EP2522709A1

EP2522709A1 - Lubricant composition

Info

Publication number: EP2522709A1
Application number: EP10842116A
Authority: EP
Inventors: Shigeki Matsui; Akira Yaguchi; Akio Mutou; Mari Nagae
Original assignee: JX Nippon Oil and Energy Corp
Current assignee: Eneos Corp
Priority date: 2010-01-07
Filing date: 2010-09-27
Publication date: 2012-11-14
Also published as: US20120283159A1; WO2011083601A1; CN102712869A; JP2011140573A; EP2522709A4; CN106318573A

Abstract

The lubricating oil composition of the invention comprises a lubricating base oil with a 100°C kinematic viscosity of 1-20 mm²/s, and (A) a viscosity index improver having a ratio M1/M2 of 0.20 or greater, between the total area of the peaks between chemical shifts of 36-38 ppm M1 and the total area of the peaks between chemical shifts of 64-66 ppm M2, with respect to the total area of all of the peaks, in the spectrum obtained by ¹³C-NMR, (B) a friction modifier, and (C) an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate.

Description

Technical Field

The present invention relates to a lubricating oil composition.

Background Art

Lubricating oils have been used in the past in internal combustion engines, gearboxes and other mechanical devices to promote smoother functioning. Internal combustion engine lubricating oils (engine oils), in particular, must exhibit a high level of performance under the high-performance, high-output and harsh operating conditions of internal combustion engines. Various additives such as anti-wear agents, metal cleaning agents, non-ash powders and antioxidants are therefore added to conventional engine oils to meet such performance demands (see Patent documents 1-3). In addition, the fuel efficiency performance required of lubricating oils has continued to increase in recent years, and this has led to application of various high-viscosity-index base oils or friction modifiers (see Patent document 4, for example).

Citation List

Patent Literature

[Patent document 1] Japanese Unexamined Patent Application Publication No. 2001-279287
[Patent document 2] Japanese Unexamined Patent Application Publication No. 2002-129182
[Patent document 3] Japanese Unexamined Patent Application Publication HEI No. 08-302378
[Patent document 4] Japanese Unexamined Patent Application Publication HEI No. 06-306384

Summary of Invention

Technical Problem

The conventional lubricating oils, however, cannot necessarily be considered adequate in terms of fuel efficiency.
For example, one common method for achieving fuel efficiency involves reducing the kinematic viscosity of the lubricating oil and increasing the viscosity index (multigrading by a combination of a low-viscosity base oil and a viscosity index improver). With such a method, however, the reduction in viscosity of the lubricating oil or the base oil composing it can reduce the lubricating performance under severe lubrication conditions (high-temperature, high-shear conditions), resulting in wear and seizing, as well as leading to problems such as fatigue fracture. In other words, with conventional lubricating oils it is difficult to impart sufficient fuel efficiency while maintaining practical performance in other ways such as durability.
Furthermore, while it is effective to raise the 150°C HTHS viscosity (the "HTHS viscosity" is also known as "high-temperature high-shear viscosity") and lower the 40°C kinematic viscosity, the 100°C kinematic viscosity and the 100°C HTHS viscosity, in order to prevent the aforementioned inconveniences and impart fuel efficiency while maintaining durability, it has been extremely difficult to satisfy all of these conditions with conventional lubricating oils. It is also known that mere reduction in viscosity increases the friction coefficient in the boundary lubrication region in which metals contact. In order to increase fuel efficiency, it is also necessary to lower the friction coefficient in the boundary lubrication region.
The present invention has been accomplished in light of these circumstances, and its object is to provide a lubricating oil composition with excellent fuel efficiency, that can sufficiently lower the 40°C kinematic viscosity, 100°C kinematic viscosity and 100°C HTHS viscosity, and sufficiently minimize increase in the friction coefficient in the boundary lubrication region, while maintaining its 150°C HTHS viscosity.

Solution to Problem

In order to solve the problems described above, the invention provides a lubricating oil composition comprising a lubricating base oil with a 100°C kinematic viscosity of 1-20 mm²/s, (A) a viscosity index improver having a ratio M1/M2 of 0.20 or greater, between the total area of the peaks between chemical shifts of 36-38 ppm M1 and the total area of the peaks between chemical shifts of 64-66 ppm M2, with respect to the total area of all of the peaks, in the spectrum obtained by ¹³C-NMR, (B) a friction modifier, and (C) an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate.
The (A) viscosity index improver is preferably a poly(meth)acrylate-based viscosity index improver.
Also, the (A) viscosity index improver preferably has a PSSI of no greater than 40 and a weight-average molecular weight/PSSI ratio of at least 1 × 10⁴.
The abbreviation "PSSI" used for the invention stands for the "Permanent Shear Stability Index" of the polymer, which is calculated according to ASTM D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index) based on data measured according to ASTM D 6278-02 (Test Method for Shear Stability of Polymer Containing Fluids Using a European Diesel Injector Apparatus).
The (B) friction modifier is preferably an organic molybdenum compound.
The (C) overbased metal salt obtained by overbasing the oil-soluble metal salt with the alkaline earth metal borate is preferably an overbased alkaline earth metal salicylate obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal borate.

