of an engine. The reduction of the viscosity of the engine oil may be a factor that increases the friction in different parts in an engine. In order to reduce the friction loss associated with the reduction of the viscosity and to prevent the abrasion, a friction modifier, an extreme pressure agent and the like become more important than heretofore.

An iron-based material and an aluminum-based material have been mainly used for a sliding part of an engine and the like, and a wide variety of materials containing aluminum and copper without being limited to an iron-based material, For example, a bearing metal was used for a material of a sliding part of a main bearing of a connecting rod bearing and the like. Although there is an orientation that the use of tin, lead and the like is limited, these elements are included in some materials. Copper and lead-containing metal materials undergo less fatigue phenomena than an excellent feature thereof, but can be corroded, which is a defect. Accordingly, the lubricant oil and the additives must have corrosion resistance for metal materials in addition to the reduction of friction loss and the prevention of abrasion.

The lubricant oil must have various capabilities as described above, and various additives are generally added to meet these various capabilities.

For example, PTL 1 describes a lubricating oil composition for an internal combustion engine containing a lubricant base oil containing therein a certain molybdenum oxysulfide dithiocarbamate, an acid amide compound, a fatty acid partial ester compound and / or an aliphatic amine compound and a specific benzotriazole derivative, respectively Contains shares.

PTL 2 describes a fuel-saving type motor oil composition containing a lubricant base oil containing therein an organic molybdenum compound in an amount of 0.02 mass% or more in terms of molybdenum (Mo) amount and an alicyclic epoxy compound contains.

PTL 3 describes a lubricant oil composition containing a lubricant base oil containing therein a certain phosphorus compound and an epoxy compound each in specific amounts.

PTL 4 describes a lubricant oil composition containing a lubricant base oil containing therein a fatty acid partial ester compound, an aliphatic amine compound and / or an acid amide compound, a specific benzotriazole derivative and a certain succinimide compound, each in specific amounts.

List of pamphlets

Patent literatures

• PTL 1: JP 2008-106199 A
• PTL 2: WO 2011/161982
• PTL 3: JP 2012-201807 A
• PTL 4: WO 2008/047550

Summary of the invention

Technical problem

The molybdenum oxysulfide dithiocarbamate (which may be referred to as "MoDTC" hereinafter) used in PTL 1 and 2 has an excellent friction-reducing effect, but has a fear of corrosivity to copper. For example, PTL 2 in Comparative Example 2 thereof describes that significant corrosion of copper occurs when MoDTC is mixed.

For suppressing the corrosion of copper, the above-mentioned PTLs use a certain benzotriazole derivative, but it is known that the use of the benzotriazole derivative is insufficient in the effect of suppressing corrosion of lead, and for example, PTL 2 in Comparative Example 4 thereof in that the elution of lead is increased when the benzotriazole derivative is mixed in a large amount.

For suppressing corrosion of lead, PTLs 2 and 3 use an epoxy compound, but there is no study for use thereof in a lubricant oil composition using an ashless friction modifier as a friction modifier.

When an ashless friction modifier is used instead of MoDTC, the content of the ashless friction modifier is necessarily increased to obtain an excellent friction-reducing effect, and the use of the ashless friction modifier causes concern for lead corrosivity. For example, PTL 4 describes a lubricant oil composition having an ashless friction modifier and a certain benzotriazole derivative, but there is room for improvement in the corrosion suppressing action of copper and lead.

As described above, a lubricant oil composition must have an excellent friction-reducing effect, but when an ashless friction modifier is used as a friction modifier, it is necessary to obtain both a corrosion-suppressing effect of copper and a corrosion-suppressing effect of lead in addition to an excellent friction-reducing effect ,

This invention was made in view of the above circumstances, and an object of this invention is to provide a lubricating oil composition using an ashless friction modifier, wherein the lubricating oil composition excellent in friction-reducing effect and also in the corrosion-suppressing effects of copper and Lead is.

the solution of the problem

• [1] Schmiermittelölzusammensetzung, enthaltend: ein Grundöl,
  • (A) ein Benzotriazol-Derivat mit der allgemeinen Formel (I):
    
    worin R¹ ein Wasserstoffatom oder eine Kohlenwasserstoff-Gruppe mit einer Zahl von Kohlenstoffatomen von 1 oder mehr und 9 oder weniger ist, die zumindest eine Art von einem Atom enthalten kann, ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom, Schwefelatom und Stickstoffatom; und R² ein Wasserstoffatom oder eine Kohlenwasserstoff-Gruppe mit einer Zahl von Kohlenstoffatomen von 1 oder mehr und 16 oder weniger ist, die zumindest eine Art eines Atoms enthalten kann, ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom, Schwefelatom und Stickstoffatom,
  • (B) eine Epoxy-Verbindung und
  • (C) einen aschelosen Friktionsmodifizierer,
  worin der aschelose Friktionsmodifizierer (C) in einer Menge von 0,20 mass% oder mehr auf der Basis der Gesamtmenge der Schmiermittelölzusammensetzung enthalten ist.
• [2] Schmierverfahren, umfassend die Verwendung der Schmiermittelölzusammensetzung gemäß Aspekt [1] bei einem Teil, das Kupfer oder Blei enthält.

As a result of many studies by these inventors, it has been found that the problem can be solved by blending a benzotriazole derivative having a particular structure and an epoxy compound with a base oil and mixing an ashless friction modifier with them in a certain amount. This invention has been completed on the basis of this finding. Specifically, this invention provides the following aspects [1] and [2].

• [1] A lubricant oil composition containing: a base oil,
  • (A) a benzotriazole derivative having the general formula (I):
    
    wherein R ^{1 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 9 or less, which may contain at least one kind of one atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom; and R ^{2 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 16 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom,
  • (B) an epoxy compound and
  • (C) an ashless friction modifier,
  wherein the ashless friction modifier (C) is contained in an amount of 0.20 mass% or more based on the total amount of the lubricant oil composition.
• [2] A lubricating method comprising using the lubricating oil composition according to aspect [1] in a part containing copper or lead.

Advantageous Effects of the Invention

According to this invention, a lubricant oil composition can be provided by using an ashless friction modifier having excellent friction-reducing effect and also excellent corrosion-suppressing effects on copper and lead.

Description of the embodiments

Preferred embodiments of this invention will be described in detail below.

[Lubricating oil composition]

worin R¹ ein Wasserstoffatom oder eine Kohlenwasserstoff-Gruppe mit einer Zahl von Kohlenstoffatomen von 1 oder mehr und 9 oder weniger ist, die zumindest eine Art von einem Atom enthalten kann, ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom, Schwefelatom und Stickstoffatom; und R² ein Wasserstoffatom oder eine Kohlenwasserstoff-Gruppe mit einer Zahl von Kohlenstoffatomen von 1 oder mehr und 16 oder weniger ist, die zumindest eine Art eines Atoms enthalten kann, ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom, Schwefelatom und Stickstoffatom, (B) eine Epoxy-Verbindung und (C) einen aschelosen Friktionsmodifizierer, worin der aschelose Friktionsmodifizierer (C) in einer Menge von 0,20 mass% oder mehr auf der Basis der Gesamtmenge der Schmiermittelölzusammensetzung enthalten ist.A lubricant oil composition according to one embodiment of this invention contains: (A) a benzotriazole derivative having the general formula (I):

wherein R ^{1 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 9 or less, which may contain at least one kind of one atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom; and R ^{2 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 16 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom, (B) an epoxy compound and (C) an ashless friction modifier, wherein the ashless friction modifier (C) is contained in an amount of 0.20 mass% or more based on the total amount of the lubricant oil composition.

The lubricant oil composition according to an embodiment of this invention contains the ashless friction modifier (C) as a friction modifier in an amount of 0.20 mass% or more based on the total amount of the lubricant oil composition and thus has an excellent friction-reducing effect. Further, the lubricant oil composition contains the ashless friction modifier (C) in a large amount, but contains the benzotriazole derivative (A) having the general formula (I) and the epoxy compound (B), and thus has an excellent corrosion-suppressing effect of copper and lead at the same time.

These effects are not those obtained from the simple combination of the respective effects expected from the use of the benzotriazole derivative and the epoxy compound separately.

The components constituting the lubricant oil composition of the one embodiment of this invention will be described below.

<Base Oil>

The base oil used in the lubricant oil composition is not particularly limited, and an arbitrary material appropriately selected from mineral oils and synthetic oils used as a base oil of a lubricant oil may be used.

Examples of the mineral oil include a mineral oil which is produced so that an atmospheric residual oil obtained by distilling a crude oil under atmospheric pressure under reduced pressure to obtain a lubricant oil fraction which is purified by performing one or more solvent deasphalting treatments. Solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining and the like and a base oil produced by isomerization of wax or GTL (gas-to-liquid) wax.

Examples of the synthetic oil include a poly-α-olefin such as a polybutene and a homopolymer or copolymer of an α-olefin (such as an ethylene-α-olefin copolymer), various esters such as a polyol ester, a dibasic acid ester and a phosphate ester; various ethers such as a polyphenyl ether, polyglycol, alkylbenzene and alkylnaphthalene. Among these synthetic oils, a poly-α-olefin and polyol esters are preferred.

In one embodiment of this invention, the mineral oil may be used alone or in combination of two or more kinds thereof as a base oil. The synthetic oil may be used alone or in combination of two or more kinds thereof. One or more types of the mineral oil and one or more types of the synthetic oil may be used in combination.

The content of the base oil is generally 65 mass% or more, preferably 70 mass% or more, and more preferably 75 mass% or more, and is preferably 97 mass% or less, and more preferably 95 mass% or less, based on the total amount of the lubricant oil composition.

While the viscosity of the base oil is not particularly limited, the kinematic viscosity at 100 ° C. is preferably in the range of 2 mm ² / s or more and 30 mm ² / s or less, more preferably 3 mm ² / s or more and 15 mm ² / s or less, and more preferably 3 mm ² / s or more and 10 mm ² / s or less.

When the kinematic viscosity at 100 ° C is 2 mm ² / s or more, the evaporation loss may become small, and when the kinematic viscosity at 100 ° C is 30 mm ² / s or less, the energy loss due to the viscosity resistance can be suppressed Preservation of a fuel consumption Improving effect. The value of kinematic viscosity at 100 ° C is measured by the method described later in Examples.

