JP5565999B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition capable of reducing lubricating resistance and further improving the energy saving performance of the lubricating oil, and more specifically, SAE xW-30 grade lubricating oil for internal combustion engines, In particular, the present invention relates to a lubricating oil composition that is suitable for diesel engine oil and that can reduce its lubricating resistance in the same viscosity grade and further improve fuel efficiency.

Engine oil is required to improve fuel efficiency from the viewpoint of environmental problems such as reduction of carbon dioxide emissions. Therefore, blending of a friction reducing agent such as MoDTC, a high molecular weight viscosity index improver, etc. (see, for example, Patent Document 1), and lowering the viscosity and increasing the viscosity index of a lubricating oil are being promoted. Here, a friction reducing agent such as MoDTC has a poor fuel saving performance and is not dependent on a friction modifier because the friction reducing effect is remarkably hindered when soot is mixed like diesel engine oil. Basic formulation, that is, lowering the viscosity of the lubricating oil and improving the viscosity index are important.
However, in lubricating oils used under severe sliding conditions, such as diesel engine oil, lowering the viscosity increases wear at sliding parts, promotes deterioration due to increased evaporation loss, and exhaust gas properties. Since it is a cause of deterioration, it is difficult to reduce the viscosity as in the SAE xW-20 grade (see, for example, Patent Document 2). Therefore, in diesel engine oil, the viscosity grade of SAE (xW-) 30 grade or higher is mainly used. Improvements are underway.
In order to improve the fuel economy performance of lubricating oils, lowering the viscosity of the base oil and increasing the viscosity index of the composition are the most common. Expected to decrease the kinematic viscosity after shearing, improving the high molecular weight polymethacrylate viscosity index It is most effective to add a certain amount of the agent. However, since the rate of decrease in kinematic viscosity after shearing in such a case is usually about 20% or more, the kinematic viscosity of the composition is set higher in advance in order to maintain the same viscosity grade even after shearing. It was necessary to keep. When such a method is used, there is a limit in improving fuel economy in all processes from the initial stage to the long-term use.
JP-A-8-302378 JP 2001-181664 A

  SUMMARY OF THE INVENTION In view of the circumstances as described above, an object of the present invention is to provide a lubricating oil composition that can further reduce the lubricating resistance in the same viscosity grade and further improve the energy saving performance of the lubricating oil, for example, SAE xW-30 grade internal combustion engine. It is intended to provide a lubricating oil composition capable of reducing the lubricating resistance of a lubricating oil for a vehicle, particularly a diesel engine oil, and further improving the fuel saving performance.

  As a result of intensive studies to solve the above problems, the present inventors have increased the viscosity index of the composition beyond a specific level in a lubricating oil of the same viscosity grade, and at a certain level the viscosity reduction rate after shearing of the composition. It has been found that the above problems can be improved by blending a viscosity index improver so as to be as follows, and the present invention has been completed.

That is, the present invention provides a lubricating base oil with a viscosity index improver having a PSSI of 30 or less, a composition having a viscosity index of 160 or more, and a 100 ° C. kinematic viscosity reduction rate after shearing of 15% or less. It is related with the lubricating oil composition characterized by mix | blending.
The present invention also relates to the lubricating oil composition, wherein the viscosity index improver is a styrene-diene copolymer viscosity index improver having a PSSI of 30 or less.
The present invention also relates to the lubricating oil composition, wherein the viscosity index improver is a polymethacrylate viscosity index improver having a PSSI of 15 or less.
The present invention also relates to the lubricating oil composition, wherein the composition has a 100 ° C. TBS viscosity of 7 mPa · s or less.
In the present invention, the composition has a 100 ° C. kinematic viscosity of 9.3 to 11.0 mm ² / s, a 40 ° C. kinematic viscosity of 40 to 60 mm ² / s, and a 100 ° C. kinematic viscosity after shearing of 9.3 mm. It is related with the said lubricating oil composition characterized by being ² / s or more.
The present invention also relates to the lubricating oil composition comprising a metal salt of a phosphorus-containing acid ester.
The present invention also relates to the lubricating oil composition comprising a metallic detergent, an ashless dispersant, and an antioxidant.
The present invention also relates to the lubricating oil composition, wherein the composition has a sulfated ash content of 0.1 to 2% by mass.

  The lubricating oil composition of the present invention, as a lubricating oil for an internal combustion engine, can reduce the lubrication resistance in the same viscosity grade and further improve the fuel saving performance.

Hereinafter, the present invention will be described in detail.
As the lubricating base oil in the lubricating oil composition of the present invention, a mineral base oil and / or a synthetic base oil used for ordinary lubricating oils can be used.

  Specifically, as the mineral base oil, the lubricating oil fraction obtained by subjecting the crude oil to atmospheric distillation obtained under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, GTL WAX (Gas Liquid Liquid) manufactured by one or more of solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc., or manufactured by slack wax, Fischer-Tropsch process, etc. Examples thereof include lubricating base oils such as wax cracking / isomerized mineral oil obtained by hydrocracking and / or isomerizing a raw material containing a wax mainly composed of n-paraffins.

  Specific examples of synthetic oils include poly α-olefins (eg, 1-octene oligomer, 1-decene oligomer, ethylene-propylene oligomer), poly α-olefin hydrides, isobutene oligomers, and hydrides of isobutene oligomers. , Isoparaffin, alkylbenzene, alkylnaphthalene, diester (eg, ditridecyl glutarate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, dioctyl sebacate, etc.), polyol ester (eg, trimethylolpropane caprylate, trimethylolpropane pelargonate, Trimethylolpropane esters such as trimethylolpropane isostearinate; pentaerythritol 2-ethylhexanoate, pentaerythritol pelar Pentaerythritol esters such as gonates), polyoxyalkylene glycols, dialkyldiphenyl ethers, and polyphenyl ethers.

  In the present invention, a mineral base oil, a synthetic base oil, or an arbitrary mixture of two or more kinds of lubricating oils selected from these can be used as the lubricating base oil. Examples thereof include one or more mineral base oils, one or more synthetic base oils, a mixed oil of one or more mineral base oils and one or more synthetic base oils, and the like.