Advantageous Effects of Invention

As mentioned above, according to the invention it is possible to provide a lubricating oil composition with excellent fuel efficiency, that can sufficiently lower the 40°C kinematic viscosity, 100°C kinematic viscosity and 100°C HTHS viscosity, and sufficiently minimize increase in the friction coefficient in the boundary lubrication region, while maintaining its 150°C HTHS viscosity. For example, with a lubricating oil composition of the invention it is possible to exhibit adequate fuel efficiency while maintaining a desired value for the 150°C HTHS viscosity, without using a synthetic oil such as a poly-α-olefin-based base oil or ester-based base oil, or a low-viscosity mineral base oil.
The lubricating oil composition of the invention is also useful for gasoline engines, diesel engines and gas engines for two-wheel vehicles, four-wheel vehicles, electric power generation and cogeneration, and the like, while it can be suitably used not only for such engines that run on fuel with a sulfur content of no greater than 50 ppm by mass, but also for ship engines, outboard motor engines and the like.

Description of Embodiments

A preferred embodiment of the invention will now be described in detail.
The lubricating oil composition of this embodiment comprises a lubricating base oil with a 100°C kinematic viscosity of 1-20 mm²/s, and (A) a viscosity index improver having a ratio M1/M2 of 0.20 or greater, between the total area of the peaks between chemical shifts of 36-38 ppm M1 and the total area of the peaks between chemical shifts of 64-66 ppm M2, with respect to the total area of all of the peaks, in the spectrum obtained by ¹³C-NMR, (B) a friction modifier, and (C) an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate.
For the lubricating oil composition of this embodiment there was used a lubricating base oil having a 100°C kinematic viscosity of 1-20 mm²/s (hereunder referred to as "lubricating base oil of this embodiment").
The lubricating base oil of this embodiment may be, for example, a purified paraffinic mineral oil produced by subjecting a lube-oil distillate obtained by atmospheric distillation and/or vacuum distillation of crude oil, to a single treatment or a combination of two or more treatments from among refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, hydroisomerization, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid cleaning and white clay treatment, or a normal paraffinic base oil or isoparaffinic base oil having a 100°C kinematic viscosity of 1-20 mm²/s.
A preferred example for the lubricating base oil of this embodiment is a base oil obtained by using one of the base oils (1)-(8) mentioned below as the raw material and purifying this stock oil and/or the lube-oil distillate recovered from the stock oil by a prescribed refining process, and recovering the lube-oil distillate.

(1) Distilled oil from atmospheric distillation of a paraffin-based crude oil and/or mixed-base crude oil.
(2) Distilled oil from vacuum distillation of a tmospheric distillation residue oil from paraffin-based crude oil and/or mixed-base crude oil (WVGO).
(3) Wax obtained by a lubricating oil dewaxing step (slack wax or the like) and/or synthetic wax obtained by a gas-to-liquid (GTL) process (Fischer-Tropsch wax, GTL wax or the like).
(4) Blended oil comprising one or more oils selected from among base oils (1)-(3) and/or mild-hydrocracked oil obtained from the blended oil.
(5) Blended oil comprising two or more selected from among base oils (1)-(4).
(6) Deasphalted oil (DAO) from base oil (1), (2), (3), (4) or (5).
(7) Mild-hydrocracked oil (MHC) obtained from base oil (6).
(8) Blended oil comprising two or more selected from among base oils (1)-(7).

The prescribed refining process described above is preferably hydrorefining such as hydrocracking or hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing or catalytic dewaxing; white clay refining with acidic white clay or active white clay, or chemical (acid or alkali) washing such as sulfuric acid treatment or caustic soda washing. According to the invention, any one of these refining processes may be used alone, or a combination of two or more thereof may be used in combination. When a combination of two or more refining processes is used, their order is not particularly restricted and it may be selected as appropriate.
The lubricating base oil of this embodiment is most preferably one of the following base oils (9) or (10) obtained by prescribed treatment of a base oil selected from among base oils (1)-(8) above or a lube-oil distillate recovered from the base oil.

(9) Hydrocracked mineral oil obtained by hydrocracking of a base oil selected from among base oils (1)-(8) above or a lube-oil distillate recovered from the base oil, dewaxing treatment such as solvent dewaxing or catalytic dewaxing of the product or a lube-oil distillate recovered from distillation of the product, or further distillation after the dewaxing treatment.
(10) Hydroisomerized mineral oil obtained by hydroisomerization of a base oil selected from among base oils (1)-(8) above or a lube-oil distillate recovered from the base oil, and dewaxing treatment such as solvent dewaxing or catalytic dewaxing of the product or a lube-oil distillate recovered from distillation of the product, or further distillation after the dewaxing treatment.