The viscosity index of the base oil is preferably 70 or more, more preferably 100 or more, and further preferably 120 or more. The base oil, which has a viscosity index of 70 or more, may have a small change in viscosity as the temperature changes.

When the viscosity index of the base oil is in the range, the viscosity characteristics of the lubricant oil composition can be easily improved. The viscosity index is an index measured by the method described later in Examples.

The base oil used preferably has an aromatic content (% C _A ) according to ring analysis of 3.0 or less and a sulfur content of 50 mass ppm or less. The% C _A value by ring analysis herein means a ratio (percentage) of an aromatic component calculated by the Ring Analysis ndM method. The sulfur content is a value measured according to JIS K2541.

The base oil having a% C _A of 3.0 or less and a sulfur content of 50 mass ppm or less may have good oxidation stability, and thereby the increase in the acid value and the formation of sludge can be suppressed, and a Lubricant oil composition with less corrosivity to a metal can be obtained.

The% C _A value is more preferably 1.0 or less, more preferably 0.5 or less, and even more preferably 0.1 or less. The sulfur content is more preferably 10 mass ppm or less, more preferably 5 mass ppm or less, and even more preferably 2 mass ppm or less.

The base oil used preferably has a paraffin content (% Cp) according to ring analysis of 65 or more, more preferably 70 or more, and further preferably 75 or more. When the paraffin content is 65 or more, the base oil may have good oxidation stability. The% Cp value according to Ring analysis herein means a ratio (percent) of a paraffin component, which is calculated by the Ring Analysis n-d-M method.

The NOACK value of the base oil is preferably 15.0 mass% or less, more preferably 14.0 mass part or less, and further preferably 13.0 mass part or less.

The value of% C _A , the value of% C _P , the sulfur content and the NOACK value are values measured according to the methods described later in the examples.

<Benzotriazole derivative (A) having the general formula (I)>

The lubricant oil composition contains the benzotriazole derivative (A) represented by the general formula (I) (which may be hereinafter referred to simply as "component (A)"). When the component (A) is contained, a lubricant oil composition containing an ashless friction modifier and excellent in the corrosion-suppressing effect of copper can be obtained.

The component (A) used in the lubricant oil composition is represented by the following general formula (I).

In the general formula (I), R ^{1 is} a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 9 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom; and R ² is a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 16 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom.

R ¹ is preferably a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 5 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom, more preferably a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 3 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom, and preferably represents a methyl group or a hydrogen atom with a view to obtaining a lubricant oil composition having excellent corrosion-suppressing effect of copper.

R ² is preferably a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 8 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom, more preferably A hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 5 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen, sulfur and nitrogen atom, more preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom, from the viewpoint of obtaining a lubricant oil composition having excellent corrosion-suppressing action of copper and lead simultaneously when the component (B) described later is used in combination.

Accordingly, the component (A) is more preferably one having the general formula (I) wherein R ^{1 is} a methyl group or a hydrogen atom and R ^{2 is} a hydrogen atom.

The content of the component (A) is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, further preferably 0.03 mass% or more and even more preferably 0.05 mass% or more on the basis the total amount of the lubricating oil composition in view of improving the corrosion-suppressing effect of copper. The content of the component (A) is preferably 0.15 mass% or less, more preferably 0.10 mass% or less, and further preferably 0.07 mass% or less, based on the total amount of the lubricant oil composition in terms of solubility.

As the component (A), the benzotriazole derivatives represented by the general formula (I) alone can be used, and two or more kinds of the benzotriazole derivatives represented by the general formula (I) having different structures can be used in combination. The preferable ranges of the total content when two or more kinds of the components (A) are used in combination are the same as the preferable ranges in the case when the component (A) is used alone.

By using the component (A) in combination with the component (B) described later, not only can the elution of copper be easily suppressed, but it can also have a better lead elution-suppressing effect than the lead elution-suppressing one Effect obtained when the component (B) alone is used, by which synergistic effect is achieved.

<Epoxy compound (B)>

The lubricant oil composition contains the epoxy compound (B) (which may be referred to simply as "component (B)" hereinafter). When the component (B) is contained, a lubricant oil composition excellent in corrosion-suppressing action of lead can be obtained although the component (A) is contained therein.

Examples of component (B) include a compound having at least one epoxy group in the molecule, and preferably a compound having two or more epoxy groups in the molecule.

Examples of the component (B) include an epoxy compound having a carbon number of 3 or more with a linear-chain or branched-chain alkyl group (1,2-epoxyalkane), a glycidyl ester-type epoxy compound and an alicyclic epoxy -Connection. The component (B) is preferably one or more selected from the group consisting of an epoxy compound having a linear-chain or branched-chain alkyl group having a number of carbon atoms of 3 or more and 26 or less (1,2 Epoxyalkane) and an alicyclic epoxy compound, and more preferably an alicyclic epoxy compound.

The number of carbon atoms of the epoxy compound having a linear-chain or branched-chain alkyl group having a carbon number of 3 or more and 26 or less (epoxyalkane) is preferably 10 or more, more preferably 12 or more and further preferably 14 or more. The number of carbon atoms thereof is preferably 22 or less, more preferably 20 or less, and further preferably 18 or less.

Examples of the epoxyalkane having a linear chain alkyl group with a number of carbon atoms of 3 or more and 26 or less include 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1 , 2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2 Epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxynonadecane, 1,2-epoxyicosane, 1,2-epoxyhenicosane, 1,2-epoxydocosan, 1,2-epoxytricosan , 1,2-epoxytetracosane, 1,2-epoxypentacosane and 1,2-epoxyhexacosane.

Examples of the epoxyalkane having a branched-chain alkyl group having a number of carbon atoms of 3 or more and 26 or less include compounds each having the above-mentioned linear-chain alkyl group having an alkyl group having a number of carbon atoms within a region having the number of carbon atoms attached to the alkyl chain moiety having the number of carbon atoms thereof bonded.

Preferred examples of the glycidyl ester type epoxy compound include a phenyl glycidyl ester, alkyl glycidyl ester and alkenyl glycidyl ester, and examples thereof include glycidyl benzoate, glycidyl 2,2-dimethyloctanoate, glycidyl acrylate and glycidyl methacrylate.

Preferred examples of the alicyclic epoxy compounds include an alicyclic epoxy compound having a carbon number of 3 or more and 18 or less, and more preferably a carbon number of 5 or more and 16 or less.

Examples of the alicyclic epoxy compound include 1,2-epoxycyclopropane, 1,2-epoxycyclobutane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloheptane, 1,2-epoxycyclooctane, 1,2-epoxycyclononane, 1 , 2-epoxycyclodecane, 1,2-epoxycyclododecane and 1,2-epoxynorbornane. Examples thereof also include an alkylated or alkenylated epoxycycloalkane having one or more alkyl groups or alkenyl groups attached to the carbon atom of the alicyclic moiety, such as 2- (7-oxabicyclo [4.1.0] hept-3-yl) - spiro (1,3-dioxane-5,3 '- [7] oxabicyclo [4.1.0] heptane, 4- (1'-methylepoxyethyl) -1,2-epoxy-2-methylcyclohexane and 4-epoxyethyl-1,2 -epoxycyclohexan.

Preferred examples of the alicyclic epoxy compounds also include an ether compound having one or more aliphatic or aromatic alkoxy groups bonded to the carbon atom of the alicyclic moiety, an imide compound and bisimide compound each having one or more imide groups. Have groups bonded to the carbon atom of the alicyclic moiety and an amide compound having one or more amide groups bonded to the carbon atom of the alicyclic moiety, and more preferable examples thereof include an ester compound having one or more carboxy Groups attached to the carbon atom of the alicyclic moiety.

More preferred examples of the alicyclic epoxy compound include a compound having two epoxidized cycloalkanes. Preferred examples of the compound having two epoxidized cycloalkanes include 3,4-epoxycycloalkyl-3,4-epoxycyclocarboxylate (wherein the alkyl groups each have a number of carbon atoms of 3 or more and 12 or less), and more preferable examples thereof include 3 , 4-epoxycyclohexylmethyl-3,4-epoxycyclohexane.

The content of the component (B) is preferably 0.05 mass% or more, more preferably 0.10 mass% or more, further preferably 0.20 mass% or more and still more preferably 0.30 mass% or more, based on the total amount of the lubricating oil composition in view of improving the corrosion-suppressing effect of lead. The content thereof is preferably 1.00 mass% or less, more preferably 0.70 mass% or less, and further preferably 0.50 mass% or less based on the total amount of the lubricant oil composition from the viewpoint of enhancing the corrosion-suppressing effect of Copper.

The content of the component (B) is preferably 0.05 mass% or more, more preferably 0.10 mass% or more, and further preferably 0.20 mass% or more, and is preferably 1.00 mass% or less, more preferably 0 , 70 parts by mass or less, and more preferably 0.50 part by mass or less based on the total amount of the lubricating oil composition from the viewpoint of suppressing the corrosion of copper and lead in a well-balanced manner.

The mass ratio ((A) / (B)) of the content of the component (A) and the component (B) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more, and is preferable 3.00 or less, more preferably 1.00 or less, and more preferably 0.60 or less from the viewpoint of suppressing the corrosion of copper and lead in a well-balanced manner.

As the component (B), the epoxy compounds may be used alone or in combination of two or more kinds thereof. The preferable ranges of the total content when two or more kinds of the components (B) are used in combination are the same as the preferable ranges in the case where the component (B) is used alone.

<Ashless friction modifier (C)>

The lubricant oil composition contains the ashless friction modifier (C) (which may be referred to simply as "component (C)" hereinafter) in an amount of 0.20 mass% or more based on the total amount of the lubricant oil composition.

When the content of the component (C) is less than 0.20 mass% based on the total amount of the lubricant oil composition, it is difficult to obtain a lubricant oil composition having excellent friction-reducing effect. The content of the component (C) is preferably 0.25 mass% or more, and more preferably 0.30 mass% or more, based on the total amount of the lubricant oil composition from the viewpoint of obtaining a lubricant oil composition having excellent friction-reducing effect.