  The viscosity index of the lubricating base oil is not particularly limited, but is preferably 90 or more, more preferably 115 or more, and further preferably 120 or more. By using a base oil having a high viscosity index, a composition having higher oxidation stability, excellent fuel economy, and low temperature viscosity characteristics can be obtained. The viscosity index of the lubricating base oil is usually 250 or less, preferably 200 or less. In the case of a mineral oil base oil, it is preferably 160 or less in view of its availability, production cost, and low temperature viscosity characteristics.

  The NOACK evaporation amount of the lubricating base oil is not particularly limited, but is usually 20% by mass or less, preferably 16% by mass, and more preferably 10 to 15% by mass. If the NOACK evaporation exceeds 20% by mass, the amount of evaporation loss of the lubricating oil tends to increase, and it is easy to cause viscosity increase and additive concentration, making it difficult to maintain fuel saving performance for a long period of time. It tends to be difficult to improve fuel efficiency.

The kinematic viscosity at 100 ° C. of the lubricating base oil is not particularly limited, but is preferably 1 to ²⁰ mm ² / s, more preferably 3.5 to ⁶ mm ² / s, and still more preferably 3.7 to 4 0.5 mm ² / s, and most preferably 3.8 to 4.2 mm ² / s. The lubricating base oil of less than kinematic viscosity of 1 mm ² / s at 100 ° C. of, the number evaporation loss of the base oil due to heat generated from the internal combustion engine, is concerned adverse effect on the viscosity increase and the exhaust gas, whereas, 20 mm ² When it exceeds / s, the power loss due to viscous resistance increases, and it tends to be difficult to maximize the fuel saving performance.

Kinematic viscosity at 40 ° C. of the lubricating base oil is not particularly limited, is preferably from 10 to 100 mm ² / s, more preferably 13~25mm ² / s, at 15 to 20 mm ² / s More preferably, it is particularly preferably 16 to 19 mm ² / s. By setting the kinematic viscosity at 40 ° C. to 100 mm ² / s or less, the viscosity index of the composition can be further increased, and fuel economy is excellent. On the other hand, from the viewpoint of preventing wear and suppressing evaporation loss, the kinematic viscosity at 40 ° C. is preferably 10 mm ² / s or more.

The% C _P of the lubricating base oil is not particularly limited, but is preferably 60 or more, more preferably 70 or more, and still more preferably 80 or more, from the viewpoint of being excellent in the effect of suppressing an increase in acid value and viscosity increase in the presence of NOx. The upper limit is not particularly limited, and may be 95 to 100 as one aspect of the present invention, but 95 or less is preferable in terms of soot dispersibility and sludge solubility.

Moreover,% C _N of the lubricating base oil is not particularly limited, from the viewpoint of excellent by suppressing the effect of acid number increase and the viscosity increase in the presence of NOx, is preferably 40 or less, more preferably 30 or less, further Preferably it is 20 or less, Most preferably, it is 15 or less.

Moreover,% C _A of the lubricating base oil is not particularly limited, the point is preferably 5 or less in the more excellent effect of suppressing acid number increase and the viscosity increase in the presence of NOx, and more preferably 2 or less, more preferably 1 or less Most preferably, it is 0.5 or less.

_Moreover,% C P _/% C _N of the lubricating base oil is not particularly limited, from the viewpoint of excellent by suppressing the effect of acid number increase and the viscosity increase in the presence of NOx, preferably 1 or more, more preferably 3 or more More preferably, it is 5 or more, particularly preferably 6 or more, and the upper limit thereof is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and more preferably 15 or less, further in terms of soot dispersibility and sludge solubility. The number is preferably 10 or less, particularly preferably 8 or less.
Herein, the _term% C A,% _C A _P and% _{C N,} is determined by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total number of carbon atoms of the aromatic carbon atoms Mean percentage of paraffin carbon to total carbon and percentage of naphthene carbon to total carbon.

  The sulfur content of the lubricating base oil is not particularly limited, but is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and 0.1% by mass or less. Is more preferable, and 0.01% by mass or less is most preferable.

  In the present invention, the lubricating base oil is preferably a mineral base oil and / or a poly α-olefin base oil. As the mineral oil base oil, hydrocracked mineral oil or wax isomerized mineral oil is particularly preferable. As the poly α-olefin base oil, an α-olefin having 6 to 18 carbon atoms, particularly an α-olefin having 6 to 12 carbon atoms is preferable. An olefin copolymer or a hydride thereof is preferred.

  Examples of the (A) viscosity index improver used in the present invention include non-dispersed or dispersed viscosity index improvers. Specifically, non-dispersed or dispersed polymethacrylates, dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or hydrides thereof, styrene-diene copolymers, styrene-maleic anhydride copolymer Among them, there can be mentioned coalesced polyalkylstyrene, etc. Among them, the weight average molecular weight is preferably 10,000 or more, more preferably 20,000 or more, further preferably 50,000 or more, particularly preferably 80,000 or more, usually 1,000,000 or less, preferably 40 Non-dispersion type viscosity index improver and / or dispersion type viscosity index improver of 10,000 or less, more preferably 300,000 or less, further preferably 200,000 or less, and particularly preferably 150,000 or less are preferably used. An improver is most preferably used.

Specifically, as the non-dispersion type viscosity index improver, a monomer (hereinafter referred to as “monomer (M-1)” selected from compounds represented by the following general formulas (1), (2) and (3): ).) Homopolymers or two or more copolymers of monomers (M-1) or hydrides thereof.
On the other hand, as the dispersion-type viscosity index improver, specifically, a monomer selected from compounds represented by the following general formulas (4) and (5) (hereinafter referred to as “monomer (M-2)”). ) Two or more types of copolymers or hydrides thereof, and one or more types of monomers (M-1) selected from the compounds represented by the general formulas (1) to (3) and a general formula Examples thereof include a copolymer of one or more monomers (M-2) selected from the compounds represented by (4) and (5), or a hydride thereof.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.
Specific examples of the alkyl group having 1 to 18 carbon atoms represented by R ² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Examples thereof include a group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group (these alkyl groups may be linear or branched).