For obtaining the lubricating base oil of (9) or (10) above, a solvent refining treatment and/or hydrofinishing treatment step may also be carried out by convenient steps if necessary.
There are no particular restrictions on the catalyst used for the hydrocracking and hydroisomerization, but there are preferably used hydrocracking catalysts comprising a hydrogenating metal (for example, one or more metals of Group VIa or metals of Group VIII of the Periodic Table) supported on a carrier which is a complex oxide with decomposing activity (for example, silica-alumina, alumina-boria, silica-zirconia or the like) or a combination of two or more of such complex oxides bound with a binder, or hydroisomerization catalysts obtained by supporting one or more metals of Group VIII having hydrogenating activity on a carrier comprising zeolite (for example, ZSM-5, zeolite beta, SAPO-11 or the like). The hydrocracking catalyst or hydroisomerization catalyst may be used as a combination of layers or a mixture.
The reaction conditions for hydrocracking and hydroisomerization are not particularly restricted, but preferably the hydrogen partial pressure is 0.1-20 MPa, the mean reaction temperature is 150-450°C, the LHSV is 0.1-3.0 hr^-1 and the hydrogen/oil ratio is 50-20,000 scf/b.
The 100°C kinematic viscosity of the lubricating base oil of this embodiment must be no greater than 20 mm²/s, and is preferably no greater than 10 mm²/s, more preferably no greater than 7 mm²/s, even more preferably no greater than 5.0 mm²/s, especially preferably no greater than 4.5 mm²/s and most preferably no greater than 4.0 mm²/s. The 100°C kinematic viscosity, on the other hand, must be 1 mm²/s or greater, and it is preferably 1.5 mm²/s or greater, more preferably 2 mm²/s or greater, even more preferably 2.5 mm²/s or greater and most preferably 3 mm²/s or greater. The 100°C kinematic viscosity according to the invention is the 100°C kinematic viscosity measured according to ASTM D-445. If the 100°C kinematic viscosity of the lubricating base oil exceeds 20 mm²/s, the low-temperature viscosity characteristic may be impaired and sufficient fuel efficiency may not be obtained, while if it is less than 1 mm²/s, oil film formation at the lubricated sections will be inadequate, resulting in inferior lubricity and potentially large evaporation loss of the lubricating oil composition.
According to the invention, lubricating base oils having a 100°C kinematic viscosity in the following ranges are preferably used after fractionation by distillation or the like.

(I) A lubricating base oil with a 100°C kinematic viscosity of at least 1.5 mm²/s and less than 3.5 mm²/s, and more preferably 2.0-3.0 mm²/s.
(II) A lubricating base oil with a 100°C kinematic viscosity of at least 3.5 mm²/s and less than 4.5 mm²/s, and more preferably 3.7-4.3 mm²/s.
(III) A lubricating base oil with a 100°C kinematic viscosity of 4.5-10 mm²/s, more preferably 4.8-9 mm²/s and most preferably 5.5-8.0 mm²/s.

The 40°C kinematic viscosity of the lubricating base oil of this embodiment is also preferably no greater than 80 mm²/s, more preferably no greater than 50 mm²/s, even more preferably no greater than 20 mm²/s, yet more preferably no greater than 18 mm²/s and most preferably no greater than 16 mm²/s. Also, the 40°C kinematic viscosity is preferably 6.0 mm²/s or greater, more preferably 8.0 mm²/s or greater, even more preferably 12 mm²/s or greater, yet more preferably 14 mm²/s or greater and most preferably 15 mm²/s or greater. If the 40°C kinematic viscosity of the lubricating base oil exceeds 80 mm²/s, the low-temperature viscosity characteristic may be impaired and sufficient fuel efficiency may not be obtained, while if it is lower than 6.0 mm²/s, oil film formation at the lubricated sections will be inadequate, resulting in inferior lubricity and potentially large evaporation loss of the lubricating oil composition. According to the invention, a lube-oil distillate having a 40°C kinematic viscosity in one of the following ranges is preferably used after fractionation by distillation or the like.

(IV) A lubricating base oil with a 40°C kinematic viscosity of at least 6.0 mm²/s and less than 12 mm²/s, and more preferably 8.0-12 mm²/s.
(V) A lubricating base oil with a 40°C kinematic viscosity of at least 12 mm²/s and less than 28 mm²/s, and more preferably 13-19 mm²/s.
(VI) A lubricating base oil with a 40°C kinematic viscosity of 28-50 mm²/s, more preferably 29-45 mm²/s and most preferably 30-40 mm²/s.

The viscosity index of the lubricating base oil of this embodiment is preferably 120 or greater. Also, the viscosity index for the lubricating base oils (I) and (IV) is preferably 120-135 and more preferably 120-130. The viscosity index for the lubricating base oils (II) and (V) is preferably 120-160, more preferably 125-150 and even more preferably 135-145. Also, the viscosity index for the lubricating base oils (III) and (VI) is preferably 120-180 and more preferably 125-160. A viscosity index below these lower limits will not only impair the viscosity-temperature characteristic, heat and oxidation stability and resistance to volatilization, but will also tend to increase the friction coefficient and potentially lower the anti-wear property. If the viscosity index exceeds the aforementioned upper limit, the low-temperature viscosity characteristic will tend to be reduced.
The viscosity index for the purpose of the invention is the viscosity index measured according to JIS K 2283-1993.
The 15°C density (ρ₁₅) of the lubricating base oil of this embodiment will also depend on the viscosity grade of the lubricating base oil component, but it is preferably no greater than the value of ρ represented by the following formula (A), i.e., ρ₁₅ ≤ ρ. $ρ = 0.0025 \times kv 100 + 0.816$

