JP5255220B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition, and in particular, relates to a lubricating oil composition that is excellent in low friction and particularly suitable as a lubricating oil for an internal combustion engine of a diesel engine or a direct injection gasoline engine.

  In general, lubricating oil is used in an internal combustion engine, an automatic transmission, a shock absorber, a drive system device such as a power steering, a gear, and the like, which are engines having a sliding portion, in order to facilitate the operation thereof. In particular, lubricating oils for internal combustion engines mainly lubricate parts such as piston rings and cylinder liners, bearings for crankshafts and connecting rods, valve mechanisms, etc., as well as cooling inside the engine, cleansing and dispersing combustion products, It acts to prevent corrosion.

  As described above, in addition to the various performances required for the lubricating oil for internal combustion engines, in recent years, low ash, low phosphorus, low sulfur for improved fuel efficiency and exhaust gas aftertreatment equipment, There is also a need to achieve a high level of trade-off performance such as improved long drain performance. In an internal combustion engine, energy loss is large in a friction part where lubricating oil is involved, and as a countermeasure for reducing friction loss and reducing fuel consumption, for example, as shown in Patent Document 1, various additives such as a friction reducing agent are added. Lubricating oil in combination with agents is used.

  Conventionally, in order to reduce the friction coefficient of lubricating oil, addition of an organic molybdenum compound typified by molybdenum dithiocarbamate or molybdenum dithiophosphate, a combination formulation of the organic molybdenum compound and a metallic detergent (see, for example, Patent Document 2), Or the combination mixing (for example, refer patent document 3) etc. of this organic molybdenum compound and a sulfur type compound is performed.

  However, in a diesel engine or a direct injection type gasoline engine, a large amount of soot generated in the piston is mixed into the engine oil. Since this soot has surface activity, it exhibits the action of adsorbing the polar additive in the oil and scraping the coating formed on the friction surface. Therefore, even under such severe friction conditions, even if an organic molybdenum compound, which is said to have the best friction reduction effect, is used, a sufficient friction reduction effect is obtained due to inhibition by soot and metal wear powder. I can't. There are few research examples to improve this, and only a few proposals have been made such as blending alkali metal borate hydrate to improve the fuel efficiency of diesel engines (see, for example, Patent Document 4). .

  On the other hand, it is known that lowering the viscosity of a lubricating oil is also effective as a means of improving fuel efficiency. A multi-component which is obtained by adding a viscosity index improver such as polymethacrylate or ethylene-propylene copolymer to a low-viscosity lubricating oil. Grade diesel engine oil is commonly used. However, the fuel efficiency reduction effect of the multi-grade diesel engine oil to which only these viscosity index improvers are added is insignificant, and cannot be said to be sufficient. For this reason, there has been a strong demand for the development of engine oil technology capable of exhibiting a sufficient fuel consumption reduction effect even in diesel engines and direct injection gasoline engines.

  By the way, for diesel engines, there is an urgent need to reduce NOx and particulate matter (SPM). In order to reduce these exhaust gases, for example, high pressure injection, exhaust gas recirculation system (EGR), oxidation catalyst, diesel The introduction of exhaust gas reduction means such as a particulate filter (DPF) or NOx storage reduction catalyst is being studied.

  However, it is known that, among the exhaust gas reduction means, in particular, the oxidation catalyst, NOx storage reduction catalyst, and DPF of the exhaust gas after-treatment device have a longer life depending on the composition of the engine oil used. For example, when a lubricating oil containing a zinc dialkyldithiophosphate (hereinafter referred to as ZnDTP) that is effective as an antiwear or antioxidant (peroxide decomposer) is used, the zinc content in ZnDTP is lost during the combustion process. By forming oxides, phosphates or sulfates and depositing them on the catalyst surface or in the filter, the purification performance of these exhaust gas aftertreatment devices may be impaired. Therefore, it is desirable not to add ZnDTP to the engine lubricating oil equipped with the exhaust gas aftertreatment device as described above, or to keep the amount added even if it is used. Moreover, since it is easy to produce the above-mentioned problem about a metal type detergent and a sulfur content, when a metal oxide and a sulfate deposit as ash content, it is desirable to reduce these content as much as possible.

  In addition, in diesel engines, particularly diesel engines equipped with EGR, soot is mixed in a large amount of lubricating oil, and there is concern about increased wear of valve systems and deterioration of high temperature cleanliness such as piston cleanliness. The Further, even in a direct-injection gasoline engine, there are concerns about the same adverse effects due to soot mixing, combustion chamber deposits and valve deposits. Therefore, simply reducing the content of ZnDTP, metallic detergents, and sulfur is accompanied by a particular difficulty, and new means for compensating for the reduction in cleanliness and wear prevention associated with the reduction have been studied. I need it.

  As a lubricating oil composition for an engine equipped with an exhaust gas aftertreatment device, a diesel engine oil composition having a sulfated ash content of 0.7% by mass or less has been proposed (see Patent Document 5). Further, engine oils containing a dispersion-type viscosity index improver have been proposed as means for improving cleanliness at the time of soot mixing and wear prevention (see Patent Documents 6 and 7). However, in these proposals, high-temperature cleanliness and base number maintenance performance when metal-based detergents are reduced are not always sufficient, and high-temperature cleanliness when ZnDTP content is reduced and wear prevention under mixing of soot Sex has not been fully examined.

  Salicylate-based detergents that reduce ZnDTP and adjust the metal ratio to 2.6 or less as a method to greatly improve the high temperature cleanability, base number maintenance, or low friction of the lubricating oil, Lubricating oil compositions containing less than 2 salicylate detergents and overbased sulfonates are known, but their anti-wear properties and friction reduction performance under soot mixing are not always sufficient, and improvements are required. (See Patent Documents 8 to 10).

Therefore, in order to maintain or improve the high temperature cleanliness and the base number maintainability at a high level, to suppress wear at the time of soot mixing that is remarkable when the blending amount of ZnDTP is reduced, and to further increase the friction reduction effect There is room for further consideration.
Japanese Patent Publication No. 3-23595 Japanese Examined Patent Publication No. 6-62983 Japanese Patent Publication No. 5-83599 Japanese Examined Patent Publication No. 1-48319 JP 2000-256690 A JP 2001-279287 A JP 2004-10799 A Japanese Patent No. 3662228 Japanese Patent No. 3709379 Japanese Patent No. 3738228

  The present invention has been made in view of such a situation, and an object of the present invention is to have a sufficiently low friction property, that is, a fuel saving property even when the lubricating oil is deteriorated in which soot and metal wear powder are mixed. That can maintain the performance of exhaust gas aftertreatment equipment for a long period of time. It is to provide a composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that a lubricating oil composition containing an additive in a specific amount and combination can solve the above problems, and has completed the present invention.

  That is, the present invention provides a lubricant base oil based on the total amount of the composition based on (A) an ashless friction modifier in an amount of 0.01 to 10% by mass, and (B) a phosphorus-containing wear inhibitor in an amount of 0.01 to 0.01%. 0.2% by mass, (C) at least (Ca) a metal detergent having a metal ratio of less than 2 and (Cb) a metal detergent having a metal ratio of 2 or more, and a metal ratio of 2.4 to 10 0.01 to 1% by mass of the metal detergent prepared so as to be a metal amount, and (D) an ashless dispersant having a weight average molecular weight of 3000 to 20000 as a nitrogen amount of 0.01 to 0.4. The present invention solves the above-mentioned problems by providing a lubricating oil composition characterized by containing a mass%.

  According to the present invention, it is possible to achieve excellent low friction and wear prevention even under soot mixing, and it is possible to reduce the ash, so that the performance of the exhaust gas aftertreatment device is sufficiently maintained over a long period of time. be able to.

  In the present invention, the component (A) is preferably a compound containing at least 3 atoms of one or more elements selected from nitrogen, oxygen and sulfur.

  In this way, even when phosphorus-containing antiwear agents, particularly ZnDTP, are reduced or not used, wear and friction under soot mixing can be greatly reduced, and low phosphorus can be achieved. Therefore, the performance of the exhaust gas aftertreatment device can be sufficiently maintained over a long period of time.

  In the present invention, the component (Ca) includes (C1a) a sulfonate detergent having a metal ratio of less than 2, (C2a) a phenate detergent having a metal ratio of less than 2, and (C3a) a salicylate detergent having a metal ratio of less than 2. Preferably, the component (Cb) is a sulfonate detergent having a metal ratio of 2 or more and / or (C2b) a phenate detergent having a metal ratio of 2 or more. It is preferable.

  By doing in this way, the wear prevention property under soot mixing, high temperature cleanliness, and low friction property can be made compatible in a higher dimension.

  Moreover, it is preferable that the lubricating oil composition of the present invention is for a diesel engine or a direct injection gasoline engine.

  The lubricating oil composition of the present invention can reduce wear and friction and is excellent in high-temperature cleanliness, and the influence at the time of soot mixing is remarkable when the compounding amount of phosphorus compounds such as ZnDTP is reduced for internal combustion engines. The diesel engine and direct-injection gasoline engine are excellent in sustainability of fuel efficiency. And the performance of the exhaust gas aftertreatment device can be sufficiently maintained over a long period of time. Therefore, in addition to being suitably used as a lubricating oil for an internal combustion engine of a vehicle equipped with an exhaust gas aftertreatment device, it is also suitably used as a diesel engine oil, a direct injection engine oil, or the like in which soot is mixed in the engine oil. Is done. It can also be used suitably for gasoline engines, diesel engines, gas engines, etc. for motorcycles, automobiles, power generation, cogeneration, etc. Not only can it be suitably used for various engines, but it is also useful for various engines for ships and outboard motors, and for other types of lubricating oil.

  Such an operation and gain of the present invention will be made clear from the best mode for carrying out the invention described below.

Hereinafter, the lubricating oil composition of the present invention will be described in detail.
The lubricating base oil used in the lubricating oil composition of the present invention (hereinafter also referred to as the composition of the present invention) is not particularly limited, and both mineral base oils and synthetic base oils should be used. Can do.

  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, Slack wax refined by one or more treatments such as hydroisomerization, solvent dewaxing, catalytic dewaxing, hydrorefining, or slack wax obtained by solvent dewaxing process, etc., and further deoiling / refining the slack wax Hydrocracking or hydrocracking synthetic waxes such as wax cracking / isomerized mineral oil and Fischer-Tropsch wax produced by hydrocracking or hydroisomerization of wax-containing components such as waxes based on normal paraffin Examples include synthetic wax decomposition / isomerized base oils produced by the isomerization technique.

  Specific examples of synthetic base oils include polybutenes or hydrides thereof; 1-octene oligomers, 1-decene oligomers, 1-dodecene oligomers, etc., having 6 to 18 carbon atoms, preferably 8 to 12 carbon atoms α. -Poly-α-olefins such as olefin oligomers or hydrides thereof; diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl sebacate; neopentyl glycol ester , Polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, and pentaerythritol pelargonate; alkyl naphthalene, alkylbenzene, and aromatic ester Examples thereof include aromatic synthetic oils such as tellurium or mixtures thereof.

Although there is no restriction | limiting in particular in the manufacturing method of the lubricating base oil used for this invention, As a preferable example of a lubricating base oil, the base oils (1)-(8) shown below are used as a raw material, The base oil obtained by refine | purifying the lubricating oil fraction collect | recovered from this raw material oil by a predetermined refinement | purification method, and collect | recovering a lubricating oil fraction can be mentioned.
(1) Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO)
(3) Wax obtained by the lubricant dewaxing process (slack wax, wax obtained by further deoiling and refining slack wax, etc.) and / or synthetic wax obtained by gas-to-liquid (GTL) process (Fischer-Tropsch wax, GTL) Wax etc.)
(4) One or two or more mixed oils selected from base oils (1) to (3) and / or mild hydrocracking treatment oils of the mixed oils (5) selected from base oils (1) to (4) 2 or more kinds of mixed oils (6) Base oil (1), (2), (3), (4) or (5) debris oil (DAO)
(7) Mild hydrocracking treatment oil (MHC) of base oil (6)
(8) Two or more mixed oils selected from base oils (1) to (7)

  The above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay purification; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning is preferable. In the present invention, one of these purification methods may be performed alone, or two or more may be combined. Moreover, when combining 2 or more types of purification methods, the order in particular is not restrict | limited, It can select suitably.