In the general formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
Specific examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as decyl, undecyl and dodecyl (these alkyl groups may be linear or branched); cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl; Methylcyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group, diethylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, Diethylcycloheptyl group, etc. A C6-C11 alkylcycloalkyl group (the substitution position of these alkyl groups with the cycloalkyl group is arbitrary); vinyl group (ethenyl group), propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl Groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, dodecenyl groups and the like alkenyl groups (these alkenyl groups may be linear or branched, and the position of the double bond is arbitrary); phenyl group, Aryl group such as naphthyl group: alkylaryl group having 7 to 12 carbon atoms such as tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group (these alkyl groups are linear And the substitution position on the aryl group is arbitrary.); Benzyl group, phenyl group Group, phenylpropyl group, phenylbutyl group, phenylpentyl group, an arylalkyl group having 7 to 12 carbon atoms such as a phenyl hexyl group (the alkyl group may be. Be branched straight-chain) can be exemplified, and the like.

In the general formula (3), Z ¹ and Z ² are each independently a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms (—OR ⁵ : R ⁵ is an alkyl group having 1 to 18 carbon atoms) or a carbon number. 1-18 monoalkylamino group (-NHR ^{6: R 6} is an alkyl group having 1 to 18 carbon atoms).

In the general formula (4), R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an alkylene group having 1 to 18 carbon atoms, E ¹ represents ¹ to 2 nitrogen atoms, and 0 to 2 oxygen atoms. 1 represents an amine residue or a heterocyclic residue, and a is 0 or 1.
Specific examples of the alkylene group having 1 to 18 carbon atoms represented by R ⁸ include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, Examples include an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group (these alkylene groups may be linear or branched).
Specific examples of the group represented by E ¹ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, Examples thereof include a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, and a pyrazino group.

In the general formula (5), R ⁹ represents a hydrogen atom or a methyl group, and E ² represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
Specific examples of the group represented by E ² include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, and a morpholino group. Pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, pyrazino group and the like.

  Preferable examples of the monomer (M-1) are specifically alkyl acrylates having 1 to 18 carbon atoms, alkyl methacrylates having 1 to 18 carbon atoms, olefins having 2 to 20 carbon atoms, styrene, methylstyrene, and anhydrous maleic acid. Examples thereof include acid esters, maleic anhydride amides and mixtures thereof.

  Preferable examples of the monomer (M-2) are specifically dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl. Examples thereof include methacrylate, N-vinyl pyrrolidone and a mixture thereof.

  Although there is no restriction | limiting in particular about the copolymerization molar ratio of the copolymer of a monomer (M-1) and a monomer (M-2), Monomer (M-1): Monomer (M-2) = 80: 20-95 : About 5 is preferable. The copolymerization method is also arbitrary. For example, a copolymer can be easily obtained by radical solution polymerization of the monomer (M-1) and the monomer (M-2) in the presence of a polymerization initiator such as benzoyl peroxide. be able to.

The PSSI (Permanent Cability Index) of the viscosity index improver used in the present invention needs to be 30 or less, preferably 20 or less, more preferably 15 or less, and still more preferably 12 or less. On the other hand, if it is too low, the effect of improving the viscosity index of the composition is small, and the effect of improving fuel economy is small.
PSSI here refers to ASTM D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index) and ASTM D 6278-02 (Test Metohd for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus). ) Means the permanent shear stability index of the polymer, calculated based on the data measured by

  The content of the viscosity index improver in the lubricating oil composition of the present invention is usually 1 to 30% by mass, preferably 5 to 25% by mass, more preferably 8 to 20% by mass, particularly based on the total amount of the composition. Preferably it is 12-18 mass%.

  In the present invention, a viscosity index improver having a PSSI of 30 or less is blended in such an amount that the viscosity index of the composition is 160 or more. Preferably, it is desirable to add an amount such that the viscosity index of the composition is 170 or more, more preferably 180 or more, and the upper limit is not particularly limited, but is usually 300 or less, preferably 250 or less, more preferably 200 or less. More preferably, it is 190 or less. By blending the viscosity index improver in such an amount that the viscosity index of the composition is 160 or more, the viscosity in the effective temperature region can be lowered and the fuel economy can be improved. In the present invention, when increasing the viscosity index, it is preferable to consider so that the blending amount of the viscosity index improver and the kinematic viscosity of the composition do not become too high. It is particularly preferable to blend so as to have a viscosity index of 200 or less. In this case, it is possible to obtain a composition that is more excellent in high-temperature cleanability.

  In the present invention, a viscosity index improver having a PSSI of 30 or less is blended so that the rate of decrease in kinematic viscosity at 100 ° C. after shearing is 15% or less. The rate of decrease in kinematic viscosity at 100 ° C. after shearing was measured after the shear test in accordance with the above ASTM D 6278-02 (Test Method for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus). It means the data ((V1-V2) / V1 × 100) (%) calculated based on the kinematic viscosity (V2) at 100 ° C. and the kinematic viscosity (V1) at 100 ° C. before the shear test.

  In the present invention, as the viscosity index improver, it is preferable to use a polymethacrylate viscosity index improver from the viewpoint of increasing the viscosity index and being excellent in energy saving improvement effect. The PSSI of the polymethacrylate viscosity index improver used in the present invention is 30 or less, preferably 15 or less, more preferably 10 or less, particularly preferably 8 or less, preferably 1 or more, more preferably 3 or more. . In particular, it is preferable to use a polymethacrylate viscosity index improver having a PSSI of 15 or less.

  In the present invention, as the viscosity index improver, it is preferable to use a styrene-diene copolymer viscosity index improver from the viewpoint of lowering the effective viscosity under high-temperature and high-shear conditions and being excellent in energy saving and high-temperature cleanability. . The PSSI of the styrene-diene copolymer viscosity index improver used in the present invention is 30 or less, preferably 15 or less, more preferably 12 or less, preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more. Especially preferably, it is 8 or more. Styrene-diene copolymer viscosity index improvers include one or more styrene monomers or (co) polymers selected from styrene, polystyrene and hydrides thereof, dienes, polydienes and hydrides thereof. One type or two or more types of diene monomers or copolymers with (co) polymers or hydrides thereof may be mentioned. Examples of the diene monomers or (co) polymers include butadiene, polybutadiene, and hydrides thereof. Preferably selected from isoprene-based monomers or (co) polymers such as butadiene-based monomers or (co) polymers, isoprene, polyisoprene and hydrides thereof, such as isoprene-based monomers or (co) polymers. More preferablyThese styrene-diene copolymer viscosity index improvers may be alternating copolymers of styrene monomers or (co) polymers with diene monomers or (co) polymers, or random copolymers. A block polymer may also be used. Among these, a block copolymer of a styrene monomer or (co) polymer and a diene monomer or (co) polymer is more preferable, and a styrene monomer or (co) polymer and a diene monomer or (copolymer). ) A block copolymer with a polymer is more preferable, and a block copolymer having a polystyrene block and a hydrogenated polyisoprene block is particularly preferable.