[In this equation, kv100 represents the 100°C kinematic viscosity (mm²/s) of the lubricating base oil.]
If ρ₁₅ > ρ, the viscosity-temperature characteristic and heat and oxidation stability, as well as the resistance to volatilization and the low-temperature viscosity characteristic, will tend to be lowered, thus potentially impairing the fuel efficiency. In addition, the efficacy of additives included in the lubricating base oil may be reduced.
Specifically, the 15°C density (ρ₁₅) of the lubricating base oil of this embodiment is preferably no greater than 0.860, more preferably no greater than 0.850, even more preferably no greater than 0.840 and most preferably no greater than 0.822.
The 15°C density for the purpose of the invention is the density measured at 15°C according to JIS K 2249-1995.
The pour point of the lubricating base oil of this embodiment will depend on the viscosity grade of the lubricating base oil, and for example, the pour point for the lubricating base oils (I) and (IV) is preferably no higher than -10°C, more preferably no higher than -12.5°C and even more preferably no higher than -15°C. Also, the pour point for the lubricating base oils (II) and (V) is preferably no higher than -10°C, more preferably no higher than -15°C and even more preferably no higher than -17.5°C. The pour point for the lubricating base oils (III) and (VI) is preferably no higher than -10°C, more preferably no higher than -12.5°C and even more preferably no higher than -15°C. If the pour point exceeds the upper limit specified above, the low-temperature flow properties of a lubricating oil employing the lubricating base oil will tend to be reduced. The pour point for the purpose of the invention is the pour point measured according to JIS K 2269-1987.
The aniline point (AP (°C)) of the lubricating base oil of the invention will also depend on the viscosity grade of the lubricating base oil, but it is preferably greater than or equal to the value of A as represented by the following formula (B), i.e., AP ≥ A. $A = 4.3 \times kv 100 + 100 (B)$