The content of the component (C) is preferably 1.00 mass% or less, more preferably 0.70 mass% or less, and further preferably 0.60 mass% or less based on the total amount of the lubricant oil composition from the viewpoint of suppressing the corrosion of Copper and lead.

The content of the component (C) is preferably 0.25 mass% or more, and more preferably 0.30 mass% or more, and is preferably 1.00 mass% or less, and more preferably 0.70 mass% or less, based on the Total amount of lubricating oil composition in view of achieving excellent friction-reducing effect and suppressing corrosion of copper and lead.

Preferred examples of the component (C) include an ashless friction modifier having at least one kind of atom selected from the group consisting of a nitrogen atom and oxygen atom in the molecule, and examples thereof include an ashless friction modifier such as an amine compound, aliphatic ester, aliphatic amide, Fatty acid, aliphatic alcohol, aliphatic ether, urea-based compound and hydrazide-based compound. Among them, more preferable examples thereof are an ashless friction modifier having at least one alkyl group or alkenyl group having a number of carbon atoms of 6 or more and 30 or less in the molecule thereof such as aliphatic ester, aliphatic amide, fatty acid, aliphatic alcohol, aliphatic Amine and aliphatic ether.

More preferable examples thereof include an ashless friction modifier having two or more hydroxy groups in the molecule of the component (C), and examples thereof include at least one selected from the group consisting of an ester compound having two or more hydroxy groups in the molecule of the component (C) (which may be referred to as "ester-based friction modifier" hereinafter), an amine compound having two or more hydroxy groups in the molecule of component (C) (hereinafter referred to as "amine-based friction modifier") can), an amide compound having two or more hydroxy groups in the molecule of the component (C) (which may be referred to as "amide-based friction modifier" hereinafter) and an ether compound having two or more hydroxy groups in the molecule Component (C) (which may be referred to as "ether-based friction modifier" hereinafter). Among them, an ester-Verb having two or more hydroxy groups in the molecule of the component (C) is preferable because the corrosion-suppressing effect due to the component (A) and the component (B) can be easily obtained.

The number of hydroxy groups in the molecule of the component (C) is preferably 2 or more and 6 or less in view of the friction-reducing effect and the solubility in the base oil.

Examples of the ester-based friction modifier include a partial ester compound such as a partial ester compound obtained by reacting a fatty acid and an aliphatic polyhydric alcohol.

The fatty acid is preferably a fatty acid having a linear-chain or branched hydrocarbon group with a number of carbon atoms of 6 or more and 32 or less, and the number of carbon atoms of the hydrocarbon group is more preferably 8 or more and 24 or less and more preferably 16 or more and 20 or less in view of the ease of obtaining the friction-reducing effect.

Examples of the linear-chain or branched hydrocarbon group having a number of carbon atoms of 6 or more and 32 or less include an alkyl group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, pentacosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontyl group; an alkenyl group such as hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, oleyl, nonadecenyl Icosenyl, henicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl and triacontenyl groups; and a hydrocarbon group having two double bonds.

Examples of the fatty acid include a saturated fatty acid such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid and lignoceric acid; and an unsaturated fatty acid such as myristoleic acid, palmitoleic acid, oleic acid and linolenic acid and an unsaturated fatty acid is preferable in view of the friction-reducing effect.

The aliphatic polyhydric alcohol may be a dihydric or higher and a hexa or less valent alcohol, and examples thereof include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and sorbitol, and glycerol is preferable in view of the friction-reducing effect.

Examples of a fatty acid partial ester compound obtained by the reaction of glycerol and the unsaturated fatty acid (which may be referred to as "glycerol ester compound" hereinafter) include a monoester such as glycerol monomyristate, glycerin monopalmitate, glycerin monooleate and a diester such as glycerin myristate, glycerin dipalmitate and glycerol dioleate, and a monoester is preferred. Examples of the partial ester compound also include a reaction product with a silicon compound or a boron compound.

More preferable examples of the monoester of the glycerol ester compound include an ester compound represented by the following general formula (II).

In the general formula (II), R ^{21 is} a hydrocarbon group having a carbon number of 1 or more and 32 or less, and R ²² to R ²⁶ are each independently a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 18 or less.

The number of carbon atoms of the hydrocarbon group represented by R ²¹ is preferably 8 or more and 32 or less, more preferably 12 or more and 24 or less, and further preferably 16 or more and 20 or less.

Examples of the hydrocarbon group represented by R ²¹ include an alkyl group, alkenyl group, alkylaryl group, cycloalkyl group and cycloalkenyl group, and among them, an alkyl group and alkenyl group are preferable, and an alkenyl group is preferable ,

Examples of the alkyl group represented by R ²¹ include a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl -, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, Icosyl, henicosyl, docosyl, tricosyl and tetracosyl group, where these groups may be a linear-chain, branched or cyclic.

Examples of the alkenyl group represented by R ²¹ include a vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl -, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, oleyl, nonadecenyl, icosenyl, henicosenyl, docosenyl, tricosenyl and tetracosenyl group, wherein these groups may be linear-chain, branched and cyclic and the Position of the double bond is arbitrary.

R ²² to R ²⁶ each independently preferably represents one selected from the group consisting of a hydrogen atom and a hydrocarbon group having a number of carbon atoms of 1 or more, 18 or less, and more preferably, a hydrogen atom. It is preferred that R ²² to R ^{26 are} each hydrogen atoms.

When R ²² to R ^{26 are} each a hydrocarbon group, the hydrocarbon groups may each be saturated or unsaturated, aliphatic or aromatic and linear-chain, branched or cyclic. When R ²² to R ^{26 are} each a hydrocarbon group, the number of carbon atoms of each of the hydrocarbon groups is independently preferably a number of carbon atoms of 1 or more and 18 or less, more preferably a number of carbon atoms of 1 or more and 12 or less, more preferably a number of carbon atoms of 1 or more and 4 or less and even more preferably a number of carbon atoms of 2.

Examples of the ester compound represented by the general formula (II) include a glycerol fatty acid monoester such as glycerol-1-laurate, glycerol-l-stearate, glycerol-l-myristate and glycerol-l-oleate, and among them, glycerol-1-oleate is preferred ,

The ester-based friction modifier may be used alone or in combination of two or more kinds thereof, and the ester compound of the general formula (II) may be used alone or in combination of two or more kinds.

Preferred examples of the amine-based friction modifier include an amine compound represented by the following general formula (III).

In the general formula (III), R ^{31 is} a hydrocarbon group having a number of carbon atoms of 1 or more and 32 or less; ^R32 to ^R39 are each independently a hydrogen atom, a hydrocarbon group having a number of carbon atoms of 1 or more and 18 or less, or an oxygen-containing hydrocarbon group having an ether bond or ester bond; and a and b are each independently a number of 1 or more and 20 or less.

When a is 2 or more, there may be plural units of R ³² to R ³⁵ , and the plural units represented by R ³² may be the same or different, and the plural units represented by R ³³ may be the same or different , the plural units represented by R ³⁴ may be the same or different, and the plural units represented by R ³⁵ may be the same or different.

When b is 2 or more, plural units represented by R ³⁶ to R ³⁹ may be present, and the plural units represented by R ³⁶ may be the same or different, the plural units represented by R ³⁷ may be the same or different be the plural units represented by R ³⁸ may be the same or different, and the plural units represented by R ³⁹ may be the same or different.

The number of carbon atoms of the hydrocarbon group represented by R ³¹ is preferably 8 or more and 32 or less, more preferably 10 or more and 24 or less, and further preferably 12 or more and 20 or less.

Examples of the hydrocarbon group represented by R ³¹ include an alkyl group, alkenyl group, alkylaryl group, cycloalkyl group and cycloalkenyl group, and among them, an alkyl group and an alkenyl group are more preferable.

Examples of the alkyl group represented by R ³¹ include a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl -, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl and tetracosyl group, wherein these groups may be linear-chain, branched or cyclic.

Examples of the alkenyl group represented by R ³¹ include a vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl -, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, oleyl, nonadecenyl, icosenyl, henicosenyl, docosenyl, tricosenyl and tetracosenyl group, wherein these groups may be linear-chain, branched or cyclic, and the position of the double bond is arbitrary.

The hydrocarbon groups represented by R ³² to R ³⁹ may each be saturated or unsaturated, aliphatic or aromatic and linear-chain, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group such as an alkyl and alkenyl group (wherein the position of the double bond is arbitrary) or an aromatic hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group such as a methyl, ethyl, propyl, butyl, butenyl, hexyl, hexenyl, octyl, octenyl, 2-ethylhexyl, nonyl, decyl , Undecyl, decenyl, dodecyl, dodecenyl, tridecyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, hexadecenyl, heptadecyl, octadecyl, octadecenyl, stearyl, isostearyl, oleyl, linoleyl -, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, dimethylcyclohexyl and trimethylcyclohexyl group; and an aromatic one Hydrocarbon group such as a phenyl, methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, trimethylphenyl, butylphenyl and naphthyl group.

When R ³² to R ^{39 are} each a hydrocarbon group, the number of carbon atoms of each of the hydrocarbon groups is independently preferably a number of carbon atoms of 1 or more and 18 or less, more preferably a number of carbon atoms of 1 or more and 12 or less, more preferably a number of carbon atoms of 1 or more and 4 or less and even more preferably a number of carbon atoms of 2.

Examples of the oxygen-containing hydrocarbon group having an ether bond or an ester bond include a group having a number of carbon atoms of 1 or more and 18 or less, and examples thereof include methoxyethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl , n-butoxymethyl, t-butoxymethyl, hexyloxymethyl, octyloxymethyl, 2-ethylhexyloxymethyl, decyloxymethyl, dodecyloxymethyl, 2-butyloctyloxymethyl, tetradecyloxymethyl, hexadecyloxymethyl, 2-hexyldodecyloxymethyl, allyloxymethyl, phenoxy , Benzyloxy, methoxyethyl, methoxypropyl, 1,1-bismethoxypropyl, 1,2-bismethoxypropyl, rethoxypropyl, (2-methoxyethoxy) propyl, (1-methyl-2-methoxy) propyl, acetyloxymethyl, Propanoyloxymethyl, Butanoyloxymethyl, Hexanoyloxymethyl, Octanoyloxymethyl, 2-Ethylhexanoyloxymethyl, Decanoyloxymethyl, Dodecanoyloxymethyl, 2-Butyloctanoyloxymethyl, Tetradecanoyloxymethyl, Hexadecanoyloxymethyl, 2-Hexyldodecanoyloxymethyl and Benzoyloxymet hyl group.