As a block copolymer having a polystyrene block and a hydrogenated polyisoprene block, for example, structural formula EP-S (wherein EP has a number average molecular weight (M _n ) before hydrogenation of 20,000 to 150,000) Hydrogenated polyisoprene block, and S is a block copolymer having a structure of a polystyrene block having a number average molecular weight (M _n ) of 10,000 to 60,000), and is particularly preferred in the present invention. It is.

Other examples of the block copolymer having a polystyrene block and a hydrogenated polyisoprene block include, for example, the structural formula EP′-S-EP ″ (where EP ′ is the number average molecular weight (M _n before hydrogenation). ) Is a first hydrogenated polyisoprene block having 40,000 to 150,000, S is a polystyrene block having a number average molecular weight (M _n ) of 25,000 to 60,000, and EP ″ is This is a second hydrogenated polyisoprene block having a number average molecular weight (M _n ) before hydrogenation of 2,500 to 30,000, and a molecular weight ratio of EP ′ / EP ″ is at least 4. Examples include asymmetric triblock copolymers.

As another example, a structure represented by (EP′-S-EP ″) _n —X (EP ′ has a number average molecular weight (M _n ) before hydrogenation of 10,000 to 100,000). 1 is a hydrogenated block of polyisoprene (I ′), S is a block of polystyrene having a number average molecular weight (M _n ) of 6,000 to 50,000, and EP ″ is a number average molecular weight before hydrogenation ( M _n ) is a hydrogenation block of a second polyisoprene (I ″) having a 2,500 to 50,000, the molecular weight ratio (M _w ) of I ′ / I ″ is at least 1.4, and X Is a nucleus composed of a polyalkenyl coupling agent, and n is one molecule of a star molecule formed by reacting 2 or more moles of polyalkenyl coupling agent per mole of (EP′-S-EP ″) arm. Is the average number of arms per) Star-like polymer, and the like.

The lubricating oil composition of the present invention preferably contains (B) a phosphorus-containing compound.
The phosphorus-containing compound is not particularly limited as long as it is a compound containing phosphorus in the molecule. For example, a phosphorus compound represented by the general formula (6), a phosphorus compound represented by the general formula (7), and the like And at least one compound selected from the group consisting of metal salts thereof, amine salts thereof, and derivatives thereof.

In Formula (6), X ¹ , X ² and X ³ each independently represent an oxygen atom or a sulfur atom, and R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom or a carbon atom having 1 to 30 carbon atoms. A hydrogen group or a substituent having 1 to 30 carbon atoms containing a hetero element such as N, S, or O is shown.

In Formula (7), X ⁴ , X ⁵ , X ⁶ and X ⁷ are each independently an oxygen atom or a sulfur atom (one or two of X ⁴ , X ⁵ and X ⁶ are a single bond or (poly) oxyalkylene) R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, or a carbon number 1 containing a hetero element such as N, S or O. -30 substituents are shown.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{10 to} R ¹⁵ include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group. It is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably an alkyl group having 3 to 18 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms. is there. These hydrocarbon groups may contain any of an oxygen atom, a nitrogen atom, and a sulfur atom in the molecule, but a hydrocarbon composed of carbon and hydrogen is desirable.

  Examples of the phosphorus compound represented by the general formula (6) include phosphorous acid, monothiophosphorous acid, dithiophosphorous acid, trithiophosphorous acid; a nitrous acid having one hydrocarbon group having 1 to 30 carbon atoms. Phosphoric acid monoester, monothiophosphorous acid monoester, dithiophosphorous acid monoester, trithiophosphorous acid monoester; phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid diester , Dithiophosphite diester, trithiophosphite diester; phosphite triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite triester, dithiophosphite triester, trithiophosphite And acid triesters; and mixtures thereof.

  Examples of the phosphorus compound represented by the general formula (7) include phosphoric acid, monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, tetrathiophosphoric acid; phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms. Monothiophosphoric acid monoester, dithiophosphoric acid monoester, trithiophosphoric acid monoester, tetrathiophosphoric acid monoester; phosphoric acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphoric acid diester, dithiophosphoric acid diester, trithiophosphoric acid Diesters, tetrathiophosphoric acid diesters; phosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphoric acid triesters, dithiophosphoric acid triesters, trithiophosphoric acid triesters, tetrathiophosphoric acid triesters; 1-30 hydrocarbon groups ~ 3 phosphonic acid, phosphonic acid monoester, phosphonic acid diester; the above phosphorus compound having a (poly) oxyalkylene group having 1 to 4 carbon atoms; β-dithiophosphorylated propionic acid or dithiophosphoric acid and olefin cyclopentadiene or ( (Methyl) Derivatives of the above phosphorus compounds such as reaction products with methacrylic acid; and mixtures thereof.

  As a salt of the phosphorus compound represented by the general formula (6) or (7), the phosphorus compound may be a metal base such as a metal oxide, metal hydroxide, metal carbonate or metal chloride, ammonia, 1 to 1 carbon atoms. Examples thereof include salts obtained by allowing a nitrogen compound such as an amine compound having only 30 hydrocarbon groups or hydroxyl group-containing hydrocarbon groups in the molecule to act to neutralize part or all of the remaining acidic hydrogen.

  Specific examples of the metal in the metal base include alkali metals such as lithium, sodium, potassium and cesium, alkaline earth metals such as calcium, magnesium and barium, zinc, copper, iron, lead, nickel, silver and manganese. And heavy metals such as molybdenum. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

Specific examples of the nitrogen compound include ammonia, monoamine, diamine, and polyamine.
Among these nitrogen compounds, aliphatic amines having an alkyl or alkenyl group having 10 to 20 carbon atoms such as decylamine, dodecylamine, dimethyldodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine (these are It may be linear or branched)).

As the phosphorus-containing compound, it is particularly desirable that at least one selected from the following (B1) to (B3) is contained as a main component in the lubricating oil composition of the present invention.
(B1) zinc dialkyldithiophosphate having a secondary alkyl group selected from 3 to 8 carbon atoms (B2) zinc dialkyldithiophosphate having a primary alkyl group selected from 3 to 8 carbon atoms (B3) phosphorus-containing acid not containing sulfur Metal salt

  As said (B1) and (B2) component, what is represented by following General formula (8) can be illustrated.