[In this equation, kv100 represents the 100°C kinematic viscosity (mm²/s) of the lubricating base oil.]
If AP < A, the viscosity-temperature characteristic, heat and oxidation stability, resistance to volatilization and low-temperature viscosity characteristic of the lubricating base oil will tend to be reduced, while the efficacy of additives when added to the lubricating base oil will also tend to be reduced.
The AP for the lubricating base oils (I) and (IV) is preferably 108°C or higher and more preferably 110°C or higher. The AP for the lubricating base oils (II) and (V) is preferably 113°C or higher and more preferably 119°C or higher. Also, the AP for the lubricating base oils (III) and (VI) is preferably 125°C or higher and more preferably 128°C or higher. The aniline point for the purpose of the invention is the aniline point measured according to JIS K 2256-1985.
The iodine value of the lubricating base oil of this embodiment is preferably no greater than 3, more preferably no greater than 2, even more preferably no greater than 1, yet more preferably no greater than 0.9 and most preferably no greater than 0.8. Although the value may be less than 0.01, in consideration of the fact that this does not produce any further significant effect and is uneconomical, the value is preferably 0.001 or greater, more preferably 0.01 or greater, even more preferably 0.03 or greater and most preferably 0.05 or greater. Limiting the iodine value of the lubricating base oil component to no greater than 3 can drastically improve the heat and oxidation stability. The "iodine value" for the purpose of the invention is the iodine value measured by the indicator titration method according to JIS K 0070, "Acid Values, Saponification Values, Iodine Values, Hydroxyl Values And Unsaponification Values Of Chemical Products".
The sulfur content in the lubricating base oil of this embodiment will depend on the sulfur content of the starting material. For example, when using a substantially sulfur-free starting material as for synthetic wax components obtained by Fischer-Tropsch reaction, it is possible to obtain a substantially sulfur-free lubricating base oil. When using a sulfur-containing starting material, such as slack wax obtained by a lubricating base oil refining process or microwax obtained by a wax refining process, the sulfur content of the obtained lubricating base oil will normally be 100 ppm by mass or greater. From the viewpoint of further improving the heat and oxidation stability and reducing sulfur, the sulfur content in the lubricating base oil of this embodiment is preferably no greater than 100 ppm by mass, more preferably no greater than 50 ppm by mass, even more preferably no greater than 10 ppm by mass and especially no greater than 5 ppm by mass.
The nitrogen content in the lubricating base oil of this embodiment is not particularly restricted, but is preferably no greater than 7 ppm by mass, more preferably no greater than 5 ppm by mass and even more preferably no greater than 3 ppm by mass. If the nitrogen content exceeds 5 ppm by mass, the heat and oxidation stability will tend to be reduced. The nitrogen content for the purpose of the invention is the nitrogen content measured according to JIS K 2609-1990.
The %C_p value of the lubricating base oil of this embodiment is preferably at least 70, and it is preferably 80-99, more preferably 85-95, even more preferably 87-94 and most preferably 90-94. If the %C_p value of the lubricating base oil is less than the aforementioned lower limit, the viscosity-temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced, while the efficacy of additives when added to the lubricating base oil will also tend to be reduced. If the %C_p value of the lubricating base oil is greater than the aforementioned upper limit, on the other hand, the additive solubility will tend to be lower.
The %C_A of the lubricating base oil of this embodiment is preferably no greater than 2, and it is more preferably no greater than 1, even more preferably no greater than 0.8 and most preferably no greater than 0.5. If the %C_A value of the lubricating base oil exceeds the aforementioned upper limit, the viscosity-temperature characteristic, heat and oxidation stability and fuel efficiency will tend to be reduced.
The %C_N value of the lubricating base oil of this embodiment is preferably no greater than 30, more preferably 4-25, even more preferably 5-13 and most preferably 5-8. If the %C_N value of the lubricating base oil exceeds the aforementioned upper limit, the viscosity-temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced. If %C_N is less than the aforementioned lower limit, the additive solubility will tend to be lower.
The %C_P, %C_N and %C_A values for the purpose of the invention are, respectively, the percentage of paraffinic carbons with respect to total carbon atoms, the percentage of naphthenic carbons with respect to total carbons and the percentage of aromatic carbons with respect to total carbons, as determined by the method of ASTM D 3238-85 (n-d-M ring analysis). That is, the preferred ranges for %C_P, %C_N and %C_A are based on values determined by these methods, and for example, %C_N may be a value exceeding 0 according to these methods even if the lubricating base oil contains no naphthene portion.
The aromatic content in the lubricating base oil of this embodiment is preferably 90% by mass or greater, more preferably 95% by mass or greater and even more preferably 99% by mass or greater based on the total mass of the lubricating base oil, while the proportion of cyclic saturated components of the saturated components is preferably no greater than 40% by mass, more preferably no greater than 35% by mass, even more preferably no greater than 30% by mass, yet more preferably no greater than 25% by mass and most preferably no greater than 21% by mass. The proportion of cyclic saturated components among the saturated components is also preferably 5% by mass or greater and more preferably 10% by mass or greater. If the saturated component content and proportion of cyclic saturated components among the saturated components both satisfy these respective conditions, it will be possible to improve the viscosity-temperature characteristic and heat and oxidation stability, while additives added to the lubricating base oil will be kept in a sufficiently stable dissolved state in the lubricating base oil so that the functions of the additives can be exhibited at a higher level. According to the invention it is also possible to improve the frictional properties of the lubricating base oil itself, and thus result in a greater friction reducing effect and therefore increased energy savings.
The "saturated components" for the purpose of the invention are measured by the method of ASTM D 2007-93.
Other methods may be used for separation of the saturated components or for compositional analysis of the cyclic saturated components and acyclic saturated components, so long as they provide similar results. Examples of other methods include the method according to ASTM D 2425-93, the method according to ASTM D 2549-91, methods of high performance liquid chromatography (HPLC), and modified forms of these methods.
