JP5788917B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition.

Conventionally, lubricating oil is used in an internal combustion engine, a transmission, and other mechanical devices in order to make the operation smooth. In particular, lubricating oil (engine oil) for internal combustion engines is required to have high performance as the performance of the internal combustion engine increases, the output increases, and the operating conditions become severe. Therefore, various additives such as antiwear agents, metallic detergents, ashless dispersants, and antioxidants are blended in conventional engine oils in order to satisfy these required performances. (See, for example, Patent Documents 1 to 3 below.) Recently, fuel efficiency required for lubricating oil has been increasing, and application of a high viscosity index base oil and various friction modifiers have been studied. (For example, refer to Patent Document 4 below.)

JP 2001-279287 A JP 2002-129182 A Japanese Patent Laid-Open No. 08-302378 Japanese Patent Laid-Open No. 06-306384

  However, conventional lubricating base oils and viscosity index improvers are not necessarily sufficient in terms of fuel economy and low temperature viscosity characteristics.

  As a general method for reducing fuel consumption, there are known a method for reducing the kinematic viscosity of a product and a multi-gradation by combining a viscosity index improvement, that is, a base oil viscosity reduction and a viscosity index improver. However, there is a concern that reduction in product viscosity or reduction in base oil viscosity will reduce lubrication performance under severe lubrication conditions (high-temperature high-shear conditions) and cause problems such as wear, seizure, and fatigue failure.

  Therefore, in order to prevent such problems and maintain durability, it is necessary to maintain a high temperature high shear viscosity (HTHS viscosity) at 150 ° C. In other words, in order to further improve fuel efficiency while maintaining other practical performance, while maintaining the HTHS viscosity at 150 ° C. at a constant level, the kinematic viscosity at 40 ° C. and 100 ° C. and the HTHS viscosity at 100 ° C. It is important to reduce and improve the viscosity index.

  The present invention has been made in view of such circumstances, and is excellent in fuel economy and lubricity, and includes synthetic oils such as poly-α-olefin base oils and ester base oils, and low-viscosity mineral oil base oils. Provided is a lubricating oil composition in which the kinematic viscosity of the lubricating oil at 40 ° C. and 100 ° C. and the HTHS viscosity at 100 ° C. are remarkably reduced while maintaining the HTHS viscosity at a certain level without using it. The purpose is to do.

In order to solve the above problems, the present invention comprises a lubricating base oil kinematic viscosity is 1~10mm 2 / ^s,% C _A of 5 or less at 100 ° C., based on the total amount of the lubricating oil composition, the weight-average and a molecular weight of 100,000 or more, PSSI is 35 or less, the poly (meth) acrylate based viscosity index improver 0.1 to 50 wt% and is the ratio of weight average molecular weight and PSSI is 0.8 × 10 ⁴ or more , The kinematic viscosity at 100 ° C. is 3 to 9.3 mm ² / s, the HTHS viscosity at 150 ° C. is 2.0 mPa · s or more, and the HTHS viscosity at 100 ° C. is 5.3 mPa · s or less. There, and provides a lubricating oil composition the ratio of the HTHS viscosity at HTHS viscosity and 100 ° C. at 0.99 ° C. is characterized in that 0.52 or more.
Further, the present invention has a kinematic viscosity at 100 ° C. is 1 to 10 mm ² / s,% and the lubricating oil base oil _{C A} is 5 or less, based on the total amount of the lubricating oil composition, a weight-average molecular weight of 50,000 or more And 0.1 to 50% by mass of a viscosity index improver having a weight average molecular weight and PSSI ratio of 0.8 × 10 ⁴ or more, and a kinematic viscosity at 100 ° C. of 3 to 9.3 mm ² / s. And a ratio of the HTHS viscosity at 150 ° C. to the HTHS viscosity at 100 ° C. is 0.50 or more.

  According to the present invention, the fuel economy and lubricity are excellent, and the HTHS viscosity is kept at a constant level without using a synthetic oil such as a poly-α-olefin base oil or an ester base oil or a low-viscosity mineral oil base oil. It is possible to provide a lubricating oil composition in which the kinematic viscosity of the lubricating oil at 40 ° C. and 100 ° C. and the HTHS viscosity at 100 ° C. are significantly reduced while maintaining the fuel efficiency.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

In the lubricating oil composition of the present invention, a kinematic viscosity of 1 to 10 mm ² / s at 100 ° C., and, in the base oil the basis of the total amount,% _{C A} of 5 or less is a lubricating base oil (hereinafter, "the The lubricating base oil according to the invention ”) is used.

Lubricant base oil according to the present invention, kinematic viscosity and% C _A is not particularly limited so far as it meets the above condition at 100 ° C.. Specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid Among paraffinic mineral oils, or normal paraffinic base oils, isoparaffinic base oils, etc., which are refined by combining one or more of purification treatments such as washing and clay treatment alone or in combination, _A base oil having% CA satisfying the above conditions can be used.

As a preferable example of the lubricating base oil according to the present invention, the following base oils (1) to (8) are used as raw materials, and the raw oil and / or a lubricating oil fraction recovered from the raw oil is determined in a predetermined manner. The base oil obtained by refine | purifying by the refining method of this, and collect | recovering lubricating oil fractions 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 (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-liquid (GTL) process, etc.
(4) One or two or more mixed oils selected from base oils (1) to (3) and / or mild hydrocracked 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 refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred. 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, the lubricating base oil according to the present invention is obtained by subjecting a base oil selected from the base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment. The following base oil (9) or (10) is particularly preferred.
(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 a dewaxing process such as or by distillation after the dewaxing process.

  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 at an advantageous step.

  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 kind of the composite oxide. Hydrogenolysis with a combination of the above combined with a binder and supporting a metal having hydrogenation ability (for example, one or more metals such as Group VIa metal or Group VIII metal in the periodic table) Hydroisomerization catalyst in which a catalyst or a support containing zeolite (for example, ZSM-5, zeolite beta, SAPO-11, etc.) is loaded with a metal having a hydrogenation ability containing at least one of Group VIII metals Are 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, and the hydrogen / oil ratio. It is preferable to set it as 50-20000 scf / b.