In said formula (8), R <^16> , R <^17> , R <^18> and R <^19> may be the same or different, and each is independently a C3-C8 cetary alkyl group or primary alkyl group, preferably carbon. A secondary alkyl group having 3 to 6 carbon atoms or a primary alkyl group having 6 to 8 carbon atoms is shown, and the same molecule may have an alkyl group having a different carbon number and an alkyl group having a different structure (secondary or primary).

  In the present invention, it is preferable to contain (B1) a zinc dialkyldithiophosphate having a secondary alkyl group selected from 3 to 8 carbon atoms in that it is easy to suppress wear under soot mixing even at a low concentration. (B2) It is preferable to contain a zinc dialkyldithiophosphate having a primary alkyl group selected from 3 to 8 carbon atoms in that the stability can be further improved and the base number maintenance performance can be significantly improved. It is most preferable to use the components (B1) and (B2) together in terms of improving the wear suppression performance and the base number maintenance performance at a high level in a well-balanced manner.

The component (B3) is a metal salt of a phosphorus-containing acid that does not contain sulfur, and all of X ^{1 to} X ³ in the general formula (6) are oxygen atoms (X ¹ , X ^2, and X ³ 1 One or two of them may be a single bond or a (poly) oxyalkylene group), and all of X ^{4 to} X ⁷ in the general formula (7) are oxygen atoms (X ⁴ , X ⁵ and X ^A typical example is a metal salt of a phosphorus compound in which one or two of ⁶ may be a single bond or a (poly) oxyalkylene group. These (B3) components can be preferably used in that the long drain performance such as high temperature cleanliness, oxidation stability, and base number maintenance can be remarkably enhanced.

  The structure of the metal salt of the phosphorus compound varies depending on the valence of the metal and the number of OH groups of the phosphorus compound, and therefore the structure is not limited at all. For example, when 1 mol of zinc oxide and 2 mol of phosphoric acid diester (one OH group) are reacted, a compound having a structure represented by the following general formula (9) is considered to be obtained as a main component. It is thought that the molecules that existed exist.

  For example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (having two OH groups) are reacted, a compound having a structure represented by the following general formula (10) is considered to be obtained as a main component. However, it is thought that polymerized molecules exist.

  Among these (B3) components, a salt of phosphorous acid diester having two alkyl groups or aryl groups having 3 to 18 carbon atoms and zinc, one alkyl group or aryl group having 3 to 18 carbon atoms Salt of phosphoric acid monoester and zinc, diester of phosphoric acid having two alkyl groups or aryl groups having 3 to 18 carbon atoms and zinc, two alkyl groups or aryl groups having 1 to 18 carbon atoms A salt of phosphonic acid monoester and zinc is preferable. These components can be arbitrarily blended in one kind or two or more kinds.

  As the phosphorus-containing compound to be contained in the lubricating oil composition of the present invention, a metal salt of a phosphorus-containing acid ester is particularly preferably used, and those having an S / P (molar ratio) of 1.5 or less are preferable, more preferably 1. Hereinafter, it is most preferably 0.

  The content of the phosphorus-containing compound in the lubricating oil composition of the present invention is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, as the amount of phosphorus, from the viewpoints of high-temperature cleanability and base number maintenance. It is. On the other hand, the amount of phosphorus is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more, particularly preferably in terms of easily suppressing wear under soot mixing. It is 0.04 mass% or more.

  The lubricating oil composition of the present invention preferably further contains at least one additive selected from the group consisting of (C) a metal detergent, (D) an ashless dispersant, and (E) an antioxidant. .

  (C) More specifically, examples of the metal detergent include sulfonate detergent, phenate detergent, and salicylate detergent.

  The structure of the sulfonate detergent is not particularly limited. For example, an alkali metal salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 100 to 1,500, preferably 200 to 700. Alternatively, alkaline earth metal salts are exemplified, and particularly, magnesium salts and / or calcium salts are preferably used. Specific examples of alkyl aromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids. As the petroleum sulfonic acid, those obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil or so-called mahoganic acid which is produced as a by-product when white oil is produced is used. As the synthetic sulfonic acid, for example, a raw material is an alkylbenzene having a linear or branched alkyl group, which is obtained as a by-product from an alkylbenzene production plant that is a raw material for detergents or is obtained by alkylating polyolefin with benzene. And a sulfonated one of this, a sulfonated dinonylnaphthalene, or the like. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or sulfuric acid is used.

In addition, as the sulfonate detergent, the above alkyl aromatic sulfonic acid may be directly reacted with an alkaline earth metal base such as magnesium and / or calcium alkaline earth metal oxide or hydroxide, or once. Not only neutral alkaline earth metal sulfonates obtained by replacing alkali metal salts such as sodium salts and potassium salts with alkaline earth metal salts, but also the above neutral alkaline earth metal sulfonates and excess alkaline earth metals Presence of basic alkaline earth metal sulfonate obtained by heating metal salt or alkaline earth metal base (hydroxide or oxide) in the presence of water, carbon dioxide and / or boric acid or borate Carbonic acid obtained by reacting the neutral alkaline earth metal sulfonate with an alkaline earth metal base under Overbased alkaline earth metal sulfonate, are also included borate overbased alkaline earth metal sulfonate.
In the present invention, the neutral alkaline earth metal sulfonate, basic alkaline earth metal sulfonate, overbased alkaline earth metal sulfonate, and a mixture thereof can be used as the sulfonate detergent.

The salicylate-based detergent is not particularly limited in its structure, but a metal salt of salicylic acid having 1 to 2 alkyl groups having 1 to 40 carbon atoms, preferably an alkali metal salt or an alkaline earth metal salt, particularly a magnesium salt And / or calcium salts are preferably used.
The salicylate detergent in the present invention preferably has a higher component ratio of the monoalkyl salicylic acid metal salt in terms of excellent low-temperature viscosity characteristics. For example, the component ratio of the monoalkyl salicylic acid metal salt is 85 to 100 mol%, and the dialkyl salicylic acid. It is preferable that the metal salt has a constituent ratio of 0 to 15 mol%, and the constituent ratio of the 3-alkyl salicylic acid metal salt is 40 to 100 mol%, and / or an (over) basic salt thereof. . In addition, the salicylate-based detergent in the present invention is preferably one containing a dialkyl salicylic acid metal salt from the viewpoint of excellent high-temperature cleanability and base number maintenance.