The aromatic content in the lubricating base oil of this embodiment is preferably no greater than 5% by mass, more preferably no greater than 4% by mass, even more preferably no greater than 3% by mass and most preferably no greater than 2% by mass, and also preferably 0.1% by mass or greater, more preferably 0.5% by mass or greater, even more preferably 1% by mass or greater and most preferably 1.5% by mass or greater, based on the total mass of the lubricating base oil. If the aromatic content exceeds the aforementioned upper limit, the viscosity-temperature characteristic, heat and oxidation stability, frictional properties, resistance to volatilization and low-temperature viscosity characteristic will tend to be reduced, while the efficacy of additives when added to the lubricating base oil will also tend to be reduced. The lubricating base oil of this embodiment may be free of aromatic components, but the solubility of additives can be further increased with an aromatic content above the aforementioned lower limit.
The aromatic content, according to the invention, is the value measured according to ASTM D 2007-93. The aromatic portion normally includes alkylbenzenes and alkylnaphthalenes, as well as anthracene, phenanthrene and their alkylated forms, compounds with four or more fused benzene rings, and heteroatom-containing aromatic compounds such as pyridines, quinolines, phenols, naphthols and the like.
A synthetic base oil may be used as the lubricating base oil of this embodiment. As synthetic base oils there may be mentioned poly-α-olefins and their hydrogenated forms, isobutene oligomers and their hydrogenated forms, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate and the like), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate and the like), polyoxyalkylene glycols, dialkyldiphenyl ethers and polyphenyl ethers, which have 100°C kinematic viscosities of less than 1-20 mm²/s, among which poly-α-olefins are preferred. As typical poly-α-olefins there may be mentioned C2-32 and preferably C6-16 α-olefin oligomers or co-oligomers (1-octene oligomers, decene oligomers, ethylene-propylene co-oligomers and the like), and their hydrogenated forms.
There are no particular restrictions on the process for producing poly-α-olefins, and as an example there may be mentioned a process wherein an α-olefin is polymerized in the presence of a polymerization catalyst such as a Friedel-Crafts catalyst comprising a complex of aluminum trichloride or boron trifluoride with water, an alcohol (ethanol, propanol, butanol or the like) and a carboxylic acid or ester.
The lubricating base oil of this embodiment may be used alone as a lubricating oil composition according to the embodiment, or the lubricating base oil of the embodiment may be combined with one or more other base oils. When the lubricating base oil of this embodiment is combined with another base oil, the proportion of the lubricating base oil of this embodiment in the total mixed base oil is preferably at least 30% by mass, more preferably at least 50% by mass and even more preferably at least 70% by mass.
There are no particular restrictions on the other base oil used in combination with the lubricating base oil of this embodiment, and as examples of mineral base oils there may be mentioned solvent refined mineral oils, hydrocracked mineral oils, hydrorefined mineral oils and solvent dewaxed base oils having 100°C kinematic viscosities of greater than 20 mm²/s and no greater than 200 mm²/s.
Other synthetic base oils to be used in combination with the lubricating base oil of this embodiment include the aforementioned synthetic base oils that have 100°C kinematic viscosities outside of the range of 1-20 mm²/s.
The (A) viscosity index improver to be used for the invention preferably has a ratio of at least 0.20 for M1/M2, as the ratio between the total area of the peaks between chemical shifts of 36-38 ppm M1 and the total area of the peaks between chemical shifts of 64-66 ppm M2, with respect to the total area of all of the peaks, in the spectrum obtained by nuclear magnetic resonance analysis (¹³C-NMR).
A (A) viscosity index improver satisfying the conditions specified above is, specifically, a non-dispersed or dispersed ester group-containing viscosity index improver, and examples include non-dispersed or dispersed poly(meth)acrylate-based viscosity index improvers, non-dispersed or dispersed olefin-(meth)acrylate copolymer-based viscosity index improvers, styrene-maleic anhydride ester copolymer-based viscosity index improvers and mixtures of the foregoing, among which non-dispersed or dispersed poly(meth)acrylate-based viscosity index improvers are preferred. Non-dispersed or dispersed polymethacrylate-based viscosity index improvers are especially preferred.
M1/M2 is preferably 0.3 or greater, even more preferably 0.4 or greater, yet more preferably 0.5 or greater and most preferably 0.6 or greater. Also, M1/M2 is preferably no greater than 3.0, even more preferably no greater than 2.0, yet more preferably no greater than 1.0 and most preferably no greater than 0.8. If M1/M2 is less than 0.20, it may not be possible to obtain the necessary fuel efficiency, and the low-temperature viscosity characteristic may also be impaired. If M1/M2 exceeds 3.0, it may not be possible to obtain the necessary fuel efficiency, and the solubility and storage stability may also be impaired.
When the viscosity index improver contains a diluting oil, the nuclear magnetic resonance analysis (¹³C-NMR) spectrum is for the polymer after separating the diluting oil by rubber film dialysis or the like.
The total area of the peaks (M1) between chemical shifts of 36-38 ppm with respect to the total area of all of the peaks, when the viscosity index improver is a poly(meth)acrylate, for example, is the ratio of the integrated intensity due to specific β-branched structures in the poly(meth)acrylate side chains with respect to the total integrated intensity of all of the carbon atoms, as measured by ¹³C-NMR, and the total area of the peaks (M2) between chemical shifts of 64-66 ppm with respect to the total area of all of the peaks is the ratio of the integrated intensity due to specific straight-chain structures in the poly(meth)acrylate side chains with respect to the total integrated intensity of all of the carbon atoms, as measured by ¹³C-NMR.
M1/M2 is the ratio between specific β-branched structures and specific straight-chain structures in the poly(meth)acrylate side chains, but another method may be used so long as an equivalent effect is obtained. For ¹³C-NMR measurement, a dilution was used as the sample, obtained by adding 3 g of heavy chloroform to 0.5 g of test sample, and the measuring method was the gated decoupling method with a measuring temperature of room temperature and a resonance frequency of 125 MHz.
The following were measured based on these results:

(a) the total integrated intensity between a chemical shift of about 10-70 ppm (the total integrated intensity attributable to all carbons in the hydrocarbon), and
(b) the total integrated intensity between a chemical shift of 36-38 ppm (the total integrated intensity attributable to specific β-branched structures), and
(c) the total integrated intensity between a chemical shift of 64-66 ppm (the total integrated intensity attributable to specific straight-chain structures),

The poly(meth)acrylate-based viscosity index improvers to be used for this embodiment (where, "poly(meth)acrylate-based", according to the invention, collectively includes polyacrylate-based compounds and polymethacrylate-based compounds) is preferably a polymer of polymerizable monomers that include (meth)acrylate monomers represented by the following formula (1) (hereunder referred to as "monomer M-1").
[In formula (1), R¹ represents hydrogen or methyl and R² represents a C1-200 straight-chain or branched hydrocarbon group.]
The poly(meth)acrylate-based compound obtained by copolymerization of a homopolymer of one monomer represented by formula (1) or a copolymerization of two or more thereof is a "non-dispersed poly(meth)acrylate", but the poly(meth)acrylate-based compound of this embodiment may also be a "dispersed poly(meth)acrylate" in which a monomer represented by formula (1) is copolymerized with one or more monomers selected from among formulas (2) and (3) (hereunder referred to as "monomer M-2" and "monomer M-3", respectively).
[In formula (2), R³ represents hydrogen or methyl, R⁴ represents a C1-18 alkylene group, E¹ represents an amine residue or heterocyclic residue containing 1-2 nitrogen atoms and 0-2 oxygen atoms, and a is 0 or 1.]
[In formula (3), R⁵ represents hydrogen or methyl and E² represents an amine residue or heterocyclic residue containing 1-2 nitrogen atoms and 0-2 oxygen atoms.]
Specific examples of groups represented by E¹ and E² include dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoylamino, morpholino, pyrrolyl, pyrrolino, pyridyl, methylpyridyl, pyrrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino and pyrazino.
Specific preferred examples for monomer M-2 and monomer M-3 include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures of the foregoing.
There are no particular restrictions on the molar ratio of copolymerization in the copolymer of monomer M-1 and monomers M-2 and M-3, but preferably it is a ratio of approximately M-1:M-2-M-3 = 99:1-80:20, more preferably 98:2-85:15 and even more preferably 95:5-90:10.
Any production process may be employed for the poly(meth)acrylate of the third embodiment, and for example, it can be easily obtained by radical solution polymerization of a mixture of monomer (M-1) and monomers (M-2) and (M-3) in the presence of a polymerization initiator such as benzoyl peroxide.
The PSSI (Permanent Shear Stability Index) of the (A) viscosity index improver is preferably no greater than 40, more preferably no greater than 35, even more preferably no greater than 30 and most preferably no greater than 25. It is also preferably 0.1 or greater, more preferably 0.5 or greater, even more preferably 2 or greater and most preferably 5 or greater. If the PSSI is less than 0.1 the viscosity index improving effect may be reduced and cost increased, while if the PSSI is greater than 40 the shear stability or storage stability may be impaired.
The weight-average molecular weight (M_W) of the (A) viscosity index improver is preferably 100,000 or greater, more preferably 200,000 or greater, even more preferably 250,000 or greater and most preferably 300,000 or greater. It is also preferably no greater than 1,000,000, more preferably no greater than 700,000, even more preferably no greater than 600,000 and most preferably no greater than 500,000. If the weight-average molecular weight is less than 100,000, the effect of improving the viscosity-temperature characteristic and viscosity index will be minimal, potentially increasing cost, while if the weight-average molecular weight is greater than 1,000,000 the shear stability, solubility in the base oil and storage stability may be impaired.
The number-average molecular weight (M_N) of the (A) viscosity index improver is preferably 50,000 or greater, more preferably 800,000 or greater, even more preferably 100,000 or greater and most preferably 120,000 or greater. It is also preferably no greater than 500,000, more preferably no greater than 300,000, even more preferably no greater than 250,000 and most preferably no greater than 200,000. If the number-average molecular weight is less than 50,000, the effect of improving the viscosity-temperature characteristic and viscosity index will be minimal, potentially increasing cost, while if the weight-average molecular weight is greater than 500,000 the shear stability, solubility in the base oil and storage stability may be impaired.
The ratio of the weight-average molecular weight and PSSI of the (A) second viscosity index improver (M_W/PSSI) is preferably 1.0 × 10⁴ or greater, more preferably 1.5 × 10⁴ or greater, even more preferably 2.0 × 10⁴ or greater, yet more preferably 2.5 × 10⁴ or greater and most preferably 3.0 × 10⁴ or greater. If the M_W/PSSI ratio is less than 1.0 × 10⁴, the viscosity-temperature characteristic, i.e. the fuel efficiency, may be impaired.
The ratio between the weight-average molecular weight and number-average molecular weight of the (A) viscosity index improver (M_W/M_N) is preferably 0.5 or greater, more preferably 1.0 or greater, even more preferably 1.5 or greater, yet more preferably 2.0 or greater and most preferably 2.1 or greater. Also, M_W/M_N is preferably no greater than 6.0, more preferably no greater than 4.0, even more preferably no greater than 3.5 and most preferably no greater than 3.0. If M_W/M_N is less than 0.5 or greater than 6.0, the viscosity-temperature characteristic may be impaired, or in other words the fuel efficiency may be reduced.
The increase in the 40°C and 100°C kinematic viscosity of the (A) viscosity index improver (ΔKV40/ΔKV100) is preferably no greater than 4.0, more preferably no greater than 3.5, even more preferably no greater than 3.0, yet more preferably no greater than 2.5, and most preferably no greater than 2.3. Also, ΔKV40/ΔKV100 is preferably 0.5 or greater, more preferably 1.0 or greater, even more preferably 1.5 or greater and most preferably 2.0 or greater.
If ΔKV40/ΔKV100 is less than 0.5 the viscosity-increasing effect or solubility may be reduced and cost may be increased, while if it exceeds 4.0 the viscosity-temperature characteristic-improving effect or low-temperature viscosity characteristic may be inferior. ΔKV40 is the amount of increase in the 40°C kinematic viscosity when the viscosity index improver is added at 3.0% to YUBASE4 by SK Corp., and ΔKV100 is the amount of increase in the 100°C kinematic viscosity when the viscosity index improver is added at 3.0% to YUBASE4 by SK Corp.
The ratio of the 100°C and 150°C HTHS viscosities of the (A) viscosity index improver (ΔHTHS100/ΔHTHS150) is preferably no greater than 2.0, more preferably no greater than 1.7, even more preferably no greater than 1.6 and most preferably no greater than 1.55. Also, ΔHTHS100/ΔHTHS150 is preferably 0.5 or greater, more preferably 1.0 or greater, even more preferably 1.2 or greater and most preferably 1.4 or greater.
If it is less than 0.5 the viscosity-increasing effect or solubility may be reduced and cost may be increased, while if it exceeds 2.0 the viscosity-temperature characteristic-improving effect or low-temperature viscosity characteristic may be inferior.
ΔHTHS100 is the amount of increase in the 100°C HTHS viscosity when the viscosity index improver is added at 3.0% to YUBASE4 by SK Corp., and ΔHTHS150 is the amount of increase in the 150°C HTHS viscosity when the viscosity index improver is added at 3.0% to YUBASE4 by SK Corp. Also, ΔHTHS100/ΔHTHS150 is the ratio between the increase in the 100°C HTHS viscosity and the increase in the 150°C HTHS viscosity. The 100°C HTHS viscosity, according to the invention, is the high-temperature high-shear viscosity at 100°C according to ASTM D4683. The 150°C HTHS viscosity is the high-temperature high-shear viscosity at 150°C according to ASTM D4683.