The 100 ° C. kinematic viscosity of the lubricating base oil according to the present invention needs to be 10 mm ² / s or less, preferably 9 mm ² / s or less, more preferably 7 mm ² / s or less, and still more preferably 5. It is 0 mm ² / s or less, particularly preferably 4.5 mm ² / s or less, and most preferably 4.0 mm ² / s or less. On the other hand, the 100 ° C. kinematic viscosity needs to be 1 mm ² / s or more, preferably 1.5 mm ² / s or more, more preferably 2 mm ² / s or more, and further preferably 2.5 mm. ² / s or more, particularly preferably 3 mm ² / s or more. The kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the 100 ° C. kinematic viscosity of the lubricating base oil component exceeds 10 mm 2 / ^s, the worse the low temperature viscosity characteristics, also there is a risk that can not be obtained sufficient fuel saving properties, the following cases 1 mm 2 / ^s Since the formation of an oil film at the lubrication site is insufficient, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.

In the present invention, it is preferable to use a lubricating base oil having a kinematic viscosity at 100 ° C. in the following range by distillation or the like.
(I) less than the kinematic viscosity at 100 ° C. is 1.5 mm ² / s or more 3.5 mm ² / s, more preferably kinematic viscosity at 2.0 to 3.0 mm ² / s lubricating base oils (II) 100 ° C. There 3.5 mm ² / s or more 4.5mm less than ² / s, more preferably a kinematic viscosity in the lubricating base oil of ^{3.5~4.1mm 2 / s (III) 100} ℃ 4.5~10mm 2 / s, more preferably from 4.8 to 9 mm ² / s, particularly preferably from 5.5 to 8.0 mm ² / s.

Further, the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present invention is preferably 80 mm ² / s or less, more preferably 50 mm ² / s or less, still more preferably 20 mm ² / s or less, and particularly preferably 18 mm ² / s. s or less, most preferably 16 mm ² / s or less. On the other hand, the 40 ° C. kinematic viscosity is preferably 6.0 mm ² / s or more, more preferably 8.0 mm ² / s or more, further preferably 12 mm ² / s or more, and particularly preferably 14 mm ² / s or more. Most preferably, it is 15 mm ² / s or more. If the 40 ° C. kinematic viscosity of the lubricating base oil component exceeds 80 mm 2 / ^s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, less 6.0 mm 2 / ^s In such a case, the oil film formation at the lubrication site is insufficient, so that the lubricity is poor, and the evaporation loss of the lubricating oil composition may be increased. Moreover, in this invention, it is preferable to fractionate and use the lubricating oil fraction whose kinematic viscosity in 40 degreeC is in the following range by distillation.
(IV) less than the kinematic viscosity at 40 ° C. is 6.0 mm ² / s or more 12 mm ² / s, more preferably 8.0~12mm ² / s lubricating base oil (V) kinematic viscosity at 40 ° C. is 12 mm ² / More than s and less than 28 mm < ² > / s, more preferably 13-19 mm < ² > / s lubricating base oil (VI) The kinematic viscosity at 40 [deg.] C. is 28-50 mm < ² > / s, more preferably 29-45 mm < ² > / s, particularly preferred. Is a lubricating base oil of 30 to 40 mm ² / s.

  The viscosity index of the lubricating base oil according to the present invention is preferably 120 or more. Moreover, the viscosity index of the lubricating base oils (I) and (IV) is preferably 120 to 135, more preferably 120 to 130. The viscosity index of the lubricating base oils (II) and (V) is preferably 120 to 160, more preferably 125 to 150, and still more preferably 135 to 145. Further, the viscosity index of the lubricating base oils (III) and (VI) is preferably 120 to 180, more preferably 125 to 160. If the viscosity index is less than the lower limit, not only the viscosity-temperature characteristics, thermal / oxidative stability and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase and the wear prevention properties tend to decrease. It is in. On the other hand, when the viscosity index exceeds the upper limit, the low-temperature viscosity characteristics tend to decrease.

  In addition, the viscosity index as used in the field of this invention means the viscosity index measured based on JISK2283-1993.

Further, the density (ρ ₁₅ ) at 15 ° C. of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil component, but is not more than the value of ρ represented by the following formula (A), that is, It is preferable that ρ ₁₅ ≦ ρ.
ρ = 0.0025 × kv100 + 0.816 (A)
[Wherein, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil component at 100 ° C. ]

When ρ ₁₅ > ρ, the viscosity-temperature characteristics and thermal / oxidation stability, as well as volatilization prevention and low-temperature viscosity characteristics tend to decrease, which may deteriorate fuel economy. Moreover, when an additive is mix | blended with a lubricating base oil component, there exists a possibility that the effectiveness of the said additive may fall.

Specifically, the density (ρ ₁₅ ) at 15 ° C. of the lubricating base oil according to the present invention is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less, particularly preferably. 0.822 or less.

  In addition, the density in 15 degreeC said by this invention means the density measured in 15 degreeC based on JISK2249-1995.

  Further, the pour point of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil. For example, the pour point of the lubricating base oils (I) and (IV) is preferably −10. ° C or lower, more preferably -12.5 ° C or lower, still more preferably -15 ° C or lower. The pour points of the lubricating base oils (II) and (V) are preferably −10 ° C. or lower, more preferably −15 ° C. or lower, and still more preferably −17.5 ° C. or lower. The pour point of the lubricating base oils (III) and (VI) is preferably −10 ° C. or lower, more preferably −12.5 ° C. or lower, and further preferably −15 ° C. or lower. When the pour point exceeds the upper limit, the low temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease. In addition, the pour point as used in the field of this invention means the pour point measured based on JISK2269-1987.

The aniline point (AP (° C.)) of the lubricating base oil of the present invention depends on the viscosity grade of the lubricating base oil, but is not less than the value of A represented by the following formula (B), that is, AP ≧ A is preferred.
A = 4.3 × kv100 + 100 (B)
[Wherein, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil at 100 ° C. ]

  When AP <A, viscosity-temperature characteristics and thermal / oxidative stability, volatilization prevention properties and low-temperature viscosity characteristics tend to decrease, and when additives are added to the lubricating base oil In addition, the effectiveness of the additive tends to decrease.