Furthermore, as the base oil, the following base oil (9) obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment Or (10) is preferable.
(9) The base oil selected from the base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like. Hydrocracked mineral oil obtained by performing dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lubricating oil fraction, or distillation after the dewaxing treatment (10) The above base oils (1) to (8) ) Or a lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic dewaxing. Hydroisomerized mineral oil obtained by performing dewaxing treatment such as or by distillation after the dewaxing treatment

The lubricating base oil in the present invention, among these ones,% _{C P} is 70 or more,% _{C A} is 1 or less, viscosity index 115 or more, the base oil CCS viscosity at -35 ° C. is not more than 3000 mPa · s ( X) is preferred.

  Further, as the base oil (X), among the base oils (9) and (10), the wax component selected from the base oil (3) or a raw material containing the wax component is hydrocracked or hydroisomerized. The base oil (X1) obtained by using as a raw material is most preferable.

  When obtaining the lubricating base oil of (9) or (10) above, as the dewaxing step, the thermal / oxidative stability and low temperature viscosity characteristics can be further enhanced, and the fatigue prevention performance of the lubricating oil composition is further enhanced. It is particularly preferable to include a contact dewaxing step. Moreover, when obtaining the lubricating base oil of (9) or (10) above, a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary.

  The catalyst used for the hydrocracking / hydroisomerization is not particularly limited, but a composite oxide having cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one or more of the composite oxides Hydrocracking catalyst in which a metal having a hydrogenation ability (for example, one or more metals such as Group VIa metal and Group VIII metal in the periodic table) supported by a binder combined with a binder is supported Or a hydroisomerization catalyst in which a support containing zeolite (for example, ZSM-5, zeolite beta, SAPO-11, etc.) is loaded with a metal having a hydrogenation ability including at least one of Group VIII metals. Preferably used. The hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.

The reaction conditions in the hydrocracking / hydroisomerization are not particularly limited, but the hydrogen partial pressure is 0.1 to 20 MPa, the average reaction temperature is 150 to 450 ° C., the LHSV is 0.1 to 3.0 hr ⁻¹ , the hydrogen / oil ratio. 50 to 20000 scf / b (meaning standard cubic feet / barrel. It is preferably a value obtained by dividing the volume of hydrogen gas in the standard state (legitimate feet) by the volume of oil (barrel, 1b = about 159 L)).

  In the case of catalytic dewaxing (catalyst dewaxing), the hydrocracking / isomerization product oil is reacted with hydrogen in the presence of a suitable dewaxing catalyst under conditions effective to lower the pour point. In catalytic dewaxing, some of the high-boiling substances in the cracking / isomerization product are converted to low-boiling substances, the low-boiling substances are separated from the heavier base oil fraction, and the base oil fraction is fractionated. Two or more kinds of lubricating base oils are obtained. The low-boiling substances can be separated before obtaining the target lubricating base oil or during fractional distillation.

  The dewaxing catalyst is not particularly limited as long as it can lower the pour point of the cracked / isomerized product oil, but the desired lubricating base oil is obtained from the cracked / isomerized product oil in a high yield. Those that can be used are preferred. As such a dewaxing catalyst, a shape selective molecular sieve (molecular sieve) is preferable, and specifically, ferrierite, mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22 ( And thealuminophosphates (SAPO) and the like. These molecular sieves are preferably used in combination with a catalytic metal component, and more preferably in combination with a noble metal. A preferable combination includes, for example, a composite of platinum and H-mordenite.

The dewaxing conditions are not particularly limited, but the temperature is preferably 200 to 500 ° C., and the hydrogen pressure is preferably 10 to 200 bar (1 MPa to 20 MPa). Also, in the case of flow-through reactor, _{H 2} processing speed is preferably 0.1~10kg / l / hr, LHSV is preferably 0.1 to 10 ^-1, more preferably 0.2～2.0H ^-1 . Dewaxing refers to a substance having an initial boiling point of 350 to 400 ° C., usually 40% by mass or less, preferably 30% by mass or less, contained in the cracked / isomerized product oil, having a boiling point lower than the initial boiling point. It is preferable to carry out the conversion to a substance having the same.

  Another preferred example of the base oil is a poly α-olefin base oil (X2) having the above properties, and specifically, an α-olefin having 6 to 16 carbon atoms, preferably 8 to 12 carbon atoms. Oligomers or co-oligomers (for example, 1-octene oligomer, 1-decene oligomer, 1-dodecene oligomer, etc.) and hydrides thereof. There is no particular limitation on the production method of this poly α-olefin base oil, but for example, aluminum trichloride, boron trifluoride or boron trifluoride and water, alcohol (for example, ethanol, propanol or butanol), carboxylic acid, Alternatively, polymerization of an α-olefin in the presence of a polymerization catalyst such as a Friedel-Crafts catalyst containing a complex with an ester (for example, ethyl acetate or ethyl propionate) can be mentioned.

The% C _P of the base oil (X) is preferably 70 or more, more preferably 80 from the viewpoint of improving thermal / oxidation stability, viscosity temperature characteristics, and high temperature cleanliness, and reducing wear and friction under soot mixing. More preferably, it is 85 or more, more preferably 90 or more, and the upper limit thereof is not particularly limited, and may be 100. However, it is preferably 97 or less, more preferably 95 in terms of superior soot dispersibility and sludge solubility. Hereinafter, it is more preferably 92 or less.

Moreover,% C _A is heat and oxidation stability and viscosity-temperature characteristics of the base oil (X), and good high temperature detergency, from the viewpoint of reducing wear and friction under mixed soot, preferably 1 or less, more preferably 0.5 or less, particularly preferably 0.2 or less.

Moreover,% C _N of base oil (X), the thermal and oxidation stability and viscosity-temperature characteristics, excellent high-temperature detergency, in that it can reduce the wear and friction under mixed soot, preferably 30 or less, more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The lower limit is not particularly limited, and is preferably 3 or more, more preferably 5 or more, more preferably in terms of excellent soot dispersibility and sludge solubility. Is 8 or more.

_Moreover,% C P _/% C _N of the base oil (X) is not particularly limited, heat and oxidation stability and viscosity-temperature characteristics, excellent high-temperature detergency, can reduce wear and friction under mixed soot In view of this, it is preferably 4 or more, more preferably 6 or more, particularly preferably 9 or more, and there is no particular upper limit on the upper limit, and preferably 40 or less, more excellent in terms of soot dispersibility and sludge solubility. Preferably it is 15 or less, More preferably, it is 12 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. That is, the preferred ranges of% C _P ,% C _N and% C _A described above are based on the values obtained by the above method. For example, even a lubricating base oil that does not contain a naphthene compound is obtained by the above method. is% C _N may indicate a value greater than zero.

  The viscosity index of the base oil (X) is preferably 115 or more, more preferably 120 or more, from the viewpoint of improving thermal / oxidation stability, viscosity temperature characteristics, and high temperature cleanliness, and reducing wear and friction under soot mixing. More preferably, it is 125 or more. Moreover, the upper limit of the viscosity index of the base oil (X) is usually 200 or less, preferably 160 or less. The above base oil (X1) preferably has a viscosity index of 130 to 160, particularly preferably 135 to 150, and the base oil (X2) has a viscosity index of 120. ~ 160 are preferred, and 120-130 are particularly preferred.

  Further, the base oil (X) has a CCS viscosity at −35 ° C. of 3000 mPa · s or less, preferably 2400 mPa · s or less, more preferably 2000 mPa · s, from the viewpoint of improving fuel economy at low temperature start. s or less, more preferably 1900 mPa · s or less, particularly preferably 1800 mPa · s or less. In particular, as the base oil (X2), a CCS viscosity at −35 ° C. is preferably 1700 mPa · s or less, more preferably 1600 mPa · s or less. In addition, by using a lower CCS viscosity as the base oil (X), a higher viscosity base oil is used as the base oil (Y) that may be used in combination with the base oil (X) described later. In addition, the content of the base oil (Y) can be increased, and while maintaining fuel efficiency at the time of low-temperature start-up, a significant improvement effect can be expected in the wear prevention property under soot mixing.

The kinematic viscosity at 100 ° C. of the base oil (X) is not particularly limited, but is 1 to ²⁰ mm ² / s, preferably ² to 8 mm ² / s, more preferably 3 to 5 mm ² / s, particularly preferably. It is 3.5 to 4.5 mm ² / s. When the kinematic viscosity at 100 ° C. of the base oil (X) exceeds 20 mm ² / s, the low-temperature viscosity characteristic deteriorates. On the other hand, when the kinematic viscosity is less than 1 mm ² / s, an oil film is formed at the lubrication point. Insufficient lubrication results in poor lubricity and increases the evaporation loss of the lubricating base oil, which is not preferable.

  Although there is no restriction | limiting in particular in the pour point of base oil (X), Preferably it is -10 degrees C or less, More preferably, it is -15 degrees C or less, More preferably, it is -17.5 degrees C or less, Base oil (X) By setting the pour point to −10 ° C. or lower, a lubricating oil composition having excellent low-temperature viscosity characteristics can be obtained. In addition, as above-mentioned base oil (X1), the thing whose pour point is -40 degreeC or more is suitable in balance with a low temperature viscosity characteristic, a viscosity index, and the economical efficiency of a dewaxing process, and -30 degreeC or more is suitable. A thing of -25 degreeC or more is especially suitable. Further, as the above base oil (X2), those having a pour point of −40 ° C. or less are preferred, those having −45 ° C. or less are more preferred, low temperature viscosity characteristics, viscosity index, and economics of the production process. Those having a temperature of -70 ° C. or more are preferable in terms of balance with the properties.

  The aniline point of the base oil (X) is not particularly limited, but is preferably 108 ° C. or higher, more preferably 115 ° C. or higher, and still more preferably 120 ° C. or higher. Although 125 degreeC or more may be sufficient as an aspect, Preferably it is 125 degrees C or less at the point which is excellent by the dispersibility of soot dispersibility and the solubility of sludge, and is excellent by the adaptability to a sealing material.

  Although there is no restriction | limiting in particular about the sulfur content of base oil (X), Preferably it is 0.1 mass% or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.01 mass% or less, Most preferably, it is 0.00. It is desirable that it is 001 mass% or less.

  The NOACK evaporation amount of the base oil (X) is not particularly limited, but is preferably 8 to 20% by mass, more preferably 10 to 16% by mass, and particularly preferably 12 to 14% by mass. It is particularly preferred because it can reduce wear and friction under easy mixing, and can suppress an increase in the viscosity of the lubricating oil in use and can easily maintain fuel economy over a long period of time. In addition, the NOACK evaporation amount as used in the field of this invention means the evaporation loss amount measured based on ASTM D 5800-95.

  Further, the iodine value of the base oil (X) is not particularly limited, but is preferably 8 or less, more preferably 6 or less, because it is excellent in high-temperature cleanliness and can reduce wear and friction under soot mixing. In view of economical efficiency in the production process, it is preferably 0.001 or more, more preferably 0.01 or more. The above base oil (X1) preferably has an iodine value of 2 or less, more preferably 1 or less, still more preferably 0.5 or less, and 0.1 The following are particularly preferred: Further, the above base oil (X2) has an iodine value of preferably 8 or less, more preferably 6 or less, and 0.001 or more, particularly preferably 0. Those having 2 to 6 are preferable, those having 0.3 to 4 are more preferable, and those having 0.4 to 1 are particularly preferable. The “iodine value” in the present invention means an iodine value measured by an indicator titration method of JIS K 0070 “acid value, saponification value, iodine value, hydroxyl value, and unsaponification value of a chemical product”. .

  In the lubricating base oil used in the present invention, the content of the base oil (X) is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass based on the total amount of the lubricating oil base oil. % Or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and may be 100% by mass, but for reasons such as solubility of the additive, sludge solubility and effectiveness of the additive, economy, etc. Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

The lubricating base oil used in the present invention preferably contains the base oil (X), but does not fall under the base oil (X) regulation among the above-described mineral base oils and synthetic base oils. One or two or more kinds of base oils selected from those can be preferably used in combination. As such base oil (Y),
(Y1) Base oil having a CCS viscosity at −35 ° C. exceeding 3000 mPa · s (for example, a base oil having a CCS viscosity at −35 ° C. exceeding 3000 mPa · s, preferably 100,000 mPa · s or less, more preferably 3500 to 15000 mPa · s. Base oil)
(Y2)% _{C P} is less than 70 base oil (e.g.,% _{C P} is less than 50 to 70, preferably a base oil of less than 60 to 70),
(Y3)% _{C A} is more than 1 base oil (e.g.,% _{C A} of 20 or less than 1, preferably 10 or less, more preferably 3 or less of the base oil)
(Y4) a base oil having a viscosity index of less than 120 (for example, a base oil having a viscosity index of preferably less than 80 to 120) and (Y5) a group that does not satisfy any two or more of the regulations of the base oil (X) oil,
Chosen from.