The alkyl group in the alkyl salicylic acid metal salt constituting the salicylate-based detergent has 10 to 40 carbon atoms, preferably 10 to 19 carbon atoms or 20 to 30 carbon atoms, more preferably 14 to 18 carbon atoms or 20 to 20 carbon atoms. 26 alkyl groups, particularly preferably an alkyl group having 14 to 18 carbon atoms. Examples of the alkyl group having 10 to 40 carbon atoms include decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heicosyl, docosyl, Examples thereof include alkyl groups having 10 to 40 carbon atoms such as a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, and a triacontyl group. These alkyl groups may be linear or branched, and may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group. In the present invention, the desired salicylic acid metal salt is used. A secondary alkyl group is particularly preferred because it is easy to obtain.
Examples of the metal in the alkyl salicylic acid metal salt include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and are preferably calcium and magnesium, and particularly preferably calcium.

  In the present invention, the salicylate detergent is an alkali metal or alkaline earth metal salicylate (neutral salt), an excess of an alkali metal or alkaline earth metal salt, an alkali metal or an alkaline earth metal base (an alkali metal or an alkali metal). A basic salt obtained by heating a hydroxide or oxide of an earth metal in the presence of water, or an alkali metal or an alkali in the presence of carbon dioxide gas, boric acid or borate. Also included are overbased salts obtained by reacting with bases such as earth metal hydroxides.

Specifically, the phenate detergent is obtained by reacting sulfur with an alkylphenol having at least one linear or branched alkyl group having 4 to 40 carbon atoms, preferably 6 to 18 carbon atoms. Alkali earth metal salts, particularly magnesium salts and / or calcium salts, of Mannich reaction products of alkylphenols obtained by reacting alkylphenol sulfides or alkylphenols with formaldehyde are preferably used.
The phenate detergent used in the present invention includes an alkali metal or alkaline earth gold phenate (neutral salt) obtained as described above, and an excess of alkali metal or alkaline earth metal salt, alkali metal or alkali. In the presence of basic salts obtained by heating an earth metal base (alkali metal or alkaline earth metal hydroxide or oxide) in the presence of water, carbon dioxide, boric acid or borate Also included are overbased salts obtained by reacting the neutral salt with a base such as an alkali metal or alkaline earth metal hydroxide.

  In the present invention, the metal detergent is preferably an alkaline earth metal detergent such as calcium or magnesium, and particularly preferably a sulfonate detergent.

Although the base number of the metal detergent used in the present invention is arbitrary, in order to achieve excellent cleanability, those having a base number of 0 to 500 mgKOH / g can be used. In order to obtain a composition having excellent performance at high temperature and particularly excellent wear resistance, the base number is preferably 150 to 450 mgKOH / g, more preferably 200 to 400 mgKOH / g.
The base number is JIS K2501, "Petroleum products and lubricants-Neutralization number test method" 7. Means the base number measured by the perchloric acid method according to the above.
Metal-based detergents are usually commercially available in a state diluted with a light lubricating base oil or the like, and are available, but generally the metal content is 1.0 to 20% by mass, preferably The thing of 2.0-16 mass% is used.

  Although the content of the metal detergent in the lubricating oil composition of the present invention is arbitrary, it is usually preferably 0.005% by mass or more, more preferably 0.05% by mass as the metal amount based on the total amount of the composition. More preferably, it is 0.08% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.25% by mass or less, and particularly preferably 0.15% by mass. It is as follows. When the content is less than 0.005% by mass, the high-temperature cleanliness and wear resistance are likely to deteriorate, and when it exceeds 1% by mass, the deterioration of the exhaust gas aftertreatment device such as DPF is easily promoted. .

(D) As the ashless dispersant, any ashless dispersant used in lubricating oils can be used. For example, at least a linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule is used. Examples thereof include one nitrogen-containing compound or a derivative thereof, or a modified product of alkenyl succinimide. One type or two or more types arbitrarily selected from these can be blended.
The alkyl group or alkenyl group has 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms. When the carbon number of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil decreases, whereas when the carbon number exceeds 400, the low-temperature fluidity of the lubricating oil composition deteriorates. Therefore, it is not preferable respectively. This alkyl group or alkenyl group may be linear or branched, but specifically, preferred are derived from olefin oligomers such as propylene, 1-butene and isobutylene, and co-oligomers of ethylene and propylene. And a branched alkyl group and a branched alkenyl group.
Although the nitrogen content of the nitrogen-containing compound mentioned as an example of the ashless dispersant is arbitrary, the nitrogen content is usually 0.01 to from the viewpoints of base number maintenance characteristics, high temperature cleanability, wear resistance, and the like. 10% by mass, preferably 0.1 to 10% by mass is used.

Specific examples of the ashless dispersant include the following compounds. One or more compounds selected from these can be used.
(D1) Succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof (D2) At least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule Benzylamine having a derivative thereof (D3) a polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof

  More specifically, examples of the (D1) succinimide include compounds represented by the following formulas (11) and (12).

In the above formula (11), R ²⁰ represents an alkyl or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and b represents an integer of 1 to 5, preferably 2 to 4.

In the above formula (12), R ²¹ and R ²² each independently represent an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and preferably a polybutenyl group. c represents an integer of 0 to 4, preferably 1 to 3.
In addition, succinimide is a so-called monotype succinimide such as the formula (11) in which succinic anhydride is added to one end of the polyamine, and succinic anhydride is added to both ends of the polyamine. There is a so-called bis-type succinimide represented by the formula (12), and the compound used in the present invention may be any of them or a mixture thereof.
The method for producing these succinimides is not particularly limited. For example, an alkyl or alkenyl succinic acid obtained by reacting an alkyl group or alkenyl group having 40 to 400 carbon atoms with maleic anhydride at 100 to 200 ° C. is reacted with a polyamine. Can be obtained. Specific examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

  More specifically, examples of (D2) benzylamine include compounds represented by the following formula (13).

In the above formula (13), R ²³ represents an alkyl or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and d represents an integer of 1 to 5, preferably 2 to 4.
The method for producing this benzylamine is not limited in any way. For example, after reacting a polyolefin such as propylene oligomer, polybutene, and ethylene-α-olefin copolymer with phenol to form alkylphenol, formaldehyde and It can be obtained by reacting polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by Mannich reaction.