^R32 to ^R39 are each independently preferably one selected from the group consisting of a hydrogen atom and a hydrocarbon group having a number of carbon atoms of 1 or more and 18 or less, and more preferably a hydrogen atom. It is preferable that R ³² to R ^{39 are} each a hydrogen atom in view of the friction-reducing effect.

Each of a and b is independently preferably an integer of 1 or more and 10 or less, more preferably 1 or more and 5 or less, more preferably 1 or more and 2 or less, and even more preferably 1.

The total number of integers represented by a and b; is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, more preferably 2 or more and 4 or less and even more preferably 2 in view of easily obtaining the friction-reducing effect.

As the amine-based friction modifier, the amine compound represented by the general formula (III) may be used alone or in combination of two or more kinds.

Examples of the amine compound represented by the general formula (III) include an amine compound having two 2-hydroxyalkyl groups, examples of which include octyldiethanolamine, decyldiethanolamine, dodecyldiethanolamine, tetradecyldiethanolamine, hexadecyldiethanolamine, stearyldiethanolamine, oleyldiethanolamine, coconut oil diethanolamine, palm oil diethanolamine, canolaol diethanolamine and Rindertalgdiethanolamin; and an amine compound having two polyalkylene structures such as polyoxyethylene octylamine, polyoxyethylene decylamine, polyoxyethylene dodecylamine, polyoxyethylene tetradecylamine, polyoxyethylene hexadecylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene tri-allyl amine, polyoxyethylene coconut oil amine, polyoxyethylene palm oil amine, polyoxyethylene lauryl amine and ethylene oxide propylene oxide stearyl amine. Among them, oleyldiethanolamine is preferable.

Preferred examples of the amide-based friction modifier include an amide compound represented by the following general formula (IV).

In the general formula (IV), R ⁴¹ may be the same as described for R ³¹ in the general formula (III), and the preferred embodiments thereof are also the same. In the general formula (IV), R ⁴² to R ^{49 may} each independently be the same as for R ³² to R ³⁹ in the general formula (III), and the preferred embodiments are also the same. In the general formula (IV), c and d are each independently an integer of 1 or more and 20 or less.

c and d are each independently preferably an integer of 1 or more and 10 or less, more preferably 1 or more and 5 or less, more preferably 1 or more and 2 or less and even more preferably 1.

The total of the integers represented by c and d is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, more preferably 2 or more and 4 or less and even more preferably 2.

When c is 2 or more, plural units represented by R ⁴² to R ⁴⁵ may be present, and the plural units represented by R ⁴² may be the same or different, the plural units represented by R ⁴³ may be the same or may be different, the plural units represented by R ⁴⁴ may be the same or different, and the plural units represented by R ⁴⁵ may be the same or different.

When d is 2 or more, there may be plural units represented by R ⁴⁶ to R ⁴⁹ , and the plural units represented by R ⁴⁶ may be the same or different, the plural units represented by R ⁴⁷ may be the same or may be different, the plural units represented by R ⁴⁸ may be the same or different, and the plural units represented by R ⁴⁹ may be the same or different.

Examples of the amide compound represented by the general formula (IV) include an amide compound having two 2-hydroxyalkyl groups, examples of which include N, N-bis (2-hydroxyethyl) octanamide, N, N-bis (2 -hydroxyethyl) decanamide, N, N-bis (2-hydroxyethyl) dodecanamide, N, N-bis (2-hydroxyethyl) tetradecanamide, N, N-bis (2-hydroxyethyl) hexadecanamide, N, N-bis (2-hydroxyethyl ) octadecanamide (which is the same as the N, N-bis (2-hydroxyethyl) stearic acid amide), N, N-bis (2-hydroxyethyl) oleamide (which is the same as oleic diethanolamide), coconut oil diethanolamide, palm oil diethanolamide, castor oil diethanolamide and beef tallow diethanolamide, and an amide Compound having two polyalkylene oxide structures such as polyoxyethylene octylamide, polyoxyethylene decylamide, polyoxyethylene dodecylamide, polyoxyethylene tetradecylamide, polyoxyethylene hexadecylamide, polyoxyethylene stearylamide, polyoxyethylene oleylamide, polyoxyethylene tri-tallowamide, polyoxyethylene coconut fatty acid amide, polyoxyethylene palmitamide, polyoxyethylene laurylamide and ethylene oxide propylene oxide stearylamide. Among them, oleic diethanolamide is preferable.

As the amide-based friction modifier, the amide compound represented by the general formula (IV) may contain alone or in combination of two or more kinds.

Examples of the ether-based friction modifier include a (poly) glycerol ether compound, and more preferably, examples thereof include a (poly) glycerol ether compound having the following formula (V). As used herein, the (poly) glycerol ether compound means both a glycerol ether and a polyglycerol ether.

In the general formula (V), R ^{51 is} a hydrocarbon group and e is an integer of 1 or more and 10 or less.

Examples of the hydrocarbon group represented by R ⁵¹ include an alkyl group having a number of carbon atoms of 1 or more and 30 or less, an alkenyl group having a carbon number of 3 or more and 30 or less, an aryl group having a carbon number of 6 or more and 30 or less and an aralkyl group having a carbon number of 7 or more and 30 or less.

The alkyl group having a number of carbon atoms of 1 or more and 30 or less represented by R ⁵¹ may be linear-chain, branched-chain or cyclic. Specific examples of the alkyl group include groups of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl , Dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, 16-methylheptadecyl, cyclopentyl, cyclohexyl, methylcyclohexyl and cyclooctyl.

The alkenyl group having a number of carbon atoms of 3 or more and 30 or less represented by R ⁵¹ may be straight-chain, branched or cyclic, and the position of the double bond is arbitrary. Specific examples of the alkenyl group include a propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, Octadecenyl, oleyl, cyclopentenyl, cyclohexenyl, methylcyclopentenyl and methylcyclohexenyl groups.

Examples of the aryl group having a number of carbon atoms of 6 or more and 30 or less, represented by R ⁵¹ , include a phenyl, naphthyl, tolyl, xylyl, cumenyl, mesityl, ethylphenyl, propylphenyl, Butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl and nonylphenyl groups.

Examples of the aralkyl group having a number of carbon atoms of 7 or more and 30 or less represented by R ⁵¹ include a benzyl group, phenethyl group, naphthylmethyl group, benzhydryl group, trity group, methylbenzyl group and methylphenethyl group.

R ⁵¹ is preferably an alkyl group or alkenyl group having a number of carbon atoms of 8 or more and 20 or less in view of the ability, availability and the like of the (poly) glycerol ether compound having the general formula (V).

e shows the degree of polymerization of a (poly) glycerin as a starting material of the (poly) glycerol ether compound having the general formula (V), an integer of 1 or more and 10 or less, and is preferably an integer of 1 or more and 3 or less in view of achieving the high friction-reducing effect.

Examples of the (poly) glycerol ether compound represented by the general formula (V) include glycerol monododecyl ether, glycerin monotetradecyl ether, glycerin monohexadecyl ether (is the same as chimyl alcohol), glycerol monooctadecyl ether (same as batyl alcohol), glycerin monooleyl ether (same as selachyl alcohol), diglycerol monododecyl ether, diglycerol monotetradecyl ether, diglycerol monohexadecyl ether, Diglycerol monooctadecyl ether, diglycerol monooleyl ether, triglycerol monododecyl ether, triglycerol monotetradecyl ether, triglycerol monohexadecyl ether, triglycerol monooctadecyl ether, and triglycerol monooleyl ether.

As the ether-based modifier, the (poly) glycerol ether compound represented by the general formula (V) may be used alone or in combination of two or more kinds thereof.

The component (C) may be used alone or in combination of two or more kinds thereof, and a compound selected from the group consisting of compounds represented by the general formulas (II) to (V) may be used alone or in combination of two or more Species can be used. The preferable ranges of the total content of the component (C) when two or more kinds thereof are used in combination is the same as the preferable ranges thereof in the case where the component (C) is used alone.

<Additional components>

The lubricant oil composition may suitably contain additional additives such as a viscosity index improver, a pour point suppressant, a cleaning dispersant, antioxidant, friction modifier other than component (C) (hereinafter simply referred to as "additional friction modifier") or antiwear agents Extreme pressure agent, rust inhibitor, surfactant or demulsifier and an anti-foaming agent in such a range, if necessary, so that the object of this invention is not impaired.

Examples of the viscosity index improver include a polymethacrylate (PMA) -based viscosity index improver (such as a polyalkyl methacrylate and polyalkyl acrylate), an olefin copolymer-based (OCP) viscosity index improver (such as ethylene-propylene copolymer (EPC) and polybutylene and a styrene-based copolymer (such as polyalkylstyrene, styrene-diene copolymer, hydrogenated styrene-diene copolymer, styrene-maleic anhydride copolymer and styrene-isobutylene copolymer). Examples of the PMA-based viscosity index improver include a dispersion type and a non-dispersion type. The dispersion-type PMA-based viscosity index improver is a homopolymer of an alkyl methacrylate or an alkyl acrylate, and a non-dispersion type PMA-based viscosity index improver is a copolymer of an alkyl methacrylate or an alkyl acrylate and a polar monomer having dispersibility ( such as diethylaminoethyl methacrylate). Similar to the PMA-based viscosity index improver, the OCP-based viscosity index improver contains a dispersion type. The weight average molecular weight of the viscosity index improver is preferably 5,000 or more and 1,500,000 or less, and for the PMA-based viscosity index improver, the weight average molecular weight thereof is preferably 20,000 or more, and more preferably 100,000 or more, and is preferable 1,000,000 or less, and more preferably 800,000 or less. For the OCP-based viscosity index improver, the weight average molecular weight thereof is preferably 10,000 or more, and more preferably 20,000 or more, and is preferably 800,000 or less, and more preferably 500,000 or less. For the styrene-based copolymer, the weight-average molecular weight is preferably 10,000 or more, and more preferably 20,000 or more, and is preferably 800,000 or less, and more preferably 650,000 or less.