Among these, (Y1) is preferable, and more preferable specific examples thereof include a well-balanced improvement in thermal / oxidative stability, viscosity temperature characteristics, high temperature cleanliness, wear and friction reduction under soot mixing of the lubricating oil composition. in that it can, (Ya) viscosity index of 80 or higher,% _{C P} is 60 or more,% _{C a} of 10 or less, 100 ° C. kinematic viscosity ^{5 mm} 2 / s or more, CCS viscosity exceeds 3000 mPa · s at -35 ° C. Base oils.

The viscosity index of the base oil (Ya) is preferably 100 or more, more preferably 120 or more, preferably 170 or less, more preferably 135 or less, and its% _CP is preferably 70 or more, more preferably 75 or more, preferably 100 or less, more preferably 85 or less, preferably the% _{C a} is 3 or less, more preferably 2 or less, more preferably 1 or less, CCS viscosity at -35 ° C. is a 3000 mPa · s It is more than 3,500 mPa · s, preferably 100000 mPa · s or less, more preferably 50000 mPa · s or less, and still more preferably 15000 mPa · s or less.

The kinematic viscosity at 100 ° C. of such base oil (Y), that is, base oils (Y1) to (Y5) or (Ya) is preferably 5 mm ² / s or more, more preferably 6 mm ² / s or more. The thickness is preferably 35 mm ² / s or less, more preferably 20 mm ² / s or less, still more preferably 12 mm ² / s or less, and particularly preferably 8 mm ² / s or less. By using a base oil (Y) having a kinematic viscosity at 100 ° C. of 5 mm ² / s or more, it has excellent anti-wear properties when mixed with soot, and it reduces evaporation loss and increases viscosity even during long-term use. It is easy to suppress and maintain low friction performance, and by using a material having a thickness of 35 mm ² / s or less, it is possible to improve low temperature startability and fuel economy during cold conditions.

  Further, the NOACK evaporation amount of such base oil (Y), that is, base oils (Y1) to (Y5) or (Ya) is not particularly limited, but is preferably 0 to 25% by mass, more preferably 2 -15% by mass, particularly preferably 5-10% by mass. By selecting a base oil (Y) with a small amount of NOACK evaporation, it is easy to maintain low friction performance by reducing evaporation loss and suppressing increase in viscosity even during long-term use. Is particularly preferable because it is easy to obtain a lubricating oil composition having excellent low-temperature viscosity characteristics.

  Further, the sulfur content of such base oil (Y), that is, (Y1) to (Y5) or (Ya) is not particularly limited, but is preferably 1% by mass or less, and more preferably 0.3%. It is not more than mass%, more preferably not more than 0.1 mass%, particularly preferably not more than 0.01 mass%. By reducing the sulfur content, it is possible to obtain a composition with further improved thermal / oxidative stability, high temperature cleanability and low friction.

  Further, the iodine value of such base oil (Y), that is, (Y1) to (Y5) or (Ya) is not particularly limited, but is excellent in high-temperature cleanliness and reduces wear and friction under soot mixing. It is preferably 8 or less, more preferably 6 or less, and preferably 0.01 or more, more preferably 1 or more, and further preferably 3 or more, in terms of economy in the production process.

  When the base oil (Y) is used for the lubricating base oil used in the present invention, the content thereof is not particularly limited, but is preferably 10% by mass or more, more preferably based on the total amount of the lubricating base oil. Is 20% by mass or more, more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass or less.

Incidentally, the lubricant base oil in the present invention has a kinematic viscosity at 100 ° C. is preferably 3 to 8 mm ² / s, more preferably 4 to 6 mm ² / s, more 4.5~5.5mm ² / s The viscosity index is preferably adjusted, and the viscosity index is preferably 110 or more, more preferably 115 or more, still more preferably 120 or more, and particularly preferably 125 or more. In addition, the sulfur content of the lubricating base oil in the present invention is not particularly limited and is preferably 0.3% by mass or less, but is preferable in that it can further increase the life-span performance such as base number maintenance. It is 0.1 mass% or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.005 mass% or less.

  Further, the NOACK evaporation amount of the lubricating base oil in the present invention is not particularly limited, but is preferably 5 to 25% by mass, more preferably 10 to 20% by mass, and particularly preferably 12 to 15% by mass. Furthermore, the low temperature viscosity characteristics of the lubricating base oil in the present invention are not particularly limited, but the CCS viscosity at −30 ° C. is preferably 20000 mPa · s or less, more preferably 7000 mPa · s or less, and further preferably 3500 mPa · s or less. It is desirable to do. Here, the CCS viscosity means a viscosity at a specific temperature measured according to JIS K 2010.

  The lubricating oil composition of the present invention contains an ashless friction modifier as the component (A). As the (A) ashless friction modifier, any compound usually used as a friction modifier for lubricating oils can be used, for example, a hydrocarbon group having 6 to 30 carbon atoms, preferably an alkyl group or an alkenyl group. In particular, there are no amine compounds, imide compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic ethers or the like having at least one linear alkyl group or linear alkenyl group having 6 to 30 carbon atoms in the molecule. Examples include ash friction modifiers, or various ashless friction modifiers having 1 to 30 carbon atoms and 2 or more nitrogen atoms. In the present invention, among these ashless friction modifiers, an ashless friction modifier having an ester bond or an amide bond is preferable, and one or more selected from nitrogen, oxygen, and sulfur are used. An ashless friction modifier having at least 3 atoms or more is preferable, and an ashless friction modifier selected from compounds having 2 or more nitrogen atoms and oxygen and / or sulfur atoms, particularly those having an amide bond Is particularly preferred.

  Examples of the amine compound include linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear aliphatic polyamines, or fatty acids thereof. An alkylene oxide adduct of a group amine can be exemplified. Examples of fatty acid esters include esters of linear or branched, preferably linear, fatty acids having 7 to 31 carbon atoms with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of fatty acid amides include amides of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms, and aliphatic monoamines or aliphatic polyamines.

  Examples of suitable ashless friction modifiers having at least 3 atoms of one or more elements selected from nitrogen, oxygen, and sulfur include trihydric or higher polyhydric alcohols such as glycerin and sorbitan and oleic acid. Examples thereof include esters with fatty acids such as compounds having two or more nitrogen atoms, oxygen atoms and / or sulfur atoms, which will be described later.

  Further, as various ashless friction modifiers selected from compounds having two or more nitrogen atoms and oxygen atoms and / or sulfur atoms, the nitrogen atoms are 2 to 10 atoms, preferably 2 to 4 atoms, particularly preferably. The compound which has 2 atoms and has an oxygen atom and / or a sulfur atom, Preferably it is 1-4 atoms, Preferably it has 1-2 atoms, The thing which has an amide bond among these is preferable. More specifically, examples thereof include hydrazide (oleic hydrazide and the like), semicarbazide (oleyl semicarbazide and the like), urea (oleyl urea and the like), ureido (oleyl and the like) exemplified in International Publication No. 2005/037967 pamphlet. Ureido, etc.), allophane amides (oleyl allophanamide, etc.) and derivatives thereof. Among these, one or more compounds selected from the group consisting of nitrogen-containing compounds represented by the following general formulas (1) and (2) and acid-modified derivatives thereof are particularly preferable.

In the general formula (1), R ¹ has a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrocarbon group having 10 to 30 carbon atoms or a functionality. A hydrocarbon group having 10 to 30 carbon atoms, more preferably an alkyl group having 12 to 24 carbon atoms, an alkenyl group or a hydrocarbon group having functionality, particularly preferably an alkenyl group having 12 to 20 carbon atoms, R ² and Each R ³ has a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms or hydrogen having functionality, preferably a hydrocarbon group having 1 to 10 carbon atoms, and functionality. A hydrocarbon group or hydrogen having 1 to 10 carbon atoms, more preferably a hydrocarbon group or hydrogen having 1 to 4 carbon atoms, more preferably hydrogen, and X ¹ represents oxygen or sulfur, preferably oxygen.

As a most preferable example of the nitrogen-containing compound represented by the general formula (1), specifically, a compound in which X ¹ is oxygen and an acid-modified derivative thereof, more specifically, X ¹ is oxygen, R ¹ Is an alkyl or alkenyl group having 12 to 24 carbon atoms, R ² and R ³ are hydrogen, dodecyl urea, tridecyl urea, tetradecyl urea, pentadecyl urea, hexadecyl urea, heptadecyl urea, octadecyl urea, oleyl urea, etc. Examples include urea compounds having an alkyl group or an alkenyl group having 12 to 24 carbon atoms and acid-modified derivatives thereof. Among these, oleyl urea (C ₁₈ H ₃₅ —NH—C (═O) —NH ₂ ) and acid-modified derivatives thereof (boric acid-modified derivatives and the like) are particularly preferable examples.

In the general formula (2), R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms, and preferably a hydrocarbon group or functionality having 10 to 30 carbon atoms. A hydrocarbon group having 10 to 30 carbon atoms, more preferably an alkyl group having 12 to 24 carbon atoms, an alkenyl group or a hydrocarbon group having functionality, particularly preferably an alkenyl group having 12 to 20 carbon atoms, and R ^{5 to} R ⁷ are each independently a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms or hydrogen having functionality, preferably a hydrocarbon group having 1 to 10 carbon atoms, and functionality. C1-C10 hydrocarbon group or hydrogen which has more preferably, C1-C4 hydrocarbon group or hydrogen, More preferably, hydrogen is shown.

Specific examples of the nitrogen-containing compound represented by the general formula (2) include a hydrazide having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms and derivatives thereof. is there. When R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, and R ^{5 to} R ⁷ are hydrogen, the hydrocarbon group having 1 to 30 carbon atoms or the functionality Any of hydrazide having a hydrocarbon group having 1 to 30 carbon atoms, R ⁴ and R ^{5 to} R ⁷ is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms having functionality. And when the remainder of R ^{5 to} R ⁷ is hydrogen, N-hydrocarbyl hydrazide having a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms having functionality (hydrocarbyl is a hydrocarbon group) Etc.).

As a most preferable example of the nitrogen-containing compound represented by the general formula (2), R ⁴ is an alkyl group or alkenyl group having 12 to 24 carbon atoms, and R ⁵ , R ⁶ and R ⁷ are hydrogen. Hydrazide compounds having an alkyl or alkenyl group having 12 to 24 carbon atoms such as tridecanoic acid hydrazide, tetradecanoic acid hydrazide, pentadecanoic acid hydrazide, hexadecanoic acid hydrazide, heptadecanoic acid hydrazide, octadecanoic acid hydrazide, oleic acid hydrazide, and erucic acid hydrazide Examples thereof include acid-modified derivatives (boric acid-modified derivatives and the like). Among these, hydrazide oleic acid _{(C 17 H 33 -C (=} O) -NH-NH 2) and acid-modified derivatives, erucic acid hydrazide _{(C 21 H 41 -C (=} O) -NH-NH 2 ) And acid-modified derivatives thereof are particularly preferred examples.

  Production methods relating to various ashless friction modifiers having 2 or more nitrogen atoms in these molecules and preferred embodiments thereof are described in detail in the above-mentioned International Publication No. 2005/037967 pamphlet. It may be contained in the lubricating oil composition of the present invention in the form of a complex or salt with an organometallic compound. These ashless friction modifiers having 2 or more nitrogen atoms and oxygen atoms and / or sulfur atoms in these molecules are equivalent to or more than the friction reducers conventionally used such as molybdenum dithiocarbamate. In addition to being able to exert a reduction effect, the friction reduction effect is hardly deteriorated even when soot is mixed, and it is particularly preferable because the effect can be easily maintained over a long period of time.

  The content of the (A) ashless friction modifier in the lubricating oil composition of the present invention is 0.01 to 10% by mass, preferably 0.1% by mass or more, more preferably, based on the total amount of the composition. It is 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. When the content of the ashless friction modifier is less than 0.01% by mass, the effect of reducing friction due to the addition tends to be insufficient. Tends to be inhibited, or the solubility of the additive tends to deteriorate.