  More specifically, examples of the (D3) polyamine include compounds represented by the following formula (14).

In the above formula (14), R ²⁴ represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and e represents an integer of 1 to 5, preferably 2 to 4.
The production method of this polyamine is not limited in any way. For example, after chlorinating a polyolefin such as propylene oligomer, polybutene, and ethylene-α-olefin copolymer, ammonia, ethylenediamine, diethylenetriamine, triethylene are added thereto. It can be obtained by reacting polyamines such as tetramine, tetraethylenepentamine, and pentaethylenehexamine.

  Specific examples of the derivative of the nitrogen-containing compound cited as an example of the ashless dispersant (D) include, for example, monocarboxylic acids having 1 to 30 carbon atoms (fatty acids, etc.) and oxalic acid to the aforementioned nitrogen-containing compounds. , Phthalic acid, trimellitic acid, pyromellitic acid and other polycarboxylic acids having 2 to 30 carbon atoms were allowed to act to neutralize or amidate some or all of the remaining amino groups and / or imino groups So-called acid-modified compounds; so-called boron-modified compounds obtained by allowing boric acid to act on the aforementioned nitrogen-containing compounds to neutralize or amidate some or all of the remaining amino groups and / or imino groups; And a sulfur-modified compound obtained by allowing a sulfur compound to act on a nitrogen-containing compound; and a modified compound in which two or more kinds of modifications selected from acid modification, boron modification, and sulfur modification are combined with the nitrogen-containing compound described above. Among these derivatives, the alkenyl succinimide boric acid-modified compound is excellent in heat resistance and antioxidant properties, and is effective in improving the base number maintenance property and the like in the lubricating oil composition of the present invention.

  When (D) the ashless dispersant is contained in the lubricating oil composition of the present invention, the content is not particularly limited, but is usually 0.01 to 20% by mass based on the total amount of the lubricating oil composition, and more Preferably it is 0.1-10 mass%. When the content of the component (D) is less than 0.01% by mass, the base number maintenance characteristics, the high temperature cleanliness and the wear prevention property cannot be further improved. Since the low temperature fluidity of the lubricating oil composition is greatly deteriorated, each is not preferable. In the present invention, when a boron-containing succinimide-based ashless dispersant is contained as the component (D), a composition superior in high-temperature cleanability can be obtained, and the content is based on the total amount of the composition. And as a boron amount, Preferably it is 0.001-0.1 mass%, More preferably, it is 0.005-0.04 mass%, More preferably, it is 0.01-0.02 mass%.

(E) Antioxidants are generally used in lubricating oils, such as ashless antioxidants such as phenolic antioxidants and amine antioxidants, and metal antioxidants such as molybdenum antioxidants. Antioxidants can be used. Since the antioxidant property of the lubricating oil composition can be further increased by adding the antioxidant, the base number maintenance property can be further increased.
As the phenolic antioxidant, the following compounds are particularly preferred as specific examples. 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'-iso Butylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,6-di-tert -Butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-α-dimethylamino-p- Cresol, 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 4,4′-thiobis ( 3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, bis ( 3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 2,2′-thio-diethylenebis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. Two or more of these may be used as a mixture.

  Examples of amine-based antioxidants include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine. You may use these in mixture of 2 or more types.

  Molybdenum-based antioxidants include organic molybdenum-based antioxidants such as sulfurized oxymolybdenum or alkylamine complexes of oxymolybdenum, oxymolybdenum sulfide or alkenyl succinimide complexes of oxymolybdenum, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate. An agent may be mentioned, and these may be used alone or in combination. Among these, sulfur sulfide oxymolybdenum or oxymolybdenum-ditridecylamine complex, oxymolybdenum sulfide or oxymolybdenum is advantageous in that it suppresses the increase in viscosity and easily maintains fuel economy for a long period of time and is superior in high temperature cleanliness It is particularly preferable to blend one or more selected from alkenyl succinimide complexes.

  You may mix | blend the said phenolic antioxidant, amine-type antioxidant, and molybdenum-type antioxidant suitably combining.

When the (E) antioxidant is contained in the lubricating oil composition of the present invention, it is preferably 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, based on the total amount of the lubricating oil composition. . Even if it exceeds 5 mass%, it is not preferable because sufficient antioxidant properties corresponding to the amount of the compound cannot be obtained. On the other hand, from the viewpoint of further improving the base number maintenance property, high temperature cleanliness, etc., it is preferably blended in an amount of 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably based on the total amount of the lubricating oil composition. 0.8% by mass or more.
In addition, when mix | blending a molybdenum type antioxidant, the compounding quantity is 0.001-0.2 mass% as a molybdenum amount on the basis of lubricating oil composition whole quantity, Preferably it is 0.005-0.1 mass%, More preferably, it is 0.01-0.04 mass%, Most preferably, it is 0.01-0.03 mass%.

  In the lubricating oil composition of the present invention, any additive generally used in lubricating oils can be blended depending on the purpose within a range that does not significantly deteriorate the performance of the lubricating oil composition of the present invention. . Examples of such additives include additives such as antiwear agents, friction modifiers, corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, antifoaming agents, and colorants. it can.

As the antiwear agent, any antiwear agent used in lubricating oils can be used. For example, sulfur-based extreme pressure agents can be used, and specific examples include dithiocarbamates, disulfides, polysulfides, sulfurized olefins, sulfurized fats and oils, and the like.
In the lubricating oil composition of the present invention, when these antiwear agents are used, the content is not particularly limited, but is preferably 0.01 to 5% by mass based on the total amount of the composition.

  As the friction modifier, an amine compound, fatty acid ester, fatty acid having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly at least one linear alkyl group or linear alkenyl group having 6 to 30 carbon atoms in the molecule. Metal-based friction such as amide, fatty acid, aliphatic alcohol, aliphatic ether, hydrazide (oleyl hydrazide, etc.), semicarbazide, urea (oleyl urea, etc.), ashless friction modifier such as ureido, biuret, molybdenum dithiocarbamate, molybdenum dithiophosphate Examples include regulators.

Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester such as glycerin monooleate and sorbitan monooleate, and amines.
Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.
Examples of the antifoaming agent include silicone, fluorosilicol, and fluoroalkyl ether.