The viscosity index improver contains, for example, the above-mentioned polymer as a resin component, and is generally commercially available in the form of a solution containing the resin component with the polymer diluted with a diluent oil such as a mineral oil in terms of handling ability and the solubility in the above base oil. The concentration of the resin component of the viscosity index improver is generally 10 mass% or more and 50 mass% or less based on the total amount of the viscosity index improver.

The viscosity index improver may be used alone or as an arbitrary combination of two or more kinds thereof. The content of the viscosity index improver is preferably 0.01 mass% or more, more preferably 0.10 mass% or more, and further preferably 0.20 mass% or more, and is preferably 5.00 mass% or less, more preferably 2, 00 mass% or less, and more preferably 1.00 mass% or less, in terms of the content of the resin component based on the total amount of the lubricant oil composition.

Examples of the pour point suppressant include an ethylene-vinyl acetate copolymer, a chlorinated paraffin-naphthalene condensate, a chlorinated paraffin-phenol condensate, a polymethacrylate-based pour point depressant (such as polyalkyl methacrylate and polyalkyl acrylate), a polyalkyl styrene , Polyvinyl acetate and polybutene and the polymethacrylate-based pour point suppressant (for example, a polymethacrylate having a weight average molecular weight (Mw) of 5,000 or more and 50,000 or less) is preferred. The pour point suppressant may be used alone or as an arbitrary combination of two or more species. The content thereof is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more, and is preferably 5.0 mass% or less, and more preferably 1.0 mass% or less, based on the total amount of the lubricant oil composition.

The cleaning dispersant may be an ashless dispersant and / or a metal-based dispersant.

The ashless dispersant may be an arbitrary ashless dispersant used for a lubricant oil. Examples thereof include a monomeric succinimide compound having the following general formula (VI-i), a dimeric succinimide compound having the following general formula (VI-ii), polybutenylbenzylamine, polybutenylamine and derivatives such as a boric acid-modified derivative of these compounds. The ashless dispersant may be used alone or as an arbitrary combination of two or more kinds thereof.

In the general formula (VI-i) and the general formula (VI-ii), R ⁶¹ , R ⁶³ and R ^{64 are} each independently an alkenyl or alkyl group having a number-average molecular weight (Mn) of 500 or more and 3,000 Or less. The number average molecular weights of R ⁶¹ , R ⁶³ and R ⁶⁴ are each independently preferably 1000 or more and 3000 or less. R ⁶² , R ⁶⁵ and R ⁶⁶ each represents an alkylene group having a number of carbon atoms of 2 or more and 5 or less.

f is an integer of 1 or more and 10 or less, and g is an integer of 0 or 1 or more and 10 or less.

When the number-average molecular weight of R ⁶¹ , R ⁶³ and R ⁶⁴ is 500 or more, the solubility in the base oil can be increased and the number-average molecular weight thereof is 3000 or less, and the detergency can be prevented from deteriorating ,

Examples of the alkenyl group represented by R ⁶¹ , R ⁶³ and R ⁶⁴ include a polybutenyl group, polyisobutenyl group and an ethylene-propylene copolymer, and examples of the alkyl group shown herein include groups obtained by Hydrogenation of these groups.

Preferred examples of the alkenyl group include a polybutenyl group and a polyisobutenyl group. The polybutenyl group can be obtained by polymerizing a mixture of 1-butene and isobutene or isobutene with high purity. Preferred examples of the alkyl group include a group obtained by hydrogenating a polybutenyl group or a group obtained by hydrogenating a polyisobutenyl group.

In the general formula (VI-i), f is preferably an integer of two or more and 5 or less, and more preferably 3 or more and 4 or less. When f is 1 or more, the detergency can be enhanced, and when f is 10 or less, solubility in the base oil can be prevented from deteriorating.

In the general formula (VI-ii), g is preferably an integer of 1 or more and 4 or less, and more preferably 2 or more and 3 or less. The value of g within the range is preferable in view of the detergency and solubility in the base oil.

The alkenyl or alkyl succinimide compound can be produced, for example, by reacting an alkenyl succinic anhydride obtained by reacting a polyolefin and maleic anhydride or an alkyl succinic anhydride obtained by hydrogenating them with a polyamine.

The monomeric succinimide compound and the dimeric succinimide compound can be produced, for example, by changing the ratio of an alkenyl succinic anhydride or an alkyl succinic anhydride in the reaction with a polyamine.

The olefin monomer used for forming the polyolefin is preferably a kind or a mixture of two or more kinds of an α-olefin having a number of carbon atoms of 2 or 8 and 8 or less, and more preferably a mixture of isobutene and butene-1.

Examples of the polyamine include a simple diamine such as ethylenediamine, propylenediamine, butylenediamine and pentylenediamine; a polyalkylenepolyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine, tributylenetetramine and pentapentylenehexamine; and a piperazine derivative such as aminoethylpiperazine.

To the alkenyl or alkyl succinimide compound, a boron derivative of the compound and / or a compound obtained by modifying the compound with an organic acid can be used. The boron derivative of the alkenyl or alkyl succinimide compound can be produced by a usual method.

For example, the boron derivative can be obtained by reacting the polyolefin with maleic anhydride to give an alkenyl succinic anhydride, which is then imidized by further reaction with an intermediate obtained by reacting the polyamine with a boron compound such as boron oxide, boron halide, boric acid , Boric anhydride, borate ester and ammonium salt of boric acid.

When the boron derivative of the alkenyl or alkyl succinimide compound is used, the boron content of the boron derivative is not particularly limited, is preferably 0.05 mass% or more, and more preferably 0.10 mass% or more, and is preferable 5.0 mass% or less, and more preferably 0.3 mass% or less, in terms of boron.

The content of the succinimide compound expressed as nitrogen atom is preferably 200 mass ppm or more, and more preferably 300 mass ppm or more, and is preferably 4000 mass ppm or less, more preferably 3000 mass ppm or less, and further preferably 2500 Mass ppm or less based on the total amount of the lubricating oil composition. When the content thereof is 200 mass ppm or more, the effect thereof can be exhibited, and the content thereof is 4000 mass ppm or less, and the effect corresponding to the addition thereof can be obtained.

The succinimide compound has corrosivity for lead, and thus is not preferably added in an amount more than necessary, and for the simultaneous maintenance of the oxidation stability of the lubricant oil and the prevention of metal corrosion, it is necessary to appropriately form the imide compound select. From the viewpoint of suppressing corrosivity to lead, the succinimide compound is preferably a dimeric polybutenyl succinimide compound having a polybutenyl group having a number-average molecular weight of 900 or more, preferably in an amount of 60 mass% or more, and more preferably 70 mass% or more, based on the total amount of nitrogen of the succinimide compound.

The succinimide compound may be used alone or in combination of two or more kinds thereof.

As the metal-based detergent, any arbitrary alkaline earth metal-based cleaning agent used for a lubricant oil may be used, and examples thereof include one or more kinds thereof selected from the group consisting of alkaline earth metal sulfonate, alkaline earth metal phenate, and alkaline earth metal salicylate.

Examples of the alkaline earth metal sulfonate include an alkaline earth metal salt having an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound, and preferred examples thereof include a magnesium salt and / or calcium salt thereof, and more preferable examples thereof include a calcium salt thereof.

Examples of the alkaline earth metal phenate include an alkaline earth metal salt of an alkylphenol, an alkylphenol sulfide or a Mannich reaction product of an alkylphenol, more preferable examples of which include a magnesium salt and / or a calcium salt thereof, and further preferred examples thereof include a calcium salt thereof.

Preferred examples of the alkaline earth metal salicylate include an alkaline earth metal salt of an alkylsalicylic acid, more preferably, examples thereof include a magnesium salt and / or a calcium salt thereof, and further preferred examples thereof include a calcium salt thereof.

The alkyl group constituting the alkaline earth metal-based detergent is preferably an alkyl group having a carbon number of 4 or more and 30 or less, and more preferably an alkyl group having a carbon number of 6 or more and 18 or less, and the alkyl group may be linear-chain or branched. The alkyl group may be a primary, secondary or tertiary alkyl group.

The alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate include: not only a neutral alkaline earth metal sulfonate, a neutral alkaline earth metal phenate and a neutral alkaline earth metal salicylate obtained, for example, the alkylaromatic sulfonic acid, the phenol, the alkylphenol sulfide, the Mannich reaction product of an alkylphenol, the alkylsalicylic acid and the like described above are directly reacted with an alkaline earth metal base such as an oxide or hydroxide of an alkaline earth metal, for example, magnesium and / or calcium, or converted to an alkali metal salt such as sodium salt and potassium salt, which is then substituted with an alkaline earth metal salt; but also a basic alkaline earth metal sulfonate, alkaline earth alkaline metal phenate and basic alkaline earth metal salicylate obtained in such a way that the neutral alkaline earth metal sulfonate, the neutral alkaline earth metal phenate and the neutral alkaline earth metal salicylate are heated with an excess amount of an alkaline earth metal salt or an alkaline earth metal base in the presence of water; and an overbased alkaline earth metal sulfonate, an overbased alkaline earth metal phenate, and an overbased alkaline earth metal salicylate obtained by reacting the neutral alkaline earth metal sulfonate, the neutral alkaline earth metal phenate, and the neutral alkaline earth metal salicylate with a carbonate salt or borate salt of an alkaline earth metal in the presence of carbon dioxide gas.

The metal-based detergent used in the present invention may be one or more selected from the group consisting of the neutral salts, the basic salts and the overbased salts described above, and a mixture of one or more from overbased salicylate, overbased phenate, and overbased sulfonate, with the neutral sulfonate being preferred in terms of detergency and abrasion resistance.

The metal-based cleaner is generally put on the market in the form of a dilution with a light base lubricant oil or the like, and is commercially available, and the metal content thereof is, for example, 1.0 mass% or more and 20 mass% or less and preferred 2.0 mass% or more and 16.0 mass% or less.