  Component (B) in the lubricating oil composition of the present invention is a phosphorus-containing wear inhibitor. The phosphorus-containing antiwear agent is not particularly limited as long as it is an antiwear agent containing phosphorus in the molecule. For example, a phosphorus compound represented by the general formula (3) or a general formula (4) is used. It is preferably at least one compound selected from the group consisting of phosphorus compounds, metal salts thereof, amine salts thereof, and derivatives thereof.

In Formula (3), X ² , X ³ and X ⁴ each independently represent an oxygen atom or a sulfur atom, and R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a carbon atom having 1 to 30 carbon atoms. Indicates a hydrogen group.

In the formula (4), X ⁵ , X ⁶ , X ⁷ and X ⁸ are each independently an oxygen atom or a sulfur atom (one or two of X ⁵ , X ⁶ and X ⁷ are a single bond or (poly) oxyalkylene) R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{8 to} R ¹³ 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. 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 one 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 (3) 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 (4) 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 the salt of the phosphorus compound represented by the general formula (3) or (4), the phosphorus compound may be a metal base such as a metal oxide, metal hydroxide, metal carbonate, 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. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

  Specific examples of the nitrogen compounds include ammonia, monoamines, diamines, and polyamines. More specifically, the same compounds as the amine compounds that constitute the amine complex of molybdenum described later in the component (E2) can be exemplified. .

  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 component (B) in the present invention, the above-mentioned phosphorus-containing antiwear agent may be contained in the lubricating oil composition of the present invention containing at least one selected from the following (B1) to (B3) as a main component. Particularly desirable.
(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 no sulfur Metal salt of acid contained

  As said (B1) and (B2) component, what is represented by following General formula (5) can be illustrated.

In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different, and are each independently a secondary alkyl group or primary alkyl group having 3 to 8 carbon atoms, preferably 3 to 6 carbon atoms. Secondary alkyl groups or primary alkyl groups having 6 to 8 carbon atoms, and may have alkyl groups having different carbon numbers and alkyl groups having different structures (secondary, primary) in the same molecule.

  In the present invention, it is preferable to contain a zinc dialkyldithiophosphate having a secondary alkyl group selected from 3 to 8 carbon atoms (B1) 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 oxidation stability can be further improved and the base number maintenance performance can be remarkably improved. It is most preferable to use the components (B1) and (B2) together in that the wear suppression performance and the base number maintenance performance under mixing can be improved at a high level with a good balance.

Note that any conventional method can be adopted as a method for producing zinc dithiophosphate, and is not particularly limited. Specifically, for example, an alkyl group corresponding to R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be used. It can be synthesized by reacting the alcohol with diphosphorus pentasulfide to produce dithiophosphoric acid and neutralizing it with zinc oxide.

The component (B3) is a metal salt of a phosphorus-containing acid that does not contain sulfur, and all of X ^{2 to} X ⁴ in the general formula (3) are oxygen atoms (X ² , X ^3, and X ⁴ 1 One or two of them may be a single bond or a (poly) oxyalkylene group), and all of X ^{5 to} X ⁸ in the general formula (4) are oxygen atoms (X ⁵ , X ⁶ and X ^A typical example is a metal salt of a phosphorus compound in which one or two of ⁷ 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 is reacted with 2 mol of phosphoric diester (one OH group), it is considered that a compound having a structure represented by the following general formula (6) is obtained as a main component. It is thought that there are some molecules

  For example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (two OH groups) are reacted, a compound having a structure represented by the following general formula (7) is considered to be obtained as a main component. However, polymerized molecules are also thought to 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. In the present invention, an alkyl phosphate metal salt having one or two alkyl groups having 4 to 12 carbon atoms is preferable, and an alkyl group having 6 to 8 carbon atoms is preferable in that it is more excellent in wear resistance under soot mixing. Mono- and / or dialkyl phosphate metal salts having one or two are more preferable, and zinc mono- and di-2-ethylhexyl phosphate are particularly preferable.

  The upper limit of the phosphorus-containing antiwear agent in the lubricating oil composition of the present invention, preferably at least one selected from the above (B1), (B2) and (B3) is 0.2% by mass or less as the phosphorus amount. The lower limit is preferably 0.1% by mass or less, more preferably 0.08% by mass or less, and particularly preferably 0.06% by mass or less. The amount is 0.01% by mass or more, preferably 0.02% by mass or more, and particularly preferably 0.04% by mass or more.

  When the content of the phosphorus-containing wear inhibitor exceeds 0.2% by mass as phosphorus, it is not preferable because the high-temperature cleanliness and the base number maintainability are remarkably deteriorated, and 0.09 to 0.2% by mass In this case, it is preferable in that wear does not remarkably occur even in the presence of soot, but it is 0.08% by mass or less in terms of lowering sulfur, lowering phosphorus, or improving high-temperature cleanability and base number maintenance. It is desirable.

  The component (C) in the lubricating oil composition of the present invention contains at least a (Ca) metal detergent having a metal ratio of less than 2 and (Cb) a metal detergent having a metal ratio of 2 or more, and the metal ratio thereof. Is a metal-based detergent prepared so as to be 2.4 to 10. There are no particular restrictions on the type of the metallic detergent used as the (Ca) component or (Cb), and examples include (C1) sulfonate detergent, (C2) phenate detergent, and (C3) salicylate detergent. Any of them can be used. Here, the metal ratio is represented by the valence of the metal element in the metal detergent × the metal element content (mol%) / the soap group content (mol%), and the soap group forms a metal salt. The other organic group is a sulfonic acid-containing group, a salicylic acid-containing group, a phenol-containing group, or the like.

  The structure of the (C1) sulfonate detergent is not particularly limited. For example, an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 100 to 1500, preferably 200 to 700 is used. An alkali metal salt or an alkaline earth metal salt is exemplified, and a magnesium salt and / or a calcium salt is particularly preferably used. Specific examples of the alkyl aromatic sulfonic acid include so-called petroleum sulfonic acid and synthetic sulfonic acid. . 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. Synthetic sulfonic acids include, for example, alkylbenzenes having linear or branched alkyl groups that are obtained as a by-product from an alkylbenzene production plant that is a raw material for detergents, or are obtained by alkylating polyolefin to benzene. As a raw material, a sulfonated one or a sulfonated dinonylnaphthalene is used. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or sulfuric acid is used.

  In the alkylation of the aromatic sulfonic acid, it is preferable to use a linear or branched (poly) olefin, for example, an oligomer of an olefin having 2 to 4 carbon atoms such as ethylene, propylene and butene. It is particularly preferable to use an ethylene oligomer. Alkali metal salts or alkaline earth metal salts of alkyl aromatic sulfonic acids alkylated with ethylene oligomers can particularly enhance the friction reducing effect.

  In addition, as the (C1) sulfonate detergent, the above alkyl aromatic sulfonic acid may be directly reacted with an alkaline earth metal base such as magnesium or / or calcium alkaline earth metal oxide or hydroxide. , 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 Basic alkaline earth metal sulfonates obtained by heating alkaline earth metal salts and alkaline earth metal bases (hydroxides and oxides) in the presence of water, carbon dioxide and / or boric acid or boron Obtained by reacting the neutral alkaline earth metal sulfonate with an alkaline earth metal base in the presence of an acid salt. Carbonate overbased alkaline earth metal sulfonate, it is also included borate overbased alkaline earth metal sulfonate.

  As the (C1) sulfonate detergent in the present invention, the above-mentioned neutral alkaline earth metal sulfonates, basic alkaline earth metal sulfonates, overbased alkaline earth metal sulfonates, and mixtures thereof can be used. .

  As the (C1) sulfonate detergent in the present invention, a calcium sulfonate detergent or a magnesium sulfonate detergent is preferably used, and a calcium sulfonate detergent is particularly preferably used.

  (C1) The sulfonate detergent is usually commercially available in a state diluted with a light lubricating base oil or the like, and is available, but generally the metal content is 1.0 to 20 mass. %, Preferably 2.0 to 16% by weight.

  The base number of the (C1) sulfonate detergent used in the present invention is arbitrary, and is usually 0 to 500 mgKOH / g, but the base number is 100 to 450 mgKOH / g, preferably 200-400 mg KOH / g.

  The base number referred to here is JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. It means the base number by the perchloric acid method measured according to the above.

  (C2) Specifically, as the phenate detergent, an alkylphenol having at least one linear or branched alkyl group having 4 to 40 carbon atoms, preferably 6 to 18 carbon atoms, is reacted with sulfur. Alkali earth metal salts, especially magnesium salts and / or calcium salts of Mannich reaction products of alkylphenols obtained by reacting alkylphenol sulfides obtained by reacting these alkylphenols with formaldehyde are preferably used.

  (C2) The phenate detergent includes an alkali metal or alkaline earth gold phenate (neutral salt) obtained as described above, and an excess alkali metal or alkaline earth metal salt, alkali metal or alkaline earth. In the presence of a basic salt obtained by heating an alkali metal base (a hydroxide or oxide of an alkali metal or alkaline earth metal) in the presence of water, carbon dioxide, boric acid or borate Also included are overbased salts obtained by reacting a neutral salt with a base such as an alkali metal or alkaline earth metal hydroxide.

  These reactions are usually carried out in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating base oil, etc.), and the metal content thereof is 1.0 to It is desirable to use 20% by mass, preferably 2.0 to 16% by mass.

  (C2) The base number of the phenate detergent may be 0 to 500 mgKOH / g, preferably 20 to 450 mgKOH / g.

  (C3) The salicylate 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 alkaline earth metal salt, In particular, a magnesium salt and / or a calcium salt is preferably used.

  As the (C3) salicylate detergent used in the lubricating oil composition of the present invention, a higher monoalkyl salicylic acid metal salt composition ratio is preferable from the viewpoint of superior low-temperature viscosity characteristics, for example, a monoalkyl salicylic acid metal salt composition. An alkyl salicylic acid metal salt having a ratio of 85 to 100 mol%, a dialkyl salicylic acid metal salt being 0 to 15 mol%, and a 3-alkyl salicylic acid metal salt being 40 to 100 mol%, and / or ) A basic salt is preferred. In addition, as the (C3) salicylate-based detergent in the present invention, one containing a dialkyl salicylic acid metal salt is preferable in that it is superior in high-temperature cleanability and base number maintainability.

  The monoalkyl salicylic acid metal salt here means an alkyl salicylic acid metal salt having one alkyl group such as a 3-alkyl salicylic acid metal salt, a 4-alkyl salicylic acid metal salt, a 5-alkyl salicylic acid metal salt, and the like. The constituent ratio of the salt is 85 to 100 mol%, preferably 88 to 98 mol%, more preferably 90 to 95 mol% with respect to 100 mol% of the alkylsalicylic acid metal salt, and an alkylsalicylic acid metal salt other than the monoalkylsalicylic acid metal salt, for example, The composition ratio of the dialkyl salicylic acid metal salt is 0 to 15 mol%, preferably 2 to 12 mol%, and more preferably 5 to 10 mol%. Moreover, the structural ratio of 3-alkyl salicylic acid metal salt is 40-100 mol% with respect to 100 mol% of alkyl salicylic acid metal salt, Preferably it is 45-80 mol%, More preferably, it is 50-60 mol%. The total composition ratio of the 4-alkyl salicylic acid metal salt and the 5-alkyl salicylic acid metal salt corresponds to the composition ratio excluding the 3-alkyl salicylic acid metal salt and the dialkyl salicylic acid metal salt with respect to 100 mol% of the alkyl salicylic acid metal salt. And 0 to 60 mol%, preferably 20 to 50 mol%, more preferably 30 to 45 mol%. By containing a small amount of a metal salt of dialkyl salicylic acid, a composition having excellent high-temperature cleanliness and low-temperature characteristics and excellent base number maintenance can be obtained, and by setting the composition ratio of 3-alkyl salicylate to 40 mol% or more, 5 -The composition ratio of the alkyl salicylic acid metal salt can be relatively lowered, and the oil solubility can be improved.

  Moreover, as an alkyl group in the alkyl salicylic acid metal salt which comprises a (C3) salicylate type detergent, it is C10-40, Preferably it is C10-19 or C20-30, More preferably, it is C14-18. Or it is a C20-C26 alkyl group, Most preferably, it is a C14-18 alkyl group. 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 metal salicylate is used. A secondary alkyl group is particularly preferred from the viewpoint of easily obtaining a salt.

  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.