  For example, the AP of the lubricating base oils (I) and (IV) is preferably 108 ° C. or higher, more preferably 110 ° C. or higher. The AP of the lubricating base oils (II) and (V) is preferably 113 ° C. or higher, more preferably 119 ° C. or higher. The AP of the lubricating base oils (III) and (VI) is preferably 125 ° C. or higher, more preferably 128 ° C. or higher. In addition, the aniline point as used in the field of this invention means the aniline point measured based on JISK2256-1985.

  The iodine value of the lubricating base oil according to the present invention is preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, particularly preferably 0.9 or less, and most preferably 0.8. It is as follows. Further, it may be less than 0.01, but from the viewpoint of small effect corresponding to it and economic efficiency, it is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.03. Above, especially preferably 0.05 or more. By setting the iodine value of the lubricating base oil component to 3 or less, the thermal and oxidation stability can be dramatically improved. In addition, the iodine value as used in the field of this invention means the iodine value measured by the indicator titration method of JISK0070 "the acid value of a chemical product, the saponification value, the iodine value, the hydroxyl value, and the unsaponification value."

  Further, the sulfur content in the lubricating base oil according to the present invention depends on the sulfur content of the raw material. For example, when a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like is used, a lubricating base oil that does not substantially contain sulfur can be obtained. In addition, when using raw materials containing sulfur such as slack wax obtained in the refining process of the lubricating base oil and microwax obtained in the refining process, the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it. In the lubricating base oil according to the present invention, the sulfur content is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, from the viewpoint of further improvement in thermal and oxidation stability and low sulfur content. More preferably, it is more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.

  Further, the nitrogen content in the lubricating base oil according to the present invention is not particularly limited, but is preferably 7 ppm by mass or less, more preferably 5 ppm by mass or less, and further preferably 3 ppm by mass or less. If the nitrogen content exceeds 5 ppm by mass, the thermal and oxidation stability tends to decrease. In addition, the nitrogen content as used in the field of this invention means the nitrogen content measured based on JISK2609-1990.

Moreover,% C _A of the lubricating base oil of the invention must be 5 or less, more preferably 2 or less, more preferably 1 or less, particularly preferably 0.5 or less. When% C _A of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties will tend to be reduced. Moreover,% C _A of the lubricating base oil of the invention may be 0% by the above-described lower limit of C _A, it is possible to further increase the solubility of additives.

Further, the% C _p of the lubricating base oil according to the present invention is preferably 70 or more, preferably 80 to 99, more preferably 85 to 95, still more preferably 87 to 94, and particularly preferably 90 to 94. It is. When% C _p of the lubricating base oil is less than the above lower limit, viscosity-temperature characteristics, thermal / oxidative stability, and friction characteristics tend to decrease, and further, when additives are blended in the lubricating base oil In addition, the effectiveness of the additive tends to decrease. Further, when the% C _p value of the lubricating base oil exceeds the upper limit value, the additive solubility will tend to be lower.

Moreover,% _{C N} of the lubricating base oil of the present invention is preferably 30 or less, more preferably 4 to 25, more preferably 5 to 13, particularly preferably from 5 to 8. If the% C _N value of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties will tend to be reduced. Moreover, when% _CN is less than the said lower limit, it exists in the tendency for the solubility of an additive to fall.

Incidentally, _say% C P in the present invention,% _C A _N and% _{C A,} obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number The percentage of the total number of naphthene carbons to the total number of carbons, and the percentage of aromatic carbons to the total number of carbons. In other words, 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 for a lubricating base oil containing no naphthene, it can be obtained by the above method. is% C _N may indicate a value greater than zero.

The content of saturated component in the lubricating base oil of the present invention, kinematic viscosity and% C _A at 100 ° C. is not particularly limited so far as it meets the above conditions, based on the lubricating base oils the total amount, preferably Is 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, and the ratio of the cyclic saturated component to the saturated component is preferably 40% by mass or less, preferably It is 35 mass% or less, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 21 mass% or less. When the content of the saturated component and the ratio of the cyclic saturated component in the saturated component satisfy the above conditions, the viscosity-temperature characteristics and the thermal / oxidative stability can be improved. When the additive is blended, the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricating base oil. Furthermore, according to the present invention, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in the friction reduction effect and an improvement in energy saving.

  The saturated content in the present invention is measured by the method described in the ASTM D 2007-93.

  In addition, a similar method that can obtain the same result can be used in the separation method of the saturated component or the composition analysis of the cyclic saturated component and the non-cyclic saturated component. For example, in addition to the above, a method described in ASTM D 2425-93, a method described in ASTM D 2549-91, a method using high performance liquid chromatography (HPLC), a method obtained by improving these methods, and the like can be given.

Also, the aromatic content in the lubricating base oil of the present invention, kinematic viscosity and% C _A at 100 ° C. is not particularly limited so far as it meets the above conditions, based on the lubricating base oils the total amount, preferably 5 % By mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. Especially preferably, it is 1.5 mass% or more. If the aromatic content exceeds the above upper limit, the viscosity-temperature characteristics, thermal / oxidative stability, friction characteristics, volatilization prevention properties, and low-temperature viscosity characteristics tend to decrease. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present invention may not contain an aromatic component, but by further increasing the solubility of the additive by setting the aromatic content to be the above lower limit or more. Can do.

  In addition, the aromatic component as used in the field of this invention means the value measured based on ASTM D 2007-93. In general, the aromatic component includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols and naphthols. Aromatic compounds having atoms are included.

  Further, the urea adduct value of the lubricating base oil according to the present invention is preferably 5% by mass or less from the viewpoint of improving the low-temperature viscosity characteristics without impairing the viscosity-temperature characteristics and obtaining high thermal conductivity. More preferably, it is 3 mass% or less, More preferably, it is 2.5 mass% or less, Most preferably, it is 2 mass% or less. In addition, the urea adduct value of the lubricating base oil component may be 0% by mass, but a sufficient low temperature viscosity characteristic and a lubricating base oil having a higher viscosity index can be obtained, and the dewaxing conditions can be relaxed. In view of excellent economic efficiency, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more.