The base number of the metal-based detergent used in the present invention is preferably 10 mgKOH / g or more, and more preferably 15 mgKOH / g or more, and is preferably 500 mgKOH / g or less, and more preferably 450 mgKOH / g or less. The metal-based detergent selected from these materials may be used alone or in combination of two or more kinds thereof. The base number given herein means a base number according to the potentiometric titration method (base number perchloric acid method) measured in accordance with JIS K2501, Petroleum products and lubricants, Determination of neutralization number.

The metal-based detergent may be contained alone or as an arbitrary combination of two or more kinds thereof. The content thereof is preferably 0.01 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more, and is preferably 10 mass% or less, more preferably 5.0 mass% or less and more preferably 3.0 mass% or less, based on the total amount of the lubricant oil composition.

Examples of the antioxidant include a phenol-based, amine-based antioxidant, or molybdenum amine-based antioxidant antioxidant.

Examples of the phenol-based antioxidant include 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-bis (2,6-di-tert-butylphenol), 4,4'-bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4, 4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-isopropylidenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-diisocyanate 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-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], and a benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C7 -C9 branched alkyl esters. Among them, the phenol-based antioxidant of the bisphenol-based antioxidant and the phenol-based antioxidant having an ester group are preferable.

The phenol-based antioxidant may be contained alone or in an arbitrary combination of two or more kinds thereof. The content thereof is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and further preferably 0.10 mass% or more, and is preferably 10 mass% or less, more preferably 5.0 mass% or less and more preferably 3.0 mass% or less, based on the total amount of the lubricant oil composition.

Examples of the amine-based antioxidant include a monoalkyldiphenylamine-based antioxidant such as monooctyldiphenylamine and monononyldiphenylamine, a dialkyldiphenylamine-based antioxidant such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4 '-Diheptyldiphenylamine, 4,4'-diocyldiphenylamine and 4,4'-dinonyldiphenylamine, a polyalkyldiphenylamine-based antioxidant such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraocyldiphenylamine and tetranonyldiphenylamine, a phenylenediamine-based antioxidant such as N, N'-diisopropyl-p-phenylenediamine , N, N'-diphenyl-p-phenylenediamine and N-cyclohexyl-N'-phenyl-p-phenylenediamine; and a naphthylamine-based antioxidant such as α-naphthylamine, phenyl-α-naphthylamine and an alkyl-substituted phenyl-α-naphthylamine, for example, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl α-naphthylamine, octylphenyl-α-naphthylamine and nonylphenyl-α-naphthylamine. Among them, the amine-based antioxidant of the dialkyldiphenylamine-based antioxidant and the naphthylamine-based antioxidant are preferred.

The amine-based antioxidant may be contained alone or as an arbitrary combination of two or more kinds thereof. The content thereof is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and further preferably 0.10 mass% or more, and is preferably 10 mass% or less, more preferably 5.0 mass% or less and more preferably 3.0 mass% or less, based on the total amount of the lubricant oil composition.

The molybdenum amine complex-based antioxidant may be a hexavalent molybdenum compound, specifically, a compound obtained by reacting molybdenum trioxide and / or molybdic acid with an amine compound such as a compound obtained by the production method according to JP 2003-252887 A ,

The amine compound which is reacted with a hexavalent molybdenum compound is not particularly limited, and examples thereof include a monoamine, diamine, polyamine and alkanolamine. Specific examples thereof include an alkylamine having an alkyl group having a carbon number of 1 or more and 30 or less (wherein the alkyl group may be linear or branched), such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine and methylpropylamine; an alkenylamine having an alkenyl group having a carbon number of 2 or more and 30 or less (wherein the alkenyl group may be linear or branched) such as ethenylamine, propenylamine, butenylamine, octenylamine and oleylamine; an alkanolamine having an alkanol group having a number of carbon atoms of 1 or more and 30 or less (wherein the alkanol group may be linear or branched) such as methanolamine, ethanolamine, methanolethanolamine and methanolpropanolamine; an alkylenediamine having an alkylene group having a carbon number of 1 or more and 30 or less, such as methylenediamine, ethylenediamine, propylenediamine and butylenediamine; a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; a compound obtained by substituting an alkyl group or alkenyl group having a number of carbon atoms of 8 or more and 20 or less on the monoamine, diamine or polyamine as described above, such as undecyldiethylamine, undecaldiethanolamine, dodecyldipropanolamine, oleyldiethanolamine, oleylpropylenediamine and stearyltetraethylenepentamine; a heterocyclic compound such as an imidazoline; an alkylene oxide adduct of these compounds; and mixtures thereof. Examples thereof further include a sulfur-containing molybdenum complex of succinimide described in JPH3-22438 B and US Pat JP 2004-2866 A ,

The antioxidant may be contained alone or as an arbitrary combination of two or more kinds thereof, and the phenol-based antioxidant and / or amine-based antioxidant are preferably used.

The total content of the antioxidant is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and further preferably 0.10 mass% or more, and is preferably 10 mass% or less, more preferably 5.0 mass% or less, and more preferably 3.0 mass% or less, based on the total amount of the lubricant oil composition.

Specific examples of the additional friction modifier and the anti-abrasion agent include a sulfur-based compound such as a dialkyl polysulfide, diarylalkyl polysulfide and diaryl polysulfide; a phosphorus-based compound such as a phosphate ester, thiophosphate ester, phosphite ester, alkyl hydrogen phosphite, phosphate ester salt and phosphite ester salt; and a metal-based organic compound such as zinc dialkyldithiophosphate (ZnDTP), zinc dithiocarbamate (ZnDTC), molybdenum oxysulfide, organophosphorodithioate (MoDTP) and molybdenum oxysulfide dithiocarbamate (MoDTC). The friction modifier and the anti-abrasion agent may be contained alone or as an arbitrary combination of two or more kinds thereof.

The additional friction modifier and the anti-abrasion agent are preferably used so that the metal content and the sulfur content in the lubricant oil composition are reduced as much as possible, and the content thereof is preferably 5.0 mass% or less, more preferably 3.0 mass%. or less, and more preferably 1.5 mass% or less, based on the total amount of the lubricant oil composition. When the additional friction modifier and the anti-abrasion agent are used, the content thereof is preferably 0.01 mass% or more based on the total amount of the lubricant oil composition.

In view of the suppression of corrosivity for copper, the content, expressed as molybdenum atom, of the sulfur-containing compound such as molybdenum oxysulfide dithiocarbamate (MoDTC) as an additional friction modifier is preferably less than 0.02 mass% and more preferably 0.01 mass% or less to the total amount of the lubricating oil composition, and it is further preferable that the compound is not contained.

Examples of the extreme pressure agent include a sulfur-based compound such as an olefin sulfide, dialkyl polysulfide, diarylalkyl polysulfide and diaryl polysulfide; and a phosphorus-based compound such as a phosphate ester, thiophosphate ester, phosphite ester, alkyl hydrogen phosphite, phosphate ester salt and phosphite ester salt. The extreme pressure medium may be contained alone or as an arbitrary combination of two or more species.

When the extreme pressure medium is used, the content of the extreme pressure medium is preferably 0.01 mass% or more and 10 mass% or less based on the total amount of the lubricant oil composition.

Examples of the rust inhibitor include a petroleum sulfonate, alkylbenzenesulfonate, dimethylnaphthalenesulfonate, alkenylsuccinate ester and a polyhydric alcohol ester. The rust inhibitor may be contained alone or as an arbitrary combination of two or more kinds thereof. The content of the rust inhibitor is preferably 0.01 mass% or more and 1.00 mass% or less, and more preferably 0.05 mass% or more and 0.50 mass% or less, based on the total amount of the lubricant oil composition in view on the effect of it.

Examples of the surfactant or the demulsifier include a polyalkylene glycol-based nonionic surfactant such as a polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether and polyoxyethylene alkyl naphthyl ether. The surfactant or demulsifier may be contained alone or as an arbitrary combination of two or more kinds thereof.

Examples of the anti-foaming agent include a silicone oil such as dimethylpolysiloxane, a fluorosilicone oil and a fluoroalkyl ether. The anti-foaming agent may be contained alone or as an arbitrary combination of two or more kinds. The content of the anti-foaming agent is preferably 0.001 mass% or more, and more preferably 0.005 mass% or more, and is preferably 0.150 mass% or less, and more preferably 0.100 mass% or less, based on the total amount of the lubricant oil composition in terms of balance between the anti-foaming effect and the economical efficiency and the like.

[Production Method of Lubricating Oil Composition for Internal Combustion Engine]

worin in der allgemeinen Formel (I) R¹ ein Wasserstoffatom oder eine Kohlenwasserstoff-Gruppe mit einer Zahl von Kohlenstoffatomen von 1 oder mehr und 9 oder weniger ist, die zumindest eine Art von einem Atom enthalten kann, ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom, Schwefelatom und Stickstoffatom; und R² ein Wasserstoffatom oder eine Kohlenwasserstoff-Gruppe mit einer Zahl von Kohlenstoffatomen von 1 oder mehr und 16 oder weniger ist, die zumindest eine Art eines Atoms enthalten kann, ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom, Schwefelatom und Stickstoffatom, (B) eine Epoxy-Verbindung und (C) einen aschelosen Friktionsmodifizierer, worin der aschelose Friktionsmodifizierer (C) in einer Menge von 0,20 mass% oder mehr auf der Basis der Gesamtmenge der Schmiermittelölzusammensetzung enthalten ist.A production method of a lubricant oil composition as an embodiment of this invention comprises mixing a base oil with (A) a benzotriazole derivative represented by the general formula (I):

wherein in the general formula (I), R ^{1 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 9 or less, which may contain at least one kind of one atom selected from the group consisting of an oxygen atom , Sulfur atom and nitrogen atom; and R ^{2 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 16 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom, (B) an epoxy compound and (C) an ashless friction modifier, wherein the ashless friction modifier (C) is contained in an amount of 0.20 mass% or more based on the total amount of the lubricant oil composition.