  (C3) The salicylate-based detergent can be produced by a known method, and is not particularly limited. For example, 1 mol or more of a polymer such as ethylene, propylene, and butene or co-polymer with respect to 1 mol of phenol A method of alkylating with a C10-40 olefin such as a coalescence, preferably a linear α-olefin such as an ethylene polymer, and carboxylating with carbon dioxide or the like, or 1 mol or more per 1 mol of salicylic acid Metals such as oxides or hydroxides of alkali metals or alkaline earth metals to olefins, preferably alkylsalicylic acid mainly composed of monoalkylsalicylic acid obtained by the alkylation method using the linear α-olefin Reaction with base or alkali metal salt such as sodium salt or potassium salt Or by replacing an alkali metal salt with an alkaline earth metal salt. Here, the reaction ratio of phenol or salicylic acid and olefin is preferably controlled to, for example, 1: 1 to 1.15 (molar ratio), more preferably 1: 1.05 to 1.1 (molar ratio). The composition ratio of the monoalkyl salicylic acid metal salt and the dialkyl salicylic acid metal salt can be controlled to a desired ratio, and by using a linear α-olefin as the olefin, a 3-alkyl salicylic acid metal salt and a 5-alkyl salicylic acid metal It is particularly preferable since the constituent ratio of the salt and the like can be easily controlled to a desired ratio, and an alkyl salicylic acid metal salt having a secondary alkyl which is preferable in the present invention can be obtained as a main component.

  The (C3) salicylate-based detergent preferably used in the lubricating oil composition of the present invention comprises an alkali metal or alkaline earth gold salicylate (neutral salt) obtained as described above and an excess of alkali metal or alkali. Basic salts obtained by heating earth metal salts, alkali metals or alkaline earth metal bases (alkali metal or alkaline earth metal hydroxides or oxides) in the presence of water, carbon dioxide gas or boron 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 presence of an acid or borate.

  These reactions are usually carried out in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating base oil, etc.), and the metal content thereof is 1.0 to It is desirable to use 20% by mass, preferably 2.0 to 16% by mass.

  As the most preferable (C3) salicylate detergent used in the present invention, the composition ratio of the monoalkyl salicylic acid metal salt is 85 to 85 because it is excellent in the balance between high temperature cleanability, base number maintenance and low temperature viscosity characteristics. 95 mol%, the composition ratio of dialkyl salicylic acid metal salt is 5 to 15 mol%, the composition ratio of 3-alkyl salicylic acid metal salt is 50 to 60 mol%, and the composition ratio of 4-alkyl salicylic acid metal salt and 5-alkyl salicylic acid metal salt is 35 to 35 mol%. 45 mol% of alkylsalicylic acid metal salt and / or (over) basic salt thereof. The alkyl group here is particularly preferably a secondary alkyl group.

  In the present invention, the base number of the (C3) salicylate detergent is usually 0 to 500 mgKOH / g, preferably 20 to 300 mgKOH / g, particularly preferably 100 to 200 mgKOH / g, and one selected from these Or two or more types can be used together. The base number referred to here is 7. JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.

  The component (C) of the present invention is a metal-based detergent having a (Ca) metal ratio of less than 2 or (Cb) metal if the metal ratio is adjusted to 2.4 to 10 As the metal detergent component having a ratio of 2 or more, any of the metal detergents (C1) to (C3) described above may be used.

  By setting the metal ratio of the component (C) within the above-described range, it is possible to further improve the high temperature cleanliness and the low friction property while sufficiently ensuring the wear prevention property under soot mixing. The metal ratio of the component (C) is preferably 3 to 8, more preferably 4 to 7, and particularly preferably 5 to 6, so that the high temperature cleanliness, the anti-wear property under soot mixing and low It can be set as the composition excellent in balance with friction property.

  In addition, the metal ratio of the component (C) that is a mixture of a plurality of metal detergents is (total) due to the metal detergent (total) metal amount (mol%) x (each) due to the metal detergent. The valence of the metal to be used / (total) the amount of soap group (mol%) attributed to (each) metal-based detergent.

  Specifically, the component (Ca) includes (C1a) a sulfonate detergent having a metal ratio of less than 2, (C2a) a phenate detergent having a metal ratio of less than 2, and (C3a) a salicylate detergent having a metal ratio of less than 2. Any of them can be preferably used, and among them, (C1a) and (C3a) are preferable, and (C1a) is particularly preferable. The preferable metal ratio as these (Ca) components is 1.5 or less, More preferably, it is 1.2 or less.

  As the component (Cb), (C1b) a sulfonate detergent having a metal ratio of 2 or more, (C2b) a phenate detergent having a metal ratio of 2 or more, and (C3b) a salicylate detergent having a metal ratio of 2 or more are preferably used. Among them, (C1b) and (C2b) are preferable, and (C1b) is particularly preferable. The preferable metal ratio as these (Cb) components is (C1b) and (C2b) being 2 to 20, more preferably 6 to 15, and (C3b) being 2 to 20, more preferably. Is 4-8.

As a specific combination of the (Ca) component and the (Cb) component,
(C1a) and (C1b) and / or (C2b),
At least one of (C2a) and (C1b) to (C3b),
(C3a) and at least one or more of (C1b) to (C3b),
A combination of
(C1a) and (C1b),
(C3a) and (C1b) and / or (C3b) are more preferred,
(C1a) and (C1b),
(C3a) and (C1b) are more preferable, and (C1a) and (C1b) are particularly preferable.

  In addition, the combination of (C1a) and (C3b) is not preferable because it not only tends to be inferior in wear preventing property at the time of soot mixing, but also may deteriorate the stability of micelles and precipitate.

  In the lubricating oil composition of the present invention, the content of the component (C) is 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass, more preferably as a metal amount, based on the total amount of the lubricating oil composition. Is 0.1-0.3 mass%, More preferably, it is 0.15-0.25 mass%.

  The component (D) in the present invention is an ashless dispersant. Ashless dispersants include succinimides having an alkenyl or alkyl group derived from polyolefin, nitrogen-containing compounds such as benzylamine, polyamine, Mannich base, boron compounds such as boric acid and borate to these nitrogen-containing compounds, Examples thereof include phosphorus compounds such as (thio) phosphoric acid and (thio) phosphate, derivatives obtained by acting an organic acid, hydroxy (poly) oxyalkylene carbonate, and the like.

  In the present invention, one or two or more arbitrarily selected from these can be blended. Here, the alkenyl group or the alkyl group may be linear or branched. Specifically, preferred are olefin oligomers such as propylene, 1-butene and isobutylene, and ethylene and propylene co-oligomers. Branched alkyl groups derived from alkenyl groups, branched alkenyl groups, and the like, and branched alkyl groups and branched structures derived from polybutene (polyisobutene) having a number average molecular weight of 700 to 5,000, particularly 900 to 5,000. An alkenyl group is preferred.

  The weight average molecular weight of the ashless dispersant used in the present invention needs to be 3000 to 20000, and preferably the weight average molecular weight of the ashless dispersant is 4000 to 15000. When the weight average molecular weight is less than 3000, the molecular weight of the non-polar polybutenyl group is small and the sludge dispersibility is poor, and the amine portion of the polar group which may become an active site for oxidative degradation is relatively increased and oxidized. On the other hand, the weight average molecular weight is preferably 20000 or less and particularly preferably 15000 or less from the viewpoint of preventing the deterioration of the low temperature viscosity characteristics. Here, the weight average molecular weight means that two columns of GHSHR-M (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation are used in series with a 150-CALC / GPC apparatus manufactured by Waters, and tetrahydrofuran is used as a solvent. By means of temperature, 23 ° C., flow rate of 1 mL / min, sample concentration of 1% by mass, sample injection amount of 75 μL, and weight average molecular weight in terms of polystyrene measured with a detector differential refractometer (RI) are meant.

  Examples of the ashless dispersant preferably used in the lubricating oil composition of the present invention include polybutenyl succinimide represented by the following general formula (8) or (9).

  PIB in the general formulas (8) and (9) represents a polybutenyl group, and is obtained from polybutene obtained by polymerizing a high-purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride catalyst or an aluminum chloride catalyst. In the polybutene mixture, those having a vinylidene structure at the terminal are usually contained in an amount of 5 to 100 mol%. From the viewpoint of excellent sludge suppression effect, n is preferably an integer of 2 to 5, and preferably an integer of 3 to 4.

  Although there is no restriction | limiting in particular as a manufacturing method of the succinimide represented by General formula (8) or (9), For example, what chlorinated the said polybutene, Preferably the said high purity isobutene is a boron fluoride type catalyst. Polybutenyl succinic acid obtained by reacting polymerized highly reactive polybutene (polyisobutene), more preferably polybutene from which chlorine and fluorine have been sufficiently removed, with maleic anhydride at 100 to 200 ° C. is converted into diethylenetriamine, triethylenetetramine. It can be obtained by reacting with a polyamine such as tetraethylenepentamine or pentaethylenehexamine.

  When producing bissuccinimide, the polybutenyl succinic acid may be reacted twice the amount (molar ratio) of the polyamine, and when producing monosuccinimide, the polybutenyl succinic acid and the polyamine, etc. What is necessary is just to make it react by quantity (molar ratio). Among these, polybutenyl bissuccinimide is preferable from the viewpoint of excellent sludge dispersibility.

  The polybutene used in the above production method may contain a trace amount of fluorine and chlorine due to the catalyst in the production process. Therefore, the fluorine and chlorine content can be reduced by an appropriate method such as an adsorption method or sufficient water washing. It is preferable to use polybutene that has been sufficiently removed. The content of fluorine or chlorine is preferably 50 mass ppm or less, more preferably 10 mass ppm or less, still more preferably 5 mass ppm or less, and particularly preferably 1 mass ppm or less.

  In the step of obtaining polybutenyl succinic anhydride by reaction of polybutene and maleic anhydride, a chlorination method using chlorine is often applied conventionally. However, this method results in a large amount of chlorine (eg, about 2000 to 3000 ppm) remaining in the succinimide final product. On the other hand, in a method that does not use chlorine, for example, when the highly reactive polybutene is used and / or in the thermal reaction method, chlorine remaining in the final product can be suppressed to an extremely low level (for example, 0 to 30 ppm). Therefore, in order to suppress the chlorine content in the lubricating oil composition to an amount in the range of 0 to 30 ppm by weight, the chlorination method is not used, and the method using the highly reactive polybutene and / or the thermal reaction method is used. The polybutenyl succinic anhydride obtained is preferably used.

  Examples of the polybutenyl succinimide derivative include compounds represented by the above general formula (8) or (9), boron compounds such as boric acid, alcohols, aldehydes, ketones, alkylphenols, cyclic carbonates, organic compounds. It can be used as a so-called modified succinimide in which an oxygen-containing organic compound such as an acid is allowed to act to neutralize or amidate part or all of the remaining amino group and / or imino group. In particular, a boron-containing alkenyl (or alkyl) succinimide obtained by a reaction with a boron compound such as boric acid is advantageous in terms of thermal and oxidation stability.

  Examples of the boron compound that acts on the compound represented by the general formula (8) or (9) include boric acid, borates, and borate esters.

  Specific examples of boric acid include orthoboric acid, metaboric acid, and tetraboric acid.

  Examples of borates include alkali metal salts, alkaline earth metal salts or ammonium salts of boric acid, and more specifically, for example, lithium metaborate, lithium tetraborate, lithium pentaborate, perborate. Lithium borate such as lithium; sodium borate such as sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate; potassium metaborate, potassium tetraborate, Potassium borates such as potassium pentaborate, potassium hexaborate and potassium octaborate; calcium borates such as calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate and calcium hexaborate ; Magnesium metaborate, magnesium diborate, trimagnesium tetraborate, pentaborate Neshiumu, magnesium borate and magnesium hexaborate acid; and ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium borate such as ammonium eight borate.

  Examples of the boric acid ester include esters of boric acid and preferably an alkyl alcohol having 1 to 6 carbon atoms. More specifically, examples thereof include monomethyl borate, dimethyl borate, trimethyl borate, and boric acid. Examples include monoethyl, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, tributyl borate and the like.

  The succinimide derivative in which the boron compound is allowed to act is preferably used since it is excellent in heat resistance and oxidation stability.

  Specific examples of the oxygen-containing organic compound that acts on the compound represented by the general formula (8) or (9) include formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, Carbon such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid, eicosanoic acid C1-C30 monocarboxylic acid, oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid and other C2-C30 polycarboxylic acids or their anhydrides, ester compounds, C2-C6 Examples include alkylene oxide and hydroxy (poly) oxyalkylene carbonate.

  By causing such an oxygen-containing organic compound to act, for example, part or all of the amino group or imino group in the compound represented by the general formula (8) or (9) is represented by the following general formula (10). Presumed to be a structure.