  Here, the “urea adduct value” in the present invention means a value measured by the following method. 100 g of weighed sample oil (lubricating base oil) is placed in a round bottom flask, 200 mg of urea, 360 ml of toluene and 40 ml of methanol are added and stirred at room temperature for 6 hours. As a result, white granular crystals are produced as urea adducts in the reaction solution. The reaction solution is filtered through a 1 micron filter to collect the produced white granular crystals, and the obtained crystals are washed 6 times with 50 ml of toluene. The recovered white crystals are put in a flask, 300 ml of pure water and 300 ml of toluene are added, and the mixture is stirred at 80 ° C. for 1 hour. The aqueous phase is separated and removed with a separatory funnel, and the toluene phase is washed three times with 300 ml of pure water. A desiccant (sodium sulfate) is added to the toluene phase for dehydration, and then toluene is distilled off. The ratio (mass percentage) of the urea adduct thus obtained to the sample oil is defined as the urea adduct value.

  In the measurement of the urea adduct value, as the urea adduct, normal paraffin remains in the isoparaffin component that adversely affects the low-temperature viscosity characteristics, the thermal conductivity deterioration component, or the lubricating base oil. In this case, the normal paraffin in the case can be collected accurately and reliably, so that it is excellent as a low temperature viscosity characteristic and thermal conductivity evaluation index of the lubricating base oil. The inventors of the present invention have analyzed by using GC and NMR that the main component of the urea adduct is a normal paraffin and an isoparaffin urea adduct having 6 or more carbon atoms from the end of the main chain to the branch position. Confirm that there is.

  In the lubricating oil composition of the present invention, the lubricating base oil according to the present invention may be used alone, and the lubricating base oil according to the present invention may be one or more of other base oils. You may use together. When the lubricating base oil according to the present invention is used in combination with another base oil, the ratio of the lubricating base oil according to the present invention in the mixed base oil is preferably 30% by mass or more. 50% by mass or more is more preferable, and 70% by mass or more is still more preferable.

Although it does not restrict | limit especially as another base oil used together with the lubricating base oil which concerns on this invention, As a mineral oil type | system | group base oil, kinematic viscosity in 100 degreeC is 1-100 mm < ² > / s, for example,% C _a does not satisfy the above condition, solvent refined mineral oils, hydrocracked mineral oil, hydrotreated mineral oil, and the like solvent dewaxing base oil.

  Synthetic base oils include poly α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate) whose kinematic viscosity at 100 ° C. does not satisfy the above conditions. Rate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, Pentaerythritol pelargonate), polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl ether, etc. Is preferred. As the poly α-olefin, typically, an α-olefin oligomer or co-oligomer having 1 to 32 carbon atoms, preferably 6 to 16 (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) and the like. Of the hydrides.

  The production method of the poly-α-olefin is not particularly limited. For example, Friedel Crafts containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester. The method of superposing | polymerizing an alpha olefin in presence of a polymerization catalyst like a catalyst is mentioned.

Further, the lubricating oil composition of the present invention has a viscosity index improver (hereinafter referred to as “the present invention”) having a weight average molecular weight of 50,000 or more and a ratio of the weight average molecular weight to PSSI of 0.8 × 10 ⁴ or more. Viscosity index improver ") is contained in the total amount of the lubricating oil composition of 0.1 to 50 mass%.

The viscosity index improver according to the present invention is not particularly limited as long as the weight average molecular weight and the ratio between the weight average molecular weight and PSSI satisfy the above conditions. Specifically, non-dispersed or dispersed poly (meth) acrylate, non-dispersed or dispersed ethylene-α-olefin copolymer or its hydride, polyisobutylene or its hydride, styrene-diene hydrogenated copolymer Among the coalesced polymer, styrene-maleic anhydride copolymer, polyalkylstyrene, and the like, those having a weight average molecular weight of 50,000 or more and a ratio of the weight average molecular weight to PSSI of 0.8 × 10 ⁴ or more can be mentioned. The viscosity index improver according to the present invention may be either non-dispersed or dispersed, but is more preferably dispersed.

［式（１）中、Ｒ^１は水素またはメチル基を示し、Ｒ^２は炭素数１６以上の直鎖状または分枝状の炭化水素基を示す。］ As a preferable example of the viscosity index improver according to the present invention, one containing one or more (meth) acrylate structural units represented by the following general formula (1), containing 1 to 70 mol% (hereinafter, For convenience, “poly (meth) acrylate viscosity index improver according to the present invention”) may be mentioned. The poly (meth) acrylate viscosity index improver according to the present invention may be either non-dispersed or dispersed, but is more preferably dispersed.

[In the formula (1), R ¹ represents hydrogen or a methyl group, and R ² represents a linear or branched hydrocarbon group having 16 or more carbon atoms. ]

R ² in the structural unit represented by the formula (1) is a linear or branched hydrocarbon group having 16 or more carbon atoms as described above, and preferably a linear or branched group having 18 or more carbon atoms. More preferably, it is a linear or branched hydrocarbon having 20 or more carbon atoms, and more preferably a branched hydrocarbon group having 20 or more carbon atoms. Moreover, the upper limit of the hydrocarbon group represented by R ² is not particularly limited, but is preferably a linear or branched hydrocarbon group having 100 or less carbon atoms. More preferably, it is a linear or branched hydrocarbon of 50 or less, more preferably a linear or branched hydrocarbon of 30 or less, particularly preferably 30 or less, a branched hydrocarbon. And most preferably 25 or less branched hydrocarbons.

  Moreover, in the polymeth (acrylate) viscosity index improver according to the present invention, the proportion of the (meth) acrylate structural unit represented by the general formula (1) in the polymer is preferably 1 to 70 mol%, more Preferably it is 60 mol% or less, More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less, Most preferably, it is 30 mol% or less. Further, it is preferably at least 3 mol%, more preferably at least 5 mol%, particularly preferably at least 10 mol%. If it exceeds 70 mol%, the effect of improving viscosity temperature characteristics and low temperature viscosity characteristics may be inferior, and if it is less than 0.5 mol%, the effect of improving viscosity temperature characteristics may be inferior.

  The polymeth (acrylate) viscosity index improver according to the present invention is a structural unit derived from an arbitrary (meth) acrylate structural unit or an arbitrary olefin other than the (meth) acrylate structural unit represented by the general formula (1). Can be included. As a preferable aspect of the polymeth (acrylate) viscosity index improver according to the present invention, one or two monomers represented by the following general formula (2) (hereinafter referred to as “monomer (M-1)”) are used. The copolymer obtained by copolymerizing the above and monomers other than a monomer (M-1) is mentioned.