In a production method of a lubricating oil composition for an internal combustion engine as an embodiment of this invention, an additional component other than the components (A) to (C) may be further mixed.

The base oil, the components (A) to (C) and the additional components are the same as those described above for the lubricant oil composition, a lubricant oil composition produced by the production method is also the same as described above, and thus the descriptions will be omitted from it.

In the production process, the components (A) to (C) and the additional component may be mixed with the base oil in any method, and the mixing method is not limited.

[Lubricating method using the lubricant oil composition]

Examples of the lubricating method using a lubricating oil composition as an embodiment of this invention include a method of loading the lubricating oil composition as an embodiment of this invention into an internal combustion engine such as an engine and lubricating the parts of the internal combustion engine. More preferred examples thereof include a method of charging the lubricating oil composition into an internal combustion engine, including parts containing copper and / or lead, and lubricating the parts of the internal combustion engine.

[Applications of Lubricating Oil Composition]

The lubricant oil composition as an embodiment of this invention can be advantageously used as a lubricant oil for an internal combustion engine such as gasoline engine, diesel engine and gas engine for an automobile such as a two-wheeled or four-wheeled vehicle, a power generator, for seagoing ships and the like. The lubricating oil composition can more advantageously be used as lubricant oil for lubricating an internal combustion engine containing parts with copper and / or lead.

The lubricant oil composition as an embodiment of this invention has an excellent friction reducing effect irrespective of the use of an ashless friction modifier as a friction modifier, and is therefore advantageous for an application requiring the reduction of a metal-based friction modifier such as MoDTC, for example, as a lubricant oil composition for one internal combustion engine under strict environmental regulations such as gasoline engine, diesel engine, engine using dimethyl ether as fuel and gas engine.

For example, the API standard and JASO standard, which are the official standards for a diselen motor oil, contain the "Cummins Corrosion Test (ASTM D6594)", and to meet these standards it is necessary to set the elution levels of copper and lead to specific values and suppress less.

The lubricating oil composition as an embodiment of this invention can be advantageously used for lubricating parts of the internal combustion engine by charging in the internal combustion engine.

Examples

This invention will be explained with reference to examples, but this invention is not limited thereto.

In the specification, the measurements of the properties of the starting materials used in Examples and Comparative Examples were determined according to the procedures described below.

Kinematic viscosity

The kinematic viscosity was a value measured according to JIS K2283 using a glass capillary viscometer.

viscosity Index

The viscosity index was a value measured according to JIS K2283.

NOACK value

The NOACK value was a value measured according to the method of ASTM D5800 (250 ° C, 1 hour).

Ring analysis (% C _A and% C _P )

The ratio (percentage) of an aromatic component and the ratio (percentage) of a paraffin component, calculated by the Ring Analysis ndM method, represented by% C _A and% C _P respectively, were measured according to ASTM D3238.

Sulfur content

The sulfur content was a value measured according to JIS K2541-6.

Contents of zinc atoms, calcium atoms, boron atoms and phosphorus atoms

The contents of the atoms were values measured according to JPI-5S-38-2003.

Content of nitrogen atoms

The content of nitrogen atoms was a value measured according to JIS K2609.

base number

The base number was a value measured by the potentiometric titration method (base number perchloric acid method) according to JIS K2501: 2003.

Weight average molecular weight (Mw) of the styrene-isobutylene copolymer

• Anlage: „GPC-900“-Säule (Produktname, hergestellt von JASCO-Corporation).
• Säule: „TSK gel GMH6“ (Produktname, hergestellt von Tosoh Corporation) x 2
• Lösungsmittel: THF
• Temperatur: 40°C
• Probenkonzentration: 0,5 mass%
• Kalibrierungskurve: Polystyrol
• Detektor: Differential-Refraktometerdetektor

The weight average molecular weight (Mw) was a value measured under the following condition and calculated with the polystyrene calibration curve, and was measured specifically under the following condition.

• Plant: "GPC-900" column (product name, manufactured by JASCO Corporation).
• Column: "TSK gel GMH6" (product name, manufactured by Tosoh Corporation) x 2
• Solvent: THF
• Temperature: 40 ° C
• Sample concentration: 0.5 mass%
• Calibration curve: polystyrene
• Detector: differential refractometer detector

The evaluation results for the lubricating oil compositions of Examples and Comparative Examples were as follows.

[Friction-reducing effect]

"High Friction Friction Machine TE77" (manufactured by Phoenix Tribology, Ltd.) was preconditioned with a test plate (material: SUJ-2, shape: 58 mm length x 37 mm width x 4 mm thickness) and a test cylinder. Pin (material: SUJ-2, shape: 15 mm diameter x 22 mm length) under conditions of an amplitude of 8 mm, a frequency of 10 Hz, an oil temperature of 80 ° C and a loading range of 50 N carried out for 10 minutes ,

Thereafter, the friction coefficient was measured under conditions of an amplitude of 8 mm, a frequency of 10 Hz, an oil temperature of 80 ° C, a load of 100 N and an operating time of 30 minutes, to evaluate the friction-reducing effect.

[Corrosion Test]

100 ml of a lubricating oil composition was placed in a glass test tube (40 mm diameter x 30 mm length) and a copper plate (25 mm x 25 mm x 1 mm) and a lead plate (25 mm x 25 mm x 1 mm) were polished and sealed in the test oil was dipped and the corrosion test was performed. The test was carried out at an oil temperature of 135 ° C for 168 hours while blowing the air at a flow rate of 5 l / h. The result was evaluated by the elution amount of copper and the elution amount of lead. The elution amounts of copper and lead were evaluated according to JPI-5S-38-2003.

[Examples 1 to 9 and Comparative Examples 1 to 11]

Lubricating oil compositions of Examples and Comparative Examples with the base oil and the components shown in Tables 2 and 3 were prepared by mixing the base oil and the components corresponding to the formulations shown in Tables 2 and 3. The lubricating oil compositions of Examples and Comparative Examples were evaluated according to the above-mentioned evaluation standards. The results obtained are shown in Tables 2 and 3.

The components according to Tables 1 to 3 are as follows.

<Base Oil>

Base oil: Hydrorefined base oil, 40 ° C Kinematic viscosity: 21 mm ² / s, 100 ° C Kinematic viscosity: 4.5 mm ² / s, Viscosity index: 135, Sulfur content: 1 ppm by mass, NOACK value: 12, 6 mass%, ndM-ring analysis:% C _A : 0.0% Cp: 78.7.

<Component (A), benzotriazole derivative having the general formula (I)>

Copper deactivator 1: (4 or 5) -methylbenzotriazole (benzotriazole derivative having the general formula (I) wherein R ^{1 is} a methyl group and R ^{2 is} a hydrogen atom.

Copper deactivator 2: 1,2,3-benzotriazole (benzotriazole derivative having the general formula (I) wherein R ¹ and R ^{2 are} a hydrogen atom).

Component (B), epoxy compound>

Lead deactivator 1: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate

Lead deactivator 2: 1,2-epoxyhexadecane

<Component (C), more frictionless modifier>

Ester-based friction modifier: glycerol monooleate (is the same as glycerol-1-oleate).

Amine-based friction modifier: oleyldiethanolamine

Amide-based friction modifier: oleic diethanolamide

Ether-Based Friction Modifier: "KIKU-LUBE (Trade Name) FM-618C" (Product of ADEKA Corporation, Oleyl Polycelyl Ether)

<Additional component>

Copper deactivator 2: "IRGAMET (trade name) 39" (manufactured by BASF AG, 1- (N, N-bis (2-ethylhexyl) aminomethyl) methylbenzotriazole, benzotriazole derivative having general formula (I) wherein R ^{1 is} a Methyl group and R ^{2 is} a hydrocarbon group having a carbon number of 17 with a nitrogen atom).

<Additional additives>

Viscosity index improver: styrene-isobutylene copolymer, weight average molecular weight (Mw): 580,000, resin amount: 10 mass%

Pour point suppressant: polymethacrylate

Metal-based cleaning agent 1: calcium sulfonate, base number (perchloric acid method): 17 mgKOH / g, calcium content 2.4 mass%.

Metal-based cleaning agent 2: calcium salicylate, base number (perchloric acid method): 225 mgKOH / g, calcium content 7.8 mass%.

Metal-based cleanser 3: calcium salicylate, base number (perchloric acid method): 350 mgKOH / g, calcium content 12.5 mass%.

Anti-wear agent: zinc dialkyldithiophosphate, zinc content: 9.0 mass%, phosphorus content: 8.2 mass%, sulfur content: 17.1 mass%.

Phenol-based antioxidant: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

Amine-based antioxidant: dialkyldiphenylamine, nitrogen content: 4.6 mass%.

Ashless dispersant 1: polybutenyl succinimide, nitrogen content: 1.0 mass%

Ashless dispersant 2: boron derivative of polybutenyl succinimide, nitrogen content: 1.2 mass%, boron content: 1.3 mass%.