R ¹⁸ in the general formula (10) is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or —O— (R ¹⁹ O) _m. A hydroxy (poly) oxyalkylene group represented by H; R ¹⁹ is an alkylene group having 1 to 4 carbon atoms; and m is an integer of 1 to 5. Among these, polybutenyl bissuccinimides mainly composed of those in which these oxygen-containing organic compounds are allowed to act on all amino groups or imino groups are preferably used since they are excellent in sludge dispersibility. Such a compound is obtained, for example, by allowing 0.5 to (n-1) mol, preferably (n-1) mol of an oxygen-containing organic compound to act on 1 mol of the compound of the general formula (8). It is done. A succinimide derivative having such an oxygen-containing organic compound acted thereon is excellent in sludge dispersibility, and in particular, one having hydroxy (poly) oxyalkylene carbonate acted thereon is preferable.

  As a preferred embodiment when the lubricating oil composition of the present invention contains an ashless dispersant, (D1) an ashless dispersant having a weight average molecular weight of 6500 or more and / or (D2) a weight average molecular weight of 3000 or more and boron It is preferable to contain an ashless dispersant, and these (D1) and (D) and (D1) and ( It is particularly preferable to use D2) together. Among these ashless dispersants, the above-mentioned polybutenyl succinimide and derivatives thereof, particularly those of the bis type are desirable.

  Here, the weight average molecular weight of (D1) component is 6500-20000, Preferably it is 8000 or more, More preferably, it is 9000 or more, Preferably it is 15000 or less, Most preferably, it is 12000 or less. Moreover, the weight average molecular weight of (D2) component is 3000-20000, Preferably it is 4000-6500, More preferably, it is 4500-5500.

  The content of the (D) ashless dispersant in the lubricating oil composition of the present invention is preferably 0.01 to 0.4% by mass in terms of nitrogen element, based on the total amount of the composition, Preferably it is 0.02 mass% or more, More preferably, it is 0.04 mass% or more, Preferably it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less, More preferably, it is 0.1 mass% It is as follows. (D) When the content of the ashless dispersant is less than the above lower limit, the wear preventing property under soot mixing becomes insufficient and a sufficient cleansing effect cannot be exhibited, while the content is the above When the upper limit is exceeded, the low-temperature viscosity characteristics and the demulsibility deteriorate, which is not preferable.

  In the case of using the component (D1), the content is preferably 0 in terms of nitrogen element based on the total amount of the composition in terms of improving the anti-wear property under soot mixing and excellent low-temperature viscosity characteristics. 0.005 to 0.1% by mass, and more preferably 0.01 to 0.04% by mass.

  In addition, when the component (D2) is used, the content is preferably 0.01% by mass or more in terms of nitrogen element based on the total amount of the composition in order to enhance sufficient high-temperature cleanability and thermal stability. More preferably, it is 0.02 mass% or more, preferably 0.3 mass% or less, more preferably 0.1 mass% or less, and still more preferably 0.04 mass% or less. For the same reason, the content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and further preferably 0.008% by mass in terms of boron element based on the total amount of the composition. % Or more, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, further preferably 0.04% by mass or less, and particularly preferably 0.02% by mass or less.

  Moreover, as (D2) component, the mass ratio (B / N ratio) of the boron content and nitrogen content is 0.1-5 normally, Preferably it is 0.1-1, More preferably, it is 0.00. It is particularly preferable to select and use one of 2 to 0.6.

  The mass ratio (B / N ratio) of boron content and nitrogen content (B / N ratio) resulting from (D) ashless dispersant in the present invention is to reduce wear and friction under soot mixing and to enhance high temperature cleanliness. In addition, it is desirable to make it contain 0.01 to 5, preferably 0.05 to 1, more preferably 0.1 to 0.4, and particularly preferably 0.1 to 0.2.

  The lubricating oil composition of the present invention has the above-described structure, reduces wear and friction under soot mixing, is excellent in high-temperature cleanliness, and can also improve startability and fuel economy in cold conditions. However, any additive commonly used in lubricating oils can be added to further improve its performance or depending on other purposes. In particular, the lubricating oil composition of the present invention preferably contains an organic molybdenum compound as the component (E).

  Examples of the organic molybdenum compound include (E1) an organic molybdenum compound selected from molybdenum dithiophosphate and molybdenum dithiocarbamate, and (E2) an organic molybdenum compound other than molybdenum dithiophosphate and molybdenum dithiocarbamate. Examples of the component (E2) include organic molybdenum compounds other than (E1), which include an organic molybdenum compound containing sulfur as a constituent element and an organic molybdenum compound not containing sulfur as a constituent element. It is particularly desirable to include the component E2) as an essential component.

  As a molybdenum dithiophosphate, the compound represented by following General formula (11) is mentioned, for example.

In the general formula (11), R ²⁰ , R ²¹ , R ²² and R ²³ may be the same or different, and have 2 to 30 carbon atoms, preferably 5 to 18 carbon atoms, more preferably 5 carbon atoms. A hydrocarbon group such as an alkyl group having ˜12 or a (alkyl) aryl group having 6 to 18 carbon atoms, preferably 10 to 15 carbon atoms. Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a sulfur atom or an oxygen atom.

  Preferred examples of the alkyl group include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, A hexadecyl group, a heptadecyl group, an octadecyl group, etc. are mentioned, These may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched.

  Preferred examples of (alkyl) aryl groups include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, Examples thereof include a decylphenyl group and a dodecylphenyl group, and the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Further, these (alkyl) aryl groups include all substituted isomers in which the substitution position of the alkyl group to the aryl group is different.

  Specific examples of preferred molybdenum dithiophosphates include molybdenum sulfide diethyldithiophosphate, molybdenum sulfide dipropyldithiophosphate, molybdenum dibutyldithiophosphate, molybdenum dipentyldithiophosphate, molybdenum dihexyldithiophosphate, molybdenum dioctyldithiophosphate, molybdenum disulfide. Decyl dithiophosphate, sulfurized molybdenum didodecyl dithiophosphate, molybdenum di (butylphenyl) dithiophosphate, molybdenum di (nonylphenyl) dithiophosphate, sulfurized oxymolybdenum diethyldithiophosphate, sulfurized oxymolybdenum dipropyldithiophosphate, sulfurized oxymolybdenum dibutyldithiophosphate, sulfurized Oki Molybdenum dipentyldithiophosphate, sulfurized oxymolybdenum dihexyldithiophosphate, sulfurized oxymolybdenum dioctyldithiophosphate, sulfurized oxymolybdenum didecyldithiophosphate, sulfurized oxymolybdenum didodecyldithiophosphate, sulfurized oxymolybdenum di (butylphenyl) dithiophosphate, sulfurized oxymolybdenum di (nonylphenyl) Examples thereof include dithiophosphate (the alkyl group may be linear or branched, and the bonding position of the alkyl group of the alkylphenyl group is arbitrary), and mixtures thereof. As these molybdenum dithiophosphates, compounds having hydrocarbon groups having different carbon numbers and / or structures in one molecule can be preferably used.

  As the molybdenum dithiocarbamate, specifically, a compound represented by the following general formula (12) can be used.

In the general formula (12), R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ may be the same or different and each has 2 to 24 carbon atoms, preferably 4 to 13 carbon atoms, or carbon atoms. A hydrocarbon group such as an (alkyl) aryl group having 6 to 24, preferably 10 to 15 carbon atoms is shown. Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ each independently represent a sulfur atom or an oxygen atom.

  Preferred examples of the alkyl group include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, A hexadecyl group, a heptadecyl group, an octadecyl group, etc. are mentioned, These may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched.

  Preferred examples of (alkyl) aryl groups include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, Examples thereof include a decylphenyl group and a dodecylphenyl group, and the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Further, these (alkyl) aryl groups include all substituted isomers in which the substitution position of the alkyl group to the aryl group is different. Examples of molybdenum dithiocarbamate other than the above structure include those having a structure in which a dithiocarbamate group is coordinated to thio or polythio-trinuclear molybdenum as disclosed in WO98 / 26030 or WO99 / 31113.

  Specific examples of preferred molybdenum dithiocarbamates include molybdenum sulfide diethyldithiocarbamate, molybdenum dipropyldithiocarbamate, molybdenum dibutyldithiocarbamate, molybdenum dipentyldithiocarbamate, molybdenum dihexyldithiocarbamate, molybdenum dihexyldithiocarbamate, molybdenum dioctyldithiocarbamate, and molybdenum disulfide. Decyl dithiocarbamate, sulfurized molybdenum didodecyl dithiocarbamate, molybdenum di (butylphenyl) dithiocarbamate, molybdenum di (nonylphenyl) dithiocarbamate, sulfurized oxymolybdenum diethyldithiocarbamate, sulfurized oxymolybdenum dipropyldithiocarbamate, sulfurized oxymolybdenum dibutyldithiocarbamate Oki Molybdenum dipentyldithiocarbamate, sulfurized oxymolybdenum dihexyldithiocarbamate, sulfurized oxymolybdenum dioctyldithiocarbamate, sulfurized oxymolybdenum didecyldithiocarbamate, sulfurized oxymolybdenum didodecyldithiocarbamate, sulfurized oxymolybdenum di (butylphenyl) dithiocarbamate, sulfurized oxymolybdenum di (nonylphenyl) Examples thereof include dithiocarbamate (the alkyl group may be linear or branched, and the bonding position of the alkyl group of the alkylphenyl group is arbitrary), and mixtures thereof. As these molybdenum dithiocarbamates, compounds having hydrocarbon groups having different carbon numbers and / or structures in one molecule can also be preferably used.

  Examples of the organic molybdenum compound (E2) other than molybdenum dithiophosphate and molybdenum dithiocarbamate include organic molybdenum compounds containing sulfur as a constituent element other than (E1). Examples of organic molybdenum compounds containing sulfur as a constituent element include molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, orthomolybdic acid, paramolybdic acid, molybdic acid such as (poly) sulfurized molybdic acid, these molybdenum Metal salts of acids, molybdates such as ammonium salts, molybdenum sulfides such as molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide and polysulfide molybdenum, molybdenum sulfides, metal salts or amine salts of sulfurized molybdenum acid, molybdenum chloride, etc. ) And sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbylthiuram disulfide, bis (di (thio) hydrocarbi Dithiophosphonates), disulfides, organic (poly) sulfides, sulfide esters, etc.) or complexes with other organic compounds, etc., or molybdenum sulfides, molybdenum sulfides, sulfides of molybdenum oxide, sulfides of molybdenum acids, etc. A complex of a sulfur-containing molybdenum compound and an amine compound, an succinimide, an organic acid, an alcohol-free organic compound such as alcohol described later in the section of an organic molybdenum compound that does not contain sulfur as a constituent element, or a structure described later Molybdenum compounds that do not contain sulfur as an element, organic compounds that do not contain sulfur, and sulfur sources (elemental sulfur, hydrogen sulfide, phosphorus pentasulfide, sulfur oxide, inorganic sulfides, hydrocarbyl (poly) sulfides, sulfurized olefins, sulfurized esters) , Sulfurized wax, sulfurized carboxylic acid, alkyl sulfide Phenol, thioacetamide, thiourea) and may include those various such sulfur-containing organic molybdenum compound obtained by reacting. These sulfur-containing organomolybdenum compounds are described in detail in, for example, JP-A-56-10591 and US Pat. No. 4,263,152.

  As the organic molybdenum compound (E2) other than molybdenum dithiophosphate and molybdenum dithiocarbamate, an organic molybdenum compound that does not contain sulfur as a constituent element can be used.

  Specific examples of organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.

The molybdenum - The molybdenum compounds constituting the amine complex, molybdenum trioxide or its hydrate _{(MoO 3 · nH 2 O)} , molybdic acid _(H 2 _MoO 4), molybdenum acid alkali metal salts _(M 2 _MoO 4; M represents an alkali metal), ammonium molybdate ((NH ₄ ) ₂ MoO ₄ or (NH ₄ ) ₆ [Mo ₇ O ₂₄ ] · 4H ₂ O), MoCl ₅ , MoOCl ₄ , MoO ₂ Cl ₂ , MoO ₂ Examples thereof include molybdenum compounds containing no sulfur such as Br ₂ and Mo ₂ O ₃ Cl ₆ . Among these molybdenum compounds, hexavalent molybdenum compounds are preferable from the viewpoint of the yield of the molybdenum-amine complex. Furthermore, from the viewpoint of availability, among the hexavalent molybdenum compounds, molybdenum trioxide or a hydrate thereof, molybdic acid, alkali metal molybdate, and ammonium molybdate are preferable.