［上記一般式（２）中、Ｒ^１は水素原子またはメチル基を示し、Ｒ^２は炭素数１６以上の直鎖状または分枝状の炭化水素基を示す。］

[In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear or branched hydrocarbon group having 16 or more carbon atoms. ]

  Although the monomer combined with the monomer (M-1) is arbitrary, for example, a monomer represented by the following general formula (3) (hereinafter referred to as “monomer (M-2)”) is preferable. The copolymer of the monomer (M-1) and the monomer (M-2) is a so-called non-dispersed poly (meth) acrylate viscosity index improver.

［上記一般式（３）中、Ｒ^３は水素原子またはメチル基を示し、Ｒ^４は炭素数１〜１５の直鎖状または分枝状の炭化水素基を示す。］

[In the general formula (3), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms. ]

  In addition, other monomers to be combined with the monomer (M-1) include a monomer represented by the following general formula (4) (hereinafter referred to as “monomer (M-3)”) and a general formula (5) below. 1 type or 2 types or more chosen from the monomer (henceforth "monomer (M-4)") to be used is suitable. The copolymer of the monomer (M-1) and the monomer (M-3) and / or (M-4) is a so-called dispersed poly (meth) acrylate viscosity index improver. The dispersed poly (meth) acrylate viscosity index improver may further contain a monomer (M-2) as a constituent monomer.

［上記一般式（４）中、Ｒ^５は水素原子またはメチル基を示し、Ｒ^６は炭素数１〜１８のアルキレン基を示し、Ｅ^１は窒素原子を１〜２個、酸素原子を０〜２個含有するアミン残基または複素環残基を示し、ａは０または１を示す。］

[In the general formula (4), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group having 1 to 18 carbon atoms, E ¹ represents ¹ to 2 nitrogen atoms and 0 to 0 oxygen atoms. 2 represents an amine residue or a heterocyclic residue, and a represents 0 or 1. ]

Specific examples of the alkylene group having 1 to 18 carbon atoms represented by R ⁶ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, Examples include an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group (these alkylene groups may be linear or branched).

Specific examples of the group represented by E ¹ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, Examples thereof include morpholino group, pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, and pyrazino group.

［上記一般式（５）中、Ｒ^７は水素原子またはメチル基を示し、Ｅ^２は窒素原子を１〜２個、酸素原子を０〜２個含有するアミン残基または複素環残基を示す。］

[In the above general formula (5), R ⁷ represents a hydrogen atom or a methyl group, and E ² represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms. . ]

Specific examples of the group represented by E ² include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, and a morpholino group. Pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, pyrazino group and the like.

  As preferable examples of the monomers (M-3) and (M-4), specifically, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, Examples thereof include morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone and a mixture thereof.

  Although there is no restriction | limiting in particular about the copolymerization molar ratio of the copolymer of a monomer (M-1) and monomer (M-2)-(M-4), Monomer (M-1): Monomer (M-2) -(M-4) = 0.5: 99.5-70: 30 is preferable, More preferably, it is 5: 95-50: 50, More preferably, it is 10: 90-40: 60.

  The production method of the viscosity index improver according to the present invention is arbitrary, but the polymeth (acrylate) viscosity index improver according to the present invention is a monomer in the presence of a polymerization initiator such as benzoyl peroxide. It can be easily obtained by radical solution polymerization of a mixture of (M-1) and monomers (M-2) to (M-4).

  The PSSI (Permanent Cability Index) of the viscosity index improver according to the present invention is preferably 40 or less, more preferably 35 or less, still more preferably 30 or less, and particularly preferably 25 or less. Further, the PSSI of the viscosity index improver according to the present invention is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and particularly preferably 20 or more. When PSSI exceeds 40, shear stability may be deteriorated. Further, when PSSI is less than 5, the effect of improving the viscosity index is small, which is not only inferior in fuel economy and low-temperature viscosity characteristics, but also in cost.

  Note that “PSSI” here conforms to ASTM D 6022-01 (Standard Practication for Calculation of Permanent Shear Stable Stability Index), and ASTM D 6278-02 (Test Method for Stood For Shar. It means the permanent shear stability index of the polymer, calculated based on the data measured by Injector Apparatus.

The weight average molecular weight ( _Mw ) of the viscosity index improver according to the present invention needs to be 50,000 or more, more preferably 100,000 or more, still more preferably 150,000 or more, and particularly preferably. 180,000 or more, and most preferably 200,000 or more. Moreover, it is preferable that it is 1 million or less, More preferably, it is 700,000 or less, More preferably, it is 600,000 or less, Especially preferably, it is 500,000 or less. If the weight average molecular weight is less than 50,000, the effect of improving the viscosity index is small and not only the fuel efficiency and low temperature viscosity characteristics are inferior, but also the cost may increase. If the weight average molecular weight exceeds 1 million, shearing will occur. Stability, solubility in base oil, and storage stability may deteriorate.

The ratio of the weight average molecular weight to number average molecular weight of the viscosity index improver according to the present invention _(M W / M _n) is preferably from 0.5 to 5.0, more preferably 1.0 to 3. 5, more preferably 1.5 to 3, particularly preferably 1.7 to 2.5. When the ratio of the weight average molecular weight to the number average molecular weight is 0.5 or less or 5.0 or more, not only the solubility in the base oil and the storage stability are deteriorated, but also the viscosity-temperature characteristics are deteriorated, and the fuel economy is improved. May get worse.

The weight average molecular weight and PSSI ratio of viscosity index improver according to the present invention _(M W / PSSI) is required to be 0.8 × 10 ⁴ or more, preferably 1.0 × 10 ⁴ or more, More preferably, it is 2 × 10 ⁴ or more, and further preferably 2.5 × 10 ⁴ or more. If M _W / PSSI is below 0.8 × 10 ^4, there is a possibility that the viscosity-temperature characteristic is deteriorated i.e. deteriorates fuel efficiency.