  When these additives are contained in the lubricating oil composition of the present invention, the content is based on the total amount of the lubricating oil composition, and 0.01% for the friction modifier, corrosion inhibitor, rust inhibitor, and demulsifier, respectively. It is usually selected in the range of ˜5% by mass, 0.005 to 1% by mass for the metal deactivator, and 0.0005 to 1% by mass for the antifoaming agent.

The kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is not particularly limited, but is preferably 4.0 to 27.0 mm ² / s, more preferably 5.6 to 16.3 mm ² / s. Yes, more preferably 9.3 to 12.5 mm ² / s, and particularly preferably 9.3 to 11.0 mm ² / s.
The kinematic viscosity at 40 ° C. is not particularly limited, but is preferably 14.0 to ²⁰⁰ mm ² / s, more preferably 20 to 110 mm ² / s, and still more preferably 40 to 60 mm ² / s. Especially preferably, it is 45-55 mm < ² > / s.
The lubricating oil composition of the present invention preferably has a kinematic viscosity at 100 ° C. after shearing of 9.3 mm ² / s or more.
The viscosity grade of the lubricating oil composition of the present invention is preferably in the range of SAE20, 30, 40, 50, more preferably in the range of SAE20, 30, especially SAE30, 0W-30, 5W-30, 10W-. 30 is preferable.

  The viscosity index of the lubricating oil composition of the present invention is usually 160 or more, preferably 170 or more, more preferably 180 or more from the viewpoint of improving the viscosity-temperature characteristics and fuel economy, shear stability and high temperature. From the point which is excellent in cleanliness and base number maintenance performance, Preferably it is 250 or less, More preferably, it is 220 or less, More preferably, it is 200 or less, Most preferably, it is 190 or less.

  The NOACK evaporation amount of the lubricating oil composition of the present invention is not particularly limited, but is usually 20% by mass or less, preferably 16% by mass, and more preferably 10-15% by mass. When the NOACK evaporation amount exceeds 20% by mass, the evaporation loss amount of the lubricating oil increases, which is not preferable.

The TBS viscosity at 150 ° C. of the lubricating oil composition of the present invention is, for example, SAE (xW−) 30 grade, 2.9 mPa · s or more in balance between sufficient oil film retention and friction reduction effect in the fluid lubrication region, The pressure is preferably less than 3.7 mPa · s, more preferably 3.2 mPa · s or less, and still more preferably 3 mPa · s or less.
The TBS viscosity at 100 ° C. of the lubricating oil composition of the present invention is, for example, SAE (xW−) 30 grade, 7 mPa · s or less with a balance between sufficient oil film retention and friction reduction effect in the fluid lubrication region. Is preferably 6.6 mPa · s or less, more preferably 6.3 mPa · s or less, further preferably 5 mPa · s or more, and more preferably 6 mPa · s or more.
The TBS (Taperd bearing simulator) viscosity here refers to the effective viscosity under high temperature and high shear, and is a method based on ASTM D4683 (Standard Test Method for Measuring Viscosity at High Shear Rate and High Temperature by Tapered Bearing Simulator). Viscosity at a shear rate of 10 ⁶ / s (provided that the temperature condition was 150 ° C. or 100 ° C.).

  The amount of sulfated ash in the lubricating oil composition of the present invention is preferably 0.1 to 2% by mass, more preferably 0.2 to 1% by mass, and still more preferably 0.4 to 0.8% by mass. It is.

  The lubricating oil composition of the present invention can be preferably used as a lubricating oil for internal combustion engines such as gasoline engines for two-wheeled vehicles, four-wheeled vehicles, power generation and marine use, diesel engines, gas engines, etc., especially for automobiles, especially diesel. It can be preferably used for engines. In addition, other lubricants that require wear prevention performance and long drain performance, such as drive system lubricants such as automatic or manual transmissions, wet brakes, hydraulic fluids, turbine oils, compressor oils, bearing oils, refrigerator oils, etc. It can also be suitably used as a lubricating oil.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Examples 1-2, Comparative Examples 1-2)
As shown in Table 1, various lubricating oils were prepared, and the friction torque reduction rate was measured. The results are shown in Table 1.

(Measurement of friction torque reduction rate)
The friction torque reduction rate was measured using the engine motoring friction test under the following conditions.
Engine: 2L class inline 4-cylinder roller type valve operated engine Engine speed: 750 to 3000 r / min
Oil temperature: 60, 80, 100 ° C
Reference oil: Commercially available 5W30 oil In addition, in the evaluation of the friction torque reduction rate, the average value of the friction torque under each measured condition was calculated, and the friction torque reduction rate was calculated as compared with the case where the reference oil was used.

  As shown in Table 1, Example 1 in which a styrene-diene copolymer viscosity index improver having a PSSI of 10 was blended with a lubricating base oil and Example 2 in which a polymethacrylate viscosity index improver having a PSSI of 5 were blended It can be seen that the friction torque reduction rate is improved with respect to the commercially available 5W-30 oil which is the reference oil. This effect is found to be a significant friction torque reduction rate as compared with Comparative Examples 1 and 2 in which a polymethacrylate viscosity index improver having a high PSSI is blended based on the conventional technical idea.

Claims (4)

Styrene-diene copolymer viscosity index improver having a polystyrene base- hydrogenated polyisoprene block with a PSSI of 10 or less and / or a polymethacrylate viscosity index with a PSSI of 10 or less in a lubricating base oil having a viscosity index of 120 or more The composition is formulated so that the viscosity index of the composition is 160 or more and the rate of decrease in kinematic viscosity at 100 ° C. after shearing is 15% or less, and the kinematic viscosity at 100 ° C. of the composition is 9.3 to 11.0 mm. ² / s, 40 ° C. kinematic viscosity is 40-60 mm ² / s, 100 ° C. kinematic viscosity after shearing is 9.3 mm ² / s or more, and 100 ° C. TBS viscosity is 7 mPa · s or less. A lubricating oil composition for an internal combustion engine. The lubricating oil composition for an internal combustion engine according to claim 1, comprising a metal salt of a phosphorus-containing acid ester. The lubricating oil composition for internal combustion engines according to claim 1 or 2 , comprising a metallic detergent, an ashless dispersant, and an antioxidant. The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 3 , wherein the amount of sulfated ash in the composition is 0.1 to 2% by mass.