  The amine compound constituting the molybdenum-amine complex is not particularly limited, and specific examples of the nitrogen compound include monoamines, diamines, polyamines, and alkanolamines. More specifically, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine , Hexadecylamine, heptadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine Decylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, methyl ethyl Alkylamines having an alkyl group having 1 to 30 carbon atoms such as amine, methylpropylamine, methylbutylamine, ethylpropylamine, ethylbutylamine, and propylbutylamine (these alkyl groups may be linear or branched); Alkenyl amines having 2 to 30 carbon atoms such as ethenylamine, propenylamine, butenylamine, octenylamine, and oleylamine (these alkenyl groups may be linear or branched); methanolamine, ethanolamine, propanolamine , Butanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine, nonanolamine, methanol ethanolamine, methanol propanolamine, methanol butanol amine Alkanolamines having 1 to 30 carbon atoms such as ethanolpropanolamine, ethanolbutanolamine, and propanolbutanolamine (these alkanol groups may be linear or branched); methylenediamine, ethylenediamine, Alkylene diamines having 1-30 carbon atoms such as propylene diamine and butylene diamine; polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine; undecyl diethylamine, undecyl diethanolamine, dodecyl dipropanol Amine, oleyl diethanolamine, oleyl propylene diamine, stearyl tetraethylene pentamine, etc. Examples thereof include compounds having an alkyl group or alkenyl group having 8 to 20 carbon atoms in the amine and heterocyclic compounds such as imidazoline; alkylene oxide adducts of these compounds; and mixtures thereof. Of these amine compounds, primary amines, secondary amines and alkanolamines are preferred.

  Carbon number of the hydrocarbon group which the amine compound which comprises a molybdenum-amine complex has becomes like this. Preferably it is 4 or more, More preferably, it is 4-30, Most preferably, it is 8-18. When the number of carbon atoms of the hydrocarbon group of the amine compound is less than 4, the solubility tends to deteriorate. Moreover, by setting the number of carbon atoms of the amine compound to 30 or less, the molybdenum content in the molybdenum-amine complex can be relatively increased, and the effect can be further enhanced with a small amount of blending.

  The molybdenum-succinimide complex is a complex of a sulfur-free molybdenum compound as exemplified in the description of the molybdenum-amine complex and a succinimide having an alkyl group or alkenyl group having 4 or more carbon atoms. Is mentioned. As the succinimide, a succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms or an alkenyl group in the molecule described in the ashless dispersant, or a carbon number of 4 to 39, preferably carbon number. Examples thereof include succinimide having 8 to 18 alkyl groups or alkenyl groups. If the alkyl group or alkenyl group in the succinimide has less than 4 carbon atoms, the solubility tends to deteriorate. A succinimide having an alkyl group or an alkenyl group having more than 30 carbon atoms and not more than 400 carbon atoms can also be used. By setting the alkyl group or alkenyl group to 30 or less carbon atoms, molybdenum-succinimide is obtained. The molybdenum content in the complex can be relatively increased, and the effect can be further enhanced with a small amount.

  Examples of the molybdenum salt of an organic acid include salts of molybdenum bases such as molybdenum oxide or molybdenum hydroxide, molybdenum carbonate or molybdenum chloride exemplified in the description of the molybdenum-amine complex with an organic acid. It is done. As an organic acid, the phosphorus containing acid which does not contain sulfur illustrated in the term of the said (B3) component, and carboxylic acid are preferable.

  The carboxylic acid constituting the carboxylic acid molybdenum salt may be either a monobasic acid or a polybasic acid.

  As the monobasic acid, a fatty acid having 2 to 30 carbon atoms, preferably 4 to 24 carbon atoms, is used. The fatty acid may be linear or branched, and may be saturated or unsaturated. . Specifically, for example, acetic acid, propionic acid, linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptane Acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecane Acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched heptadecane Acid, linear or branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, linear or branched Henicosanoic acid, linear or branched Saturated fatty acids such as cosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid, acrylic acid, linear or branched butenoic acid, linear or branched pentenoic acid, Linear or branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenoic acid, linear or branched decenoic acid, Linear or branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, Linear or branched hexadecenoic acid, linear or branched heptadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecene Acid, linear or branched Unsaturated fatty acids such as cocenoic acid, linear or branched heicosenoic acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid, and the like And the like.

  Moreover, as a monobasic acid, in addition to the above fatty acid, a monocyclic or polycyclic carboxylic acid (which may have a hydroxyl group) may be used, and the carbon number thereof is preferably 4 to 30, and more preferably. Is 7-30. The monocyclic or polycyclic carboxylic acid is an aromatic carboxylic acid having 0 to 3, preferably 1 to 2 linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Or cycloalkyl carboxylic acid etc. are mentioned, More specifically, (alkyl) benzene carboxylic acid, (alkyl) naphthalene carboxylic acid, (alkyl) cycloalkyl carboxylic acid, etc. can be illustrated. Preferable examples of the monocyclic or polycyclic carboxylic acid include benzoic acid, salicylic acid, alkylbenzoic acid, alkylsalicylic acid, and cyclohexanecarboxylic acid.

  Examples of polybasic acids include dibasic acids, tribasic acids, and tetrabasic acids. The polybasic acid may be a chain polybasic acid or a cyclic polybasic acid. Further, in the case of a chain polybasic acid, it may be either linear or branched, and may be either saturated or unsaturated. As the chain polybasic acid, a chain dibasic acid having 2 to 16 carbon atoms is preferable. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear Or branched pentanedioic acid, linear or branched hexanedioic acid, linear or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched nonane diacid Acid, linear or branched decanedioic acid, linear or branched undecanedioic acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or Branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or branched hexadecanedioic acid, linear or branched hexenedioic acid, linear or branched heptenedioic acid Linear or branched octene diacid, linear or branched nonene diacid, linear or branched Branched decenedioic acid, linear or branched undecenedioic acid, linear or branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched tetradecenedioic acid And linear or branched heptadecene diacid, linear or branched hexadecene diacid, alkenyl succinic acid, and mixtures thereof. As the cyclic polybasic acid, 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid alicyclic dicarboxylic acid, phthalic acid or other aromatic dicarboxylic acid, trimellitic acid or other aromatic Examples thereof include aromatic tetracarboxylic acids such as tricarboxylic acid and pyromellitic acid.

  Examples of the molybdenum salt of alcohol include a salt of a molybdenum compound not containing sulfur as exemplified in the description of the molybdenum-amine complex and an alcohol. The alcohol is a monohydric alcohol, polyhydric alcohol, polyhydric alcohol. Any of a partial ester or partial ether compound of alcohol, a nitrogen compound having a hydroxyl group (alkanolamine, etc.), etc. may be used. Molybdic acid is a strong acid and forms an ester by reaction with alcohol. The ester of molybdic acid and alcohol is also included in the molybdenum salt of alcohol in the present invention.

  As the monohydric alcohol, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. Such alcohols may be linear or branched, and saturated. Or may be unsaturated. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecane Decanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecanol, linear or branched icosa Lumpur, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as linear or branched tetracosanol, and mixtures thereof.

  Moreover, as a polyhydric alcohol, the thing of 2-10 valence is preferable, Preferably it is 2-6 valence. Specific examples of the 2 to 10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 of propylene glycol). Monomer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3 -Dihydric alcohols such as propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2- Octamers such as diglycerin, triglyceride Phosphorus, tetraglycerin, etc.), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polyhydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof That.

  Examples of the partial ester of the polyhydric alcohol include compounds in which a part of the hydroxyl group of the polyhydric alcohol exemplified in the description of the polyhydric alcohol has been hydrocarbyl esterified, among which glycerin monooleate and glycerin dioleate. Sorbitan monooleate, sorbitandiolate, pentaerythritol monooleate, polyethylene glycol monooleate, polyglycerin monooleate and the like are preferable.

  Moreover, as the partial ether of the polyhydric alcohol, an ether bond is formed by condensation of polyhydric alcohols, a compound in which a part of the hydroxyl groups of the polyhydric alcohol exemplified in the description of the polyhydric alcohol is hydrocarbyl etherified. Compounds (such as sorbitan condensate) and the like, among which 3-octadecyloxy-1,2-propanediol, 3-octadecenyloxy-1,2-propanediol, polyethylene glycol alkyl ether and the like are preferable.

  Examples of the nitrogen compound having a hydroxyl group include alkanolamines exemplified in the description of the molybdenum-amine complex, and alkanolamides (diethanolamide, etc.) in which the amino group of the alkanol is amidated. Among them, stearyldiethanolamine Polyethylene glycol stearylamine, polyethylene glycol dioleylamine, hydroxyethyl laurylamine, oleic acid diethanolamide and the like are preferable.

  (E) As the organic molybdenum compound, it is preferable to use one or more sulfur-containing organic molybdenum compounds (E1) selected from molybdenum dithiophosphate and molybdenum dithiocarbamate because they are excellent in initial friction reduction effect. . Moreover, it is preferable to use organic molybdenum compounds (E2) other than molybdenum dithiophosphate and molybdenum dithiocarbamate because they are excellent in high-temperature cleanliness, suppress an increase in viscosity, and easily maintain fuel saving performance for a long period of time. As the component (E2), among those exemplified above, a sulfur-containing molybdenum compound (for example, molybdenum sulfide, molybdenum oxysulfide, sulfide of molybdic acid, etc.) and an organic compound not containing sulfur as a constituent element (an amine compound, Complexes or salts with succinimides, alcohols, carboxylic acids, etc., molybdenum compounds that do not contain sulfur as constituent elements (oxymolybdenum, molybdic acid, etc.), and organic compounds that do not contain sulfur as constituent elements (amine compounds, succinic acid) Imide, alcohol, carboxylic acid, etc.) or molybdenum, a sulfur-containing molybdenum compound or a molybdenum compound that does not contain sulfur as a constituent element, an organic molybdenum that does not contain sulfur as a constituent element, and a sulfur source One or more organic molybdation selected from compounds Thing is preferable.

  In the present invention, it is particularly preferable to use (E2) in that it is excellent in high-temperature cleanliness, and a composition excellent in sustainability of initial fuel saving performance can be obtained even under soot mixing.

  In the composition of the present invention, when an organic molybdenum compound is used, the content is not particularly limited, but is preferably 0.001% by mass or more, preferably 0.001% by mass or more in terms of molybdenum element based on the total amount of the composition. It is 005 mass% or more, More preferably, it is 0.01 mass% or more. Moreover, it is preferably 0.2% by mass or less, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less. When the content is less than 0.001% by mass, the heat / oxidation stability of the lubricating oil composition becomes insufficient, and in particular, it tends to be impossible to maintain excellent cleanliness over a long period of time. On the other hand, when the content exceeds 0.2% by mass, an effect commensurate with the content cannot be obtained, and the storage stability of the lubricating oil composition tends to decrease.

  Examples of additives other than the organomolybdenum compound (E) that can be preferably added to the lubricating oil composition of the present invention include ashless antioxidants, organometallic antioxidants, viscosity index improvers, (B List of additives such as anti-wear agents other than components), metallic detergents other than component (C), corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, antifoaming agents, and colorants. Can do.

  As the ashless antioxidant, any ashless antioxidants such as phenolic antioxidants and amine antioxidants that are generally used in lubricating oils can be used. By adding the antioxidant, the antioxidant property of the lubricating oil composition can be further enhanced, and the oxidation stability, high temperature cleanability and base number maintaining property of the composition of the present invention can be further enhanced.

  Examples of phenolic antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′. -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl) 6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethylphenol), 4,4′-thiobis (2-methyl-6) -Tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl-4- Hydroxy-5-tert-butylbenzyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 2,2′-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3-methyl-5-tert-butyl-4-hydroxyphenyl substituted fatty acid esters and the like are preferable examples. Can do. You may use these in mixture of 2 or more types.

  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.

  In addition, as the organometallic antioxidant, a known organometallic antioxidant containing a metal and having an antioxidant effect can be used, and the component (E2) of the organomolybdenum compounds described above Can be preferably used.

  You may mix | blend the said phenolic antioxidant, amine-type antioxidant, and organometallic antioxidant in combination.