  The content of the viscosity index improver according to the present invention is required to be 0.1 to 50% by mass, preferably 0.5 to 40% by mass, and more preferably 1 to 30%, based on the total amount of the composition. % By mass, particularly preferably 5 to 20% by mass. When the content of the viscosity index improver is less than 0.1% by mass, the effect of improving the viscosity index and the effect of reducing the product viscosity are reduced, and thus there is a possibility that the fuel economy cannot be improved. Also, if it exceeds 50% by mass, the product cost will increase significantly and the viscosity of the base oil will need to be reduced. Therefore, the lubrication performance under severe lubrication conditions (high temperature and high shear conditions) will be reduced and wear will be reduced. There is a concern that defects such as burn-in, seizure and fatigue failure may be the cause.

  In addition, the lubricating oil composition of the present invention includes, in addition to the viscosity index improver according to the present invention described above, an ordinary general non-dispersed or dispersed poly (meth) acrylate, non-dispersed or dispersed ethylene-α. -An olefin copolymer or a hydrogenated product thereof, polyisobutylene or a hydrogenated product thereof, a styrene-diene hydrogenated copolymer, a styrene-maleic anhydride ester copolymer, a polyalkylstyrene or the like may further be contained.

  In the lubricating oil composition of the present invention, a friction modifier selected from an organic molybdenum compound and an ashless friction modifier can be further contained in order to improve fuel economy performance.

  Examples of the organic molybdenum compound used in the present invention include organic molybdenum compounds containing sulfur such as molybdenum dithiophosphate and molybdenum dithiocarbamate.

  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 a mixture thereof. As these molybdenum dithiocarbamates, compounds having hydrocarbon groups having different carbon numbers and / or structures in one molecule can also be preferably used.

  In addition, organic molybdenum compounds containing sulfur other than these 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 metal salts of molybdate, molybdenum salts 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 molybdenum sulfides, chlorides Molybdenum halides such as molybdenum) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydro) (Rubyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfurized ester, etc.) or other organic compounds, or the above-mentioned sulfur-containing molybdenum compounds such as molybdenum sulfide or sulfurized molybdic acid and alkenyl succinimide complexes, etc. Can be mentioned.

  As the organic molybdenum compound, an organic molybdenum compound containing no 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.

  In the lubricating oil composition of the present invention, when an organic molybdenum compound is used, its content is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0, in terms of molybdenum element, based on the total amount of the composition. 0.005% by mass or more, more preferably 0.01% by mass or more, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less, particularly Preferably it is 0.03 mass% or less. When the content is less than 0.001% by mass, the thermal and 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.

  As the ashless friction modifier used in the present invention, any compound usually used as a friction modifier for lubricating oils can be used, for example, an alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly the number of carbon atoms. Ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic ethers and the like having at least one 6-30 linear alkyl group or linear alkenyl group in the molecule. It is done. One or more compounds selected from the group consisting of nitrogen-containing compounds represented by the following general formulas (6) and (7) and acid-modified derivatives thereof, and various examples exemplified in International Publication No. 2005/037967 Ashless friction modifiers may be mentioned.

In the general formula (6), R ⁸ 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 20 carbon atoms, an alkenyl group or a hydrocarbon group having functionality, particularly preferably an alkenyl group having 12 to 20 carbon atoms, and R ⁹ and R ¹⁰ each independently 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, or 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 represents oxygen or sulfur, preferably oxygen.

In the general formula (7), R ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms having functionality, 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 20 carbon atoms, an alkenyl group or a hydrocarbon group having functionality, particularly preferably an alkenyl group having 12 to 20 carbon atoms, and R ¹² _, R ¹³ and R ¹⁴ 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. , A functional hydrocarbon group having 1 to 10 carbon atoms or hydrogen, more preferably a hydrocarbon group having 1 to 4 carbon atoms or hydrogen, and even more preferably hydrogen.

Specific examples of the nitrogen-containing compound represented by the general formula (7) include hydrazides having 1 to 30 carbon atoms or functional hydrocarbon groups having 1 to 30 carbon atoms and derivatives thereof. is there. When R ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, and R ^{12 to} R ¹⁴ 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 ¹¹ and R ^{12 to} R ¹⁴ 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 ^{12 to} R ¹⁴ is hydrogen, N-hydrocarbyl hydrazide having a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms (hydrocarbyl is a hydrocarbon group) Etc.).

  When the ashless friction modifier is used in the lubricating oil composition of the present invention, the content of the ashless friction modifier is preferably 0.01% by mass or more, more preferably 0.1% by mass, based on the total amount of the composition. % Or more, more preferably 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more 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, and when the content exceeds 3% by mass, the effect of an antiwear additive or the like. Tends to be inhibited, or the solubility of the additive tends to deteriorate.

  In the present invention, either one of the organic molybdenum compound or the ashless friction modifier may be used, or both may be used in combination, but it is more preferable to use the ashless friction modifier.

  In order to further improve the performance, the lubricating oil composition of the present invention may contain any additive generally used in lubricating oils depending on the purpose. Examples of such additives include metal detergents, ashless dispersants, antioxidants, antiwear agents (or extreme pressure agents), corrosion inhibitors, rust inhibitors, pour point depressants, demulsifiers, metals Examples thereof include additives such as an inactivating agent and an antifoaming agent.

  Metal-based detergents include alkali salts such as alkali metal sulfonates or alkaline earth metal sulfonates, alkali metal phenates or alkaline earth metal phenates, and alkali metal salicylates or alkaline earth metal salicylates, basic normal salts or overbased salts. Etc. In the present invention, one or more alkali metal or alkaline earth metal detergents selected from the group consisting of these, particularly alkaline earth metal detergents can be preferably used. In particular, a magnesium salt and / or a calcium salt is preferable, and a calcium salt is more preferably used.

  As the ashless dispersant, any ashless dispersant used in lubricating oils can be used. For example, a mono- or mono-chain having at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule. Bisuccinimide, benzylamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or these And modified products of boron compounds, carboxylic acids, phosphoric acids, and the like. In use, one kind or two or more kinds arbitrarily selected from these can be blended.

  Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum. Specifically, for example, as a phenol-based ashless antioxidant, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert- Butylphenol) and the like are amine-based ashless antioxidants such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine.

  As the antiwear agent (or extreme pressure agent), any antiwear agent / extreme pressure agent used in lubricating oils can be used. For example, sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used. Specifically, phosphites, thiophosphites, dithiophosphites, trithiophosphites Esters, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithiocarbamate, molybdenum dithiocarbamate, disulfide , Polysulfides, sulfurized olefins, sulfurized fats and oils, and the like. Among these, addition of a sulfur-based extreme pressure agent is preferable, and sulfurized fats and oils are particularly preferable.