Anti-foaming agent: dimethylpolysiloxane

The blending amounts of the additional additives are in Table 1 shown. Table 1 component Mixing rate (mass%) ^{* 1} Viscosity index improvers 7.00 Pour point depressant 0.20 Detergents based on metal 1 0, 65 Detergents based on metal 2 1, 00 Detergents based on metal 3 0.80 Anti-abrasive 1.10 Phenol-based antioxidant 0, 50 Antioxidant based on amine 0, 90 Ashless dispersant 1 5, 00 Ashless dispersant 2 1, 00 Anti-foaming agents 0.10 total 18.25 * 1: Mixing amount based on the total amount of the lubricant oil composition Table 2 unit Example 1 Ex. 2 Example 3 Example 4 Example 5 formulation base oil - rest rest rest rest rest Component (A) Copper deactivator 1 mass% 0, 05 0, 05 0, 02 0.05 0.10 Copper deactivator 2 mass% - - - - - Component (B) Lead deactivator 1 mass% 0, 30 0.50 0, 30 0, 30 0.30 Lead deactivator 2 mass% - - - - - Component (C) Ester-based friction modifier mass% 0, 30 0, 60 - - - Friction modifier based on amine mass% - - 0, 60 - - Amide-based friction modifier mass% - - - 0, 60 - Ether-based friction modifier mass% - - - - 0, 60 Copper deactivator 3 mass% - - - - - Additional additives mass% 18.25 18.25 18.25 18.25 18.25 total mass% 100.00 100.00 100.00 100.00 100.00 Properties of the composition Corrosion Test Copper (Cu) -eluted amount Mass ppm twelve 9 17 16 7 Lead (Pb) -elevated amount Mass ppm 18 23 24 less than 10 30 Friction Test friction coefficient - 0,117 0.115 0.105 0.112 0.115 Table 2 (continued) unit Example 6 Example 7 Ex. 8 Ex. 9 formulation base oil - rest rest rest rest Component (A) Copper deactivator 1 mass% 0.05 0.05 0.05 - Copper deactivator 2 mass% - - - 0.05 Component (B) Lead deactivator 1 mass% - 0.10 0.30 0.30 Lead deactivator 2 mass% 0, 30 - - - Component (C) Ester-based friction modifier mass% 0, 60 0, 60 0, 60 0, 60 Friction modifier based on amine mass% - - - - Amide-based friction modifier mass% - - - - Ether-based friction modifier mass% - - - - Copper deactivator 3 mass% - - - - Additional additives mass% 18.25 18.25 18.25 18.25 total mass% 100.00 100.00 100.00 100.00 Properties of the composition Corrosion Test Copper (Cu) -eluted amount Mass ppm 18 10 15 twelve Lead (Pb) -elevated amount Mass ppm 38 44 27 30 Friction Test friction coefficient - 0.114 0.114 0.115 0,117 Table 3 unit CEx. 1 CEx. 2 CEx. 3 CEx. 4 CEx. 5 formulation base oil - rest rest rest rest rest Component (A) Copper deactivator 1 mass% - - - - - Copper deactivator 2 mass% - - - - - Component (B) Lead deactivator 1 mass% 0.30 0.30 0, 30 0, 30 0, 30 Lead deactivator 2 mass% - - - - - Component (C) Ester-based friction modifier mass% 0, 30 - - - 0.30 Friction modifier based on amine mass% - 0, 30 - - - Amide-based friction modifier mass% - - 0, 30 - - Ether-based friction modifier mass% - - - 0, 30 - Copper deactivator 3 mass% 0.05 0.05 0, 05 0.05 - Additional additives mass% 18, 25 18.25 18.25 18.25 18.25 total mass% 100.00 100.00 100.00 100.00 100.00 Properties of the composition Corrosion Test Copper (Cu) -eluted amount Mass ppm 100 73 63 104 80 Lead (Pb) -elevated amount Mass ppm 40 21 32 21 33 Friction Test friction coefficient - 0,117 0.108 0.115 0,117 0.116 Table 3 (continued) unit CEx. 6 CEx. 7 CEx. 8th CEx. 9 CEx. 10 CEx. 11 formulation base oil - rest rest rest rest rest rest Component (A) Copper deactivator 1 mass% - - - - - - Copper deactivator 2 mass% - - - - - - Component (B) Lead deactivator 1 mass% - - - - - - Lead deactivator 2 mass% - - - - - - Component (C) Ester-based friction modifier mass% 0.30 - - - 0.10 - Friction modifier based on amine mass% - 0.30 - - - - Amide-based friction modifier mass% - - 0.30 - - - Ether-based friction modifier mass% - - - 0, 30 - - Copper deactivator 3 mass% 0, 05 0.05 0.05 0.05 - - Additional additives mass% 18.25 18, 25 18.25 18.25 18.25 18.25 total mass% 100.00 100.00 100.00 100.00 100.00 100.00 Properties of the composition Corrosion Test Copper (Cu) -eluted amount Mass ppm 17 32 28 25 35 18 Lead (Pb) -elevated amount Mass ppm 174 112 103 108 72 52 Friction Test friction coefficient - 0.118 0.109 0,119 0,120 0,129 0.132

From the results of Tables 2 and 3, it can be seen that it was confirmed that the lubricating oil compositions of Examples 1 to 9 were excellent in the friction-reducing action and corrosion-suppressing action of parts containing copper and lead.

On the other hand, it was confirmed that the lubricant oil composition of Comparative Examples 1 to 11 did not have a good corrosion-suppressing effect of the parts containing copper and lead.

Specifically, the following things were confirmed. The values of the contents of the additives in the following description are each a content based on the total amount of the lubricant oil composition.

The lubricant oil composition of Comparative Example 11 did not contain the components (A) to (C), but contained only the base oil and the additional additives, and it was found that in this case a sufficient friction reducing effect was not obtained and the composition as a lubricant oil composition was not beneficial.

The lubricant oil composition of Comparative Example 10 contained 0.10 mass% of the component (C) in addition to the base oil and the additional additives, but a sufficient friction reducing effect was not obtained because the content of the component (C) was only 0.10 mass%. was. Due to the contained component (C), such a result was obtained that the corrosion of copper and lead progressed further as compared with the lubricant oil composition of Comparative Example 11 irrespective of the small content of the component (C).

The lubricant oil compositions of Comparative Examples 6 to 9 contained 0.30 mass% of the component (C) different from each other in addition to the base oil and the additional additives, and further contained 0.05 mass% of the copper deactivator 3. In Comparative Examples 6 to 9, such a result was obtained that a friction reducing effect was obtained by the large content of the component (C) of 0.30 mass%, but the corrosion of lead progressed because the components (A) and (B) progressed. not included.

The lubricant oil composition of Comparative Example 5 contained 0.30 mass% of the lead deactivator as the component (B) instead of the copper deactivator in the lubricant oil composition of Comparative Example 6, and in this case, such a result was obtained that the corrosion of lead was suppressed. but the corrosion of copper continued.

The lubricant oil composition of Comparative Example 1 contained 0.05 mass% of the copper deactivator 3 and 0.30 mass% of the lead deactivator 1 as the component (B) for obtaining the corrosion-suppressing effects of copper and lead simultaneously. Such a result was surprisingly obtained that the corrosion of copper significantly occurred with the lubricant oil composition of Comparative Example 1.

Similarly, the lubricant oil compositions of Comparative Examples 2 to 4 wherein the kind of the component (C) used in Comparative Example 1 was changed, such a result that the corrosion of copper was not sufficiently suppressed, same as in Comparative Example 1.

On the other hand, the lubricating oil compositions of Examples 1 to 9 of this invention contained the ashless friction modifier as component (C) in a large amount, thus providing an excellent friction-reducing effect. Further, it was confirmed that regardless of the large amount of the component (C), excellent corrosion-suppressing effect of the parts with copper and lead was obtained due to the contained components (A) and (B).

Further, it was surprisingly confirmed that the lubricating oil compositions of Examples 1 to 9 of this invention have excellent corrosion-suppressing action of copper and lead even compared to the lubricant oil composition of Comparative Example 11 which did not contain the components (A) to (C). Accordingly, it was confirmed that not only the above-mentioned drawback caused by the combination use of the copper deactivator and the lead deactivator was avoided, but also a lubricating oil composition was obtained which had the friction-reducing effect and also with respect to the Corrosion suppression effect of parts containing copper and lead was excellent due to the synergistic effect of the combination of components (A) and (B) independently of the ashless friction modifier used in the lubricant oil composition.

Industrial applicability

The lubricant oil composition of this invention is a lubricant oil composition which uses an ashless friction modifier and is excellent in the friction-reducing action and also the corrosion-suppressing effect of copper and lead. As a result, is the lubricating oil composition is advantageous as a lubricating oil composition for parts containing copper and lead, and is more advantageous as a lubricating oil composition for an internal combustion engine using the parts. Further, the lubricating oil composition has an excellent friction reducing effect irrespective of the action of an ashless friction modifier as a friction modifier and is therefore advantageous for an application requiring a reduction of a metal-based friction modifier such as MoDTC, for example, as a lubricating oil composition for an internal combustion engine under severe Environmental regulations such as gasoline engine, diesel engine, engine using dimethyl ether as fuel and gas engine.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• JP 2008106199 A [0008]
• WO 2011/161982 [0008]
• JP 2012201807 A [0008]
• WO 2008/047550 [0008]
• JP 2003252887 A [0159]
• JP 2004002866 A [0160]

Claims (9)

A lubricant oil composition containing: a base oil, (A) a benzotriazole derivative having the general formula (I):

wherein R ^{1 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 9 or less, which may contain at least one kind of one atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom; and R ^{2 is} a hydrogen atom or a hydrocarbon group having a number of carbon atoms of 1 or more and 16 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, sulfur atom and nitrogen atom, (B) an epoxy compound and (C) an ashless friction modifier, wherein the ashless friction modifier (C) is contained in an amount of 0.20 mass% or more based on the total amount of the lubricant oil composition. Lubricating oil composition according to Claim 1 wherein a content of the component (A) is 0.01 mass% or more and 0.15 mass% or less based on the total amount of the lubricant oil composition. Lubricating oil composition according to Claim 1 or 2 wherein a content of the component (B) is 0.05 mass% or more and 1.00 mass% or less based on the total amount of the lubricant oil composition. Lubricating oil composition according to one of Claims 1 to 3 wherein R ² in the general formula (I) is a hydrogen atom or a hydrocarbon group having a carbon atom number of 1 or more and 8 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom , Sulfur atom and nitrogen atom. Lubricating oil composition according to one of Claims 1 to 4 wherein R ¹ in the general formula (I) is a hydrogen atom or a hydrocarbon group having a carbon number of 1 or more and 5 or less, which may contain at least one kind of atom selected from the group consisting of an oxygen atom, Sulfur atom and nitrogen atom. Lubricating oil composition according to one of Claims 1 to 5 wherein R ² in the general formula (I) is a hydrogen atom. Lubricating oil composition according to one of Claims 1 to 6 wherein R ¹ in the general formula (I) is a methyl group or a halogen atom. Lubricating oil composition according to one of Claims 1 to 7 wherein the component (B) is at least one selected from the group consisting of an epoxy compound having a number of carbon atoms of 3 or more with a linear or branched alkyl group and an alicyclic epoxy compound. Lubricating oil composition according to one of Claims 1 to 8th wherein component (B) is an alicyclic epoxy compound.