  When the antioxidant is contained in the lubricating oil composition of the present invention, the content is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total amount of the lubricating oil composition. Preferably it is 0.5-5 mass%. When the content exceeds 20% by mass, sufficient performance corresponding to the blending amount cannot be obtained. On the other hand, when the content is less than 0.01% by mass, the effect of improving the base number maintenance property is small. Each is not preferred.

  Examples of the viscosity index improver include non-dispersed or dispersed viscosity index improvers. Specifically, non-dispersed or dispersed polymethacrylates, non-dispersed or dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or hydrides thereof, styrene-diene hydrogenated copolymers, Examples thereof include styrene-maleic anhydride ester copolymers, polymethacrylate-styrene copolymers, polymethacrylate-olefin copolymers, and polyalkylstyrenes. When the viscosity index improver is contained, the content is usually 0.1 to 20% by mass, preferably 1 to 15% by mass, and more preferably 3 to 10% by mass based on the total amount of the composition.

  As the antiwear agent other than the component (B), for example, a sulfur-based extreme pressure agent can be used, and an effect of suppressing wear under soot mixing can be expected.

  Examples of the sulfur-based extreme pressure agent include disulfides, polysulfides, sulfurized olefins, sulfurized oils and fats, sulfur-containing compounds such as sulfurized esters, dithiocarbamates, and zinc dithiocarbamates, and sulfurized oils and fats are most preferable. Among these compounds, the sulfur content in the sulfur-based extreme pressure agent is preferably 1 to 40% by mass, more preferably 5 to 20% by mass, and still more preferably 5 to 15% by mass. . Even if the sulfur content in the sulfur-based extreme pressure agent is too high, the effect of suppressing wear under soot mixing does not become an effect commensurate with the sulfur content, on the other hand, there is a possibility that the base number maintenance performance deteriorates, When the sulfur content in the sulfur-based extreme pressure agent is small, the effect of suppressing wear under soot mixing is small. As other antiwear agents, known ones such as boric acid esters, ashless antiwear agents, and metal antiwear agents can be used.

  In the lubricating oil composition of the present invention, the content of the anti-wear agent other than the component (B) is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass based on the total amount of the composition. %.

  Examples of the metal detergent other than the component (C) include known naphthenate detergents and phosphonate detergents. The content in the case of using these is usually selected in the range of 0.005 to 0.5% by mass as a metal amount based on the total amount of the composition.

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

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

  Examples of the 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.

  As the pour point depressant, a known pour point depressant can be arbitrarily selected according to the properties of the lubricating base oil, but the weight average molecular weight is more than 50,000 and not more than 150,000, preferably 80 1 to 120,000 polymethacrylates are preferred.

  As the antifoaming agent, any compound usually used as an antifoaming agent for lubricating oil can be used, and examples thereof include silicones such as dimethyl silicone and fluorosilicone. One or two or more compounds arbitrarily selected from these can be blended in any amount. Examples of antifoaming agents include silicone oil, alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, methyl salicylate and o-hydroxybenzyl alcohol, aluminum stearate, potassium oleate, N-dialkyl-allylamine Nitroaminoalkanol, aromatic amine salt of isoamyl octyl phosphate, alkylalkylene diphosphate, metal derivative of thioether, metal derivative of disulfide, fluorine compound of aliphatic hydrocarbon, triethylsilane, dichlorosilane, alkylphenyl polyethylene glycol ether sulfide, fluoro Examples thereof include alkyl ethers.

  As the colorant, any compound that is usually used can be used, and any amount can be blended. Usually, the blending amount is 0.001 to 1.0% by mass based on the total amount of the composition. is there.

  When these additives are contained in the lubricating oil composition of the present invention, the content is based on the total amount of the composition, 0.005 to 5% by mass for the corrosion inhibitor, the rust inhibitor, and the demulsifier, respectively, and the metal inertness. 0.005 to 1% by mass for the agent, 0.01 to 1% by mass for the pour point depressant, 0.0001 to 1% by mass for the antifoaming agent, and 0.001 to 1.0% by mass for the colorant. Usually selected by range.

  The sulfur content in the lubricating oil composition of the present invention is not particularly limited, but is preferably 0.3% by mass or less, more preferably 0.26% by mass or less, and 0.2% by mass or less. It is particularly preferred. When the sulfur content exceeds 0.3% by mass, the lifetimes of the oxidation catalyst, NOx storage reduction catalyst, and DPF of the exhaust gas aftertreatment device tend to be shortened. Further, the sulfated ash content of the lubricating oil composition of the present invention is preferably 1.2% by mass or less, more preferably 1.0% by mass or less, and still more preferably from the viewpoint of maintaining the performance of the exhaust gas aftertreatment device. Is 0.9% by mass or less, preferably 0.3% by mass or more, particularly 0.7% by mass or more, so that wear and friction under soot mixing can be reduced and high temperature cleanliness is also excellent. A composition can be obtained.

The kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is usually 5 to 30 mm ² / s in that the lubricity of the engine or the like can be properly maintained, but it is easy to maintain the wear prevention property under soot mixing, It is preferably 8 to 25 mm ² / s, more preferably 9.3 to 16.3 mm ² / s, and particularly preferably 9.3 to 11.5 mm ² / s in that the frictional resistance due to stirring resistance can be suppressed.

  The viscosity index of the lubricating oil composition of the present invention is usually 140 or more, preferably 150 or more, more preferably 160 or more, and still more preferably 170 or more, from the viewpoint of improving the viscosity-temperature characteristics and fuel economy. In view of excellent shear stability, high-temperature cleanability and base number maintenance performance, it is preferably 250 or less, more preferably 200 or less, and even more preferably 190 or less.

  Furthermore, the lubricating oil composition of the present invention has a TBS viscosity at 150 ° C. of preferably 2.6 mPa · s or more, particularly 2.9 to 3.7 mPa · s, thereby further reducing wear particularly during soot mixing. The CCS viscosity at −25 ° C. is 3500 mPa · s or lower, or the CCS viscosity at −30 ° C. is 3250 mPa · s or lower. Thus, a lubricating oil composition suitable as 0W-20, 5W-20, 0W-30, 5W-30 grade engine oil, particularly 0W-30 engine oil can be obtained.

  The lubricating oil composition of the present invention is excellent in high-temperature cleanability, and particularly suppresses an increase in wear and friction due to soot mixing that is noticeable when the amount of phosphorus compound such as ZnDTP is reduced, and maintains this over a long period of time. This can easily reduce the influence on the exhaust gas aftertreatment device. Therefore, the lubricating oil composition is suitable for diesel engines and direct injection gasoline engines equipped with exhaust gas aftertreatment devices such as DPF and various catalysts. Moreover, it can be used not only for engines for such applications, but also for gasoline engines, diesel engines, gas engines for motorcycles, automobiles, power generation, cogeneration, etc. Not only can it be suitably used for these various engines using fuel of 50 mass ppm or less, but it is also useful for various engines for ships and outboard motors. Further, a low sulfur fuel, for example, a fuel having a sulfur content of 50 mass ppm or less, more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less (for example, gasoline, light oil, kerosene, alcohol, dimethyl ether, LPG, natural gas, (Hydrogen, GTL (Gas Liquid) fuel, etc.) are suitable for lubricating oil for internal combustion engines. Further, since the lubricating oil composition of the present invention is also excellent in oxidation stability, lubricating oil for drive systems such as automatic or manual transmissions, grease, wet brake oil, hydraulic hydraulic oil, turbine oil, compressor oil, bearing oil Also, it can be suitably used as a lubricating oil such as refrigerator oil.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

A total of eight types of lubricating oil compositions of Examples 1 to 3, Reference Examples 4 to 5 and Comparative Examples 1 to 3 were prepared so as to have the compositions shown in Table 1. Base oil O-1 (X2) is an α-olefin oligomer hydride (poly α-olefin hydride) having 8 to 12 carbon atoms, and base oil O-2 (Ya) is a hydrocracked mineral oil. The ratio of the base oil is based on the total amount of the base oil, and the amount of each additive is based on the total amount of the composition. About these lubricating oil compositions, the high-speed four-ball abrasion test and the HFRR friction test were done, and the performance was evaluated. The evaluation method is as follows. The evaluation results are also shown in Table 1.

(High-speed four-ball wear test)
In order to prepare soot-containing oil in a simulated manner, carbon black is dispersed by 1.5% by mass in the test oil, and after the four-ball wear test is performed in accordance with JPI-5S-32-90 under the following test conditions. The wear scar diameter was measured. In this test, the smaller the wear scar diameter, the better the wear resistance.
(Test conditions)
Rotation speed: 1500rpm
Load: 294N
Test oil temperature: 110 ° C
Test time: 1 hour

(HFRR friction test)
The oil in which 1.5% by mass of new oil and carbon black was dispersed was used as a test oil, and the friction coefficient was measured under the following conditions using an HFRR friction tester. The results obtained are listed in Table 1. In this test, the smaller the coefficient of friction, the better the fuel economy, and the smaller the coefficient of friction after the addition of carbon black, the better the maintenance of the friction reduction effect.
(Test conditions)
Weight: 200g
Test oil temperature: 100 ° C
Amplitude: 1 mm
Frequency: 50Hz
Test time: 60 minutes Friction coefficient measurement: Friction coefficients from 50 minutes to 60 minutes after the start of the test were averaged.

As shown in Table 1, the lubricating oil compositions of Examples 1 to 3 and Reference Examples 4 to 5 are excellent in wear prevention when carbon black is dispersed, and have a small coefficient of friction with new oil. In particular, the lubricating oil compositions of Examples 1 to 3 prepared by adjusting the metal ratio of the metal detergent to 5 or more are Comparative Examples 1 to 3 having a metal ratio of less than 2.4, or the metal ratio is 3 or less. Compared to Reference Example 4, it can be seen that the coefficient of friction at the time of carbon black dispersion is small, and the friction reducing performance under soot mixing is remarkably excellent.

  In addition, the lubricating oil compositions of Examples 1 to 5 have a low ash type in which the sulfated ash content is in the range of 0.7 to 0.9% by mass. Therefore, it is possible to sufficiently maintain the performance of the exhaust gas aftertreatment device over a long period of time. In addition, the lubricating oil compositions of Examples 1 to 5 satisfy the SAE 0W and 5W viscosity grade standards, and also satisfy the SAE 30 viscosity grade standards. Therefore, as is clear from the results of the examples, not only is it particularly excellent in wear prevention and fuel saving in the presence of soot, it is also excellent in wear prevention and fuel saving even under normal use conditions. Or it is excellent also in the low temperature startability at the time of the cold in a cold district, and fuel-saving performance.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification. Lubricating oil compositions with such changes are also included in the technical scope of the present invention. Must be understood as.

Claims (7)

In lubricating base oil, based on the total amount of the composition,
(A) 0.01 to 10% by mass of an ashless friction modifier having an amide bond ,
(B) (B3) 0.01-0.2% by mass of phosphorus-containing antiwear agent comprising a metal salt of a phosphorus-containing acid that does not contain sulfur as the amount of phosphorus,
(C) At least (Ca) a metal detergent having a metal ratio of less than 2 and (Cb) a metal detergent having a metal ratio of 2 or more, and adjusted so that the metal ratio is 5 to 8. 0.01-1% by mass with metal detergent as metal amount, and 0.01-0.4% by mass with (D) ashless dispersant having a weight average molecular weight of 3000-20000 as nitrogen amount
A lubricating oil composition characterized by comprising. The lubricating oil composition according to claim 1, wherein the component (A) is a compound having an amide bond and a compound having 2 or more nitrogen atoms . The (Ca) component is selected from (C1a) a sulfonate detergent having a metal ratio of less than 2, (C2a) a phenate detergent having a metal ratio of less than 2, and (C3a) a salicylate detergent having a metal ratio of less than 2. The lubricating oil composition according to claim 1, wherein the lubricating oil composition is at least one kind. The lubrication according to claim 3, wherein the component (Ca) is (C1a) a sulfonate detergent having a metal ratio of less than 2 and / or (C3a) a salicylate detergent having a metal ratio of less than 2. Oil composition. Wherein (Cb) component, (C1b) according to claim 1 or 2, characterized in that the metal ratio is 2 or more sulfonate-based detergent and / or (C2b) metal ratio is 2 or more phenate detergents Lubricating oil composition. The component (Cb) is (C1b) a sulfonate detergent having a metal ratio of 2 or more and / or (C2b) a phenate detergent having a metal ratio of 2 or more. Lubricating oil composition. The lubricating oil composition according to any one of claims 1 to 6 , which is suitably used for a diesel engine or a direct injection gasoline engine.