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

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

  As the pour point depressant, for example, a polymethacrylate polymer compatible with the lubricating base oil to be used can be used.

  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 thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.

Examples of antifoaming agents include silicone oils having a kinematic viscosity at 25 ° C. of less than 0.1 to 100 mm ² / s, alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, methyl salicylates and o. -Hydroxybenzyl alcohol etc. are mentioned.

  When these additives are contained in the lubricating oil composition of the present invention, the content thereof is 0.01 to 10% by mass based on the total amount of the composition.

Kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is required to be 3~9.3mm ² / s, preferably 8.5 mm ² / s or less, more preferably ^{8 mm} 2 / s or less, More preferably, it is 7.8 mm < ² > / s or less, Most preferably, it is 7.6 mm < ² > / s or less. Further, the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is preferably 4 mm ² / s or more, more preferably 5 mm ² / s or more, further preferably 6 mm ² / s or more, particularly preferably 7 mm ² / s. That's it. When the kinematic viscosity at 100 ° C. is less than 3 mm ² / s, there is a risk of insufficient lubricity, and when it exceeds 9.3 mm ² / s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.

The kinematic viscosity at 40 ° C. of the lubricating oil composition of the present invention is preferably 4 to 50 mm ² / s, preferably 40 mm ² / s or less, more preferably 35 mm ² / s or less, and particularly preferably 32 mm ² / s. s or less, most preferably 30 mm ² / s or less. Further, the kinematic viscosity at 40 ° C. of the lubricating oil composition of the present invention is preferably 10 mm ² / s or more, more preferably 20 mm ² / s or more, further preferably 25 mm ² / s or more, particularly preferably 27 mm ² / s. That's it. If the kinematic viscosity at 40 ° C. is less than 4 mm ² / s, there is a risk of insufficient lubricity, and if it exceeds 50 mm ² / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.

  The viscosity index of the lubricating oil composition of the present invention is preferably in the range of 140 to 300, more preferably 190 or more, still more preferably 200 or more, still more preferably 210 or more, and particularly preferably 220 or more. When the viscosity index of the lubricating oil composition of the present invention is less than 140, it may be difficult to improve fuel economy while maintaining the HTHS viscosity, and further reduce the low temperature viscosity at -35 ° C. May be difficult. In addition, when the viscosity index of the lubricating oil composition of the present invention is 300 or more, low temperature fluidity is deteriorated, and there is a risk of problems due to insufficient solubility of additives and compatibility with sealing materials. There is.

  The HTHS viscosity at 150 ° C. of the lubricating oil composition of the present invention is preferably 3.5 mPa · s or less, more preferably 3.0 mPa · s or less, still more preferably 2.8 mPa · s or less, particularly preferably. 2.7 mPa · s or less. Further, it is preferably 2.0 mPa · s or more, more preferably 2.3 mPa · s or more, further preferably 2.4 mPa · s or more, particularly preferably 2.5 mPa · s or more, and most preferably 2.6 mPa · s or more. It is. The HTHS viscosity at 150 ° C. here refers to the high temperature and high shear viscosity at 150 ° C. defined in ASTM D4683. When the HTHS viscosity at 150 ° C. is less than 2.0 mPa · s, there is a risk of insufficient lubricity, and when it exceeds 3.5 mPa · s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.

  The HTHS viscosity at 100 ° C. of the lubricating oil composition of the present invention is preferably 5.3 mPa · s or less, more preferably 5.0 mPa · s or less, still more preferably 4.8 mPa · s or less, particularly preferably. It is 4.7 mPa · s or less. Further, it is preferably 3.5 mPa · s or more, more preferably 3.8 mPa · s or more, particularly preferably 4.0 mPa · s or more, and most preferably 4.2 mPa · s or more. The HTHS viscosity at 100 ° C. here refers to the high temperature and high shear viscosity at 100 ° C. defined in ASTM D4683. When the HTHS viscosity at 100 ° C. is less than 3.5 mPa · s, there is a risk of insufficient lubricity, and when it exceeds 5.3 mPa · s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.

  In addition, the ratio of the HTHS viscosity at 150 ° C. to the HTHS viscosity at 100 ° C. (HTHS viscosity at 150 ° C./HTHS viscosity at 100 ° C.) of the lubricating oil composition of the present invention must be 0.50 or more. More preferably, it is 0.52 or more, More preferably, it is 0.54, Especially preferably, it is 0.55 or more, Most preferably, it is 0.56 or more. If the ratio is less than 0.50, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained.

  The lubricating oil composition of the present invention is excellent in fuel economy and lubricity, and has an HTHS viscosity without using a synthetic oil such as a poly-α-olefin base oil or an ester base oil or a low-viscosity mineral oil base oil. While maintaining a constant level, the kinematic viscosity at 40 ° C. and 100 ° C. and the HTHS viscosity at 100 ° C. of the lubricating oil, which are effective for improving fuel efficiency, are remarkably reduced. The lubricating oil composition of the present invention having such excellent characteristics can be suitably used as fuel-saving engine oils such as fuel-saving gasoline engine oil and fuel-saving diesel engine oil.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Examples 1-4, Comparative Examples 1-5)
In Examples 1 to 4 and Comparative Examples 1 to 5, lubricating oil compositions having the compositions shown in Table 2 were prepared using the base oils and additives shown below, respectively. Table 1 shows the properties of the base oils O-1 and O-2.
(Base oil)
O-1 (base oil 1): mineral oil obtained by hydrocracking / hydroisomerizing n-paraffin-containing oil O-2 (base oil 2): hydrocracked base oil (additive)
A-1 (viscosity index improver 1): PSSI = 20, MW = 400,000, Mw / PSSI = 2 × 10 ⁴ polymethacrylate (methyl methacrylate, dimethylaminoethyl methacrylate total 70 mol%, general formula ( methacrylate 2) ^{R 2} in is an alkyl group of 16 carbon atoms, the general formula (2) methacrylate ^{R 2} is an alkyl group of 18 carbon atoms in the general formula (2) ^{R 2} is 20 carbon atoms in the 20 mol% in total of all the alkyl groups of the alkyl group, and R ² in the general formula (2) is polymerized with 10 mol% of the methacrylate in which the branched alkyl group having 22 carbon atoms is polymerized. Methacrylate additive)
A-2 (viscosity index improver 2): PSSI = 16, MW = 300,000, Mw / PSSI = 1.9 × 10 ⁴ polymethacrylate (methyl methacrylate, R ² in the general formula (2) has 16 carbon atoms Dispersion type polymethacrylate-based additive having -22-alkyl methacrylate and dimethylaminoethyl methacrylate as main structural units)
A-3 (viscosity index improver 3): polymethacrylate (PS) = 5, MW = 80,000, Mw / PSSI = 1.6 × 10 ⁴ polymethyl methacrylate (methyl methacrylate, R ⁴ in the general formula (3) is 12 carbon atoms Non-dispersed polymethacrylate additive having methacrylate as main constituent unit of ˜15 alkyl groups)
A-4 (viscosity index improver 4): PSSI = 0.1, MW = 50,000, Mw / PSSI = 5 × 10 ⁵ polymethacrylate (methyl methacrylate, R ⁴ in the general formula (3) has 12 carbon atoms A non-dispersed polymethacrylate-based additive having as main structural units a methacrylate which is an alkyl group of ˜15 and a methacrylate wherein R ² in the general formula (2) is an alkyl group having 16 carbon atoms)
A-5 (viscosity index improver 5): Polymethacrylate having PSSI = 0 and Mw = 20,000 (methyl methacrylate and methacrylate in which R ² in the general formula (2) is an alkyl group having 16 to 22 carbon atoms. Non-dispersed polymethacrylate additive as main structural unit)
A-6 (viscosity index improver 6): polymethacrylate of PSSI = 40, MW = 300,000, Mw / PSSI = 0.75 × 10 ⁴ (methyl methacrylate, R ⁴ in the general formula (3) is 12 carbon atoms methacrylate is a linear alkyl group of the general formula (3) methacrylate R ⁴ is a linear alkyl group of 13 carbon atoms, the general formula (3) in R ⁴ is the number 14 linear carbon A methacrylate that is an alkyl group, a methacrylate in which R ⁴ in the general formula (3) is a linear alkyl group having 15 carbon atoms, and a dispersed polymethacrylate-based additive having dimethylaminoethyl methacrylate as a main constituent unit )
A-7 (viscosity index improver 7): PSSI = 40, MW = 350,000, Mw / PSSI = 0.9 × 10 ⁴ polymethacrylate (methyl methacrylate, R ² in the general formula (2) has 16 carbon atoms Dispersion type polymethacrylate-based additive having -22-alkyl methacrylate and dimethylaminoethyl methacrylate as main structural units)
B-1 (friction modifier 1): glycerin monooleate B-2 (friction modifier 2): oleyl urea B-3 (friction modifier 3): molybdenum dithiocarbamate C-1 (ashless dispersant 1): polybutenyl Succinimide (bis type, Mw 10,000, nitrogen content 0.5% by mass)
C-2 (ashless dispersant 2): boric acid-modified polybutenyl succinimide (bis type, Mw 4,000, nitrogen content 1.4% by mass, boron content 0.5% by mass)
D-1 (Ashless antioxidant 1): Amine-based D-2 (Ashless antioxidant 2): Phenol-based E-1 (metal detergent): Ca salicylate (Ca 6.3%)
F-1 (antiwear agent 1): secondary ZDTP (Zn 7.2 mass%, P 6.2 mass%)
F-2 (Abrasion inhibitor 2): Dithiocarbamate

[Evaluation of lubricating oil composition]
The lubricating oil compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were measured for kinematic viscosity at 40 ° C. or 100 ° C., viscosity index, HTHS viscosity at 100 ° C. or 150 ° C., and CCS viscosity at −35 ° C. . Each physical property value was measured by the following evaluation method. The obtained results are shown in Table 2.
(1) Kinematic viscosity: ASTM D-445
(2) Viscosity index: JIS K 2283-1993
(3) HTHS viscosity: ASTM D4683
(4) CCS viscosity: ASTM D5293
(5) Measurement of friction torque: Using a 2000 cc DOHC engine, the friction torque under the conditions of 1500 rpm and 80 ° C. was measured. The friction torque reduction rate was calculated using MoDTC blended 0W-20 oil, which is a commercially available fuel-saving engine oil, as a reference oil.

As shown in Table 2, the lubricating oil compositions of Examples 1 to 4 and Comparative Examples 1 to 5 have the same HTHS viscosity at 150 ° C., but the lubricating oil compositions of Comparative Examples 1 to 5 In comparison, the lubricating oil compositions of Examples 1 to 4 have low 40 ° C. kinematic viscosity, 100 ° C. kinematic viscosity, 100 ° C. HTHS viscosity, and CCS viscosity, and further, the HTHS viscosity at 150 ° C. and the HTHS viscosity at 100 ° C. The ratio was large, and the low temperature viscosity and viscosity temperature characteristics were good. From this result, the lubricating oil composition of the present invention is excellent in fuel economy and lubricity, without using a synthetic oil such as a poly-α-olefin base oil or an ester base oil or a low viscosity mineral oil base oil. The lubricating oil composition has a kinematic viscosity at 40 ° C. and 100 ° C. and a HTHS viscosity at 100 ° C. that are effective for improving fuel efficiency while maintaining the HTHS viscosity at a constant level. Recognize.

Claims (1)

_A lubricating base oil having a kinematic viscosity at 100 ° C. of 1 to 10 mm ² / s and a% CA of 5 or less;
Based on the total amount of the lubricating oil composition, a weight average molecular weight of 100,000 or more, PSSI is 35 or less, the poly (meth) acrylate based viscosity is the ratio of weight average molecular weight and PSSI is 0.8 × 10 ⁴ or more Index improver 0.1-50 mass%,
The kinematic viscosity at 100 ° C. is 3 to 9.3 mm ² / s, the HTHS viscosity at 150 ° C. is 2.0 mPa · s or more, and the HTHS viscosity at 100 ° C. is 5.3 mPa · s or less. and a lubricating oil composition the ratio of the HTHS viscosity at HTHS viscosity and 100 ° C. at 0.99 ° C. is characterized in that 0.52 or more.