The (A) viscosity index improver content of the lubricating oil composition of this embodiment is preferably 0.01-50% by mass, more preferably 0.5-40% by mass, even more preferably 1-30% by mass, yet more preferably 3-20% by mass and most preferably 5-10% by mass, based on the total mass of the lubricating oil composition. If the (A) viscosity index improver content is less than 0.1% by mass, the viscosity index improving effect or product viscosity reducing effect will be minimal, potentially preventing improvement in fuel efficiency. A content of greater than 50% by mass will drastically increase production cost while requiring reduced base oil viscosity, and can thus risk lowering the lubricating performance under severe lubrication conditions (high-temperature, high-shear conditions), as well as causing problems such as wear, seizing and fatigue fracture.
A viscosity index improver other than component (A) may also be used as a viscosity index improver in the lubricating oil composition of this embodiment. Specific examples include non-dispersed or dispersed ethylene-α-olefin copolymers or their hydrogenated forms, polyisobutylene or its hydrogenated forms, styrene-diene hydrogenated copolymers and polyalkylstyrenes.
The lubricating oil composition of this embodiment comprises (B) a friction modifier. This can increase the fuel efficiency performance compared to a composition not having such a construction. The (B) friction modifier may consist of one or more friction modifiers selected from among organic molybdenum compounds and ash-free friction modifiers.
As organic molybdenum compounds to be used for this embodiment there may be mentioned sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), complexes of molybdenum compounds (for example, molybdenum oxides such as molybdenum dioxide and molybdenum trioxide, molybdic acids such as orthomolybdic acid, paramolybdic acid and (poly)molybdic sulfide acid, molybdic acid salts such as metal salts or ammonium salts of these molybdic acids, molybdenum sulfides such as molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide and polymolybdenum sulfide, molybdic sulfide, metal salts or amine salts of molybdic sulfide, molybdenum halides such as molybdenum chloride, and the like), with sulfur-containing organic compounds (for example, alkyl (thio)xanthates, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbylthiuram disulfide, bis(di(thio)hydrocarbyl dithiophosphonate)disulfide, organic (poly)sulfides, sulfurized esters and the like), or other organic compounds, or complexes of sulfur-containing molybdenum compounds such as molybdenum sulfide and molybdic sulfide with alkenylsuccinic acid imides.
The organic molybdenum compound used may be an organic molybdenum compound containing no sulfur as a constituent element. As organic molybdenum compounds containing no sulfur as a constituent element there may be mentioned, specifically, molybdenum-amine complexes, molybdenum-succinic acid imide complexes, organic acid molybdenum salts, alcohol molybdenum salts and the like, among which molybdenum-amine complexes, organic acid molybdenum salts and alcohol molybdenum salts are preferred.
When an organic molybdenum compound is used in the lubricating oil composition of this embodiment, there are no particular restrictions on the content, but it is preferably 0.001% by mass or greater, more preferably 0.005% by mass or greater, even more preferably 0.01% by mass or greater and most preferably 0.03% by mass or greater, and also preferably no greater than 0.2% by mass, more preferably no greater than 0.1% by mass, even more preferably no greater than 0.08% by mass and most preferably no greater than 0.06% by mass, in terms of molybdenum element based on the total mass of the lubricating oil composition. If the content is less than 0.001% by mass the heat and oxidation stability of the lubricating oil composition will be insufficient, and in particular it may not be possible to maintain superior cleanability for prolonged periods. On the other hand, if the content is greater than 0.2% by mass the effect will not be commensurate with the increased amount, and the storage stability of the lubricating oil composition will tend to be reduced.
As ash-free friction modifiers there may be used any compounds that are commonly used as friction modifiers for lubricating oils, examples of which include C6-50 compounds comprising in the molecule one or more hetero elements selected from among oxygen atoms, nitrogen atoms and sulfur atoms. More specifically, these include ash-free friction modifiers, including amine compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic ethers, urea-based compounds and hydrazide-based compounds, having in the molecule at least one C6-30 alkyl group or alkenyl group, and particularly at least one C6-30 straight-chain alkyl, straight-chain alkenyl, branched alkyl or branched alkenyl group.
The ash-free friction modifier content in the lubricating oil composition of this embodiment is preferably 0.01% by mass or greater, more preferably 0.1% by mass or greater and even more preferably 0.3% by mass or greater, and preferably no greater than 3% by mass, more preferably no greater than 2% by mass and even more preferably no greater than 1% by mass, based on the total mass of the lubricating oil composition. If the ash-free friction modifier content is less than 0.01 % by mass the friction reducing effect by the addition will tend to be insufficient, while if it is greater than 3% by mass, the effects of the wear resistance additives may be inhibited, or the solubility of the additives may be reduced.
According to this embodiment, the (B) friction modifier is preferably a molybdenum-based friction modifier, more preferably a sulfur-containing organic molybdenum compound, and even more preferably molybdenum dithiocarbamate.
The lubricating oil composition of this embodiment comprises (C) an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate (hereunder referred to as "(C) first overbased metal salt"). This can increase the fuel efficiency performance compared to a composition not having such a construction.
The (C) first overbased metal salt used for this embodiment can be obtained by reacting an oil-soluble metal salt such as an oil-soluble alkaline earth metal sulfonate, alkaline earth metal salicylate, alkaline earth metal phenate or alkaline earth metal phosphonate, with an alkaline earth metal hydroxide or oxide, and with a boric acid or boric anhydride. The alkaline earth metal may be magnesium, calcium or barium, but is preferably calcium. The oil-soluble metal salt used is preferably an alkaline earth metal salicylate.
The base value of the (C) first overbased metal salt is preferably 50 mgKOH/g or greater, more preferably 100 mgKOH/g or greater, even more preferably 150 mgKOH/g or greater and most preferably 200 or greater. It is also preferably no greater than 500 mgKOH/g, more preferably no greater than 400 mgKOH/g and most preferably no greater than 300 mgKOH/g. The base value, for the purpose of the invention, is the value measured according to JIS K 2501 5.2.3.
Also, the particle size of the (C) first overbased metal salt is preferably no greater than 0.1 µm and more preferably no greater than 0.05 µm.
Any production process may be employed for the (C) first overbased metal salt, and for example, it may be obtained by reacting the aforementioned oil-soluble metal salt, alkaline earth metal hydroxide or oxide with boric acid or boric anhydride for 2-8 hours at 20-200°C in the presence of water, an alcohol such as methanol, ethanol, propanol or butanol and a diluting solvent such as benzene, toluene or xylene, and then heating the mixture at 100-200°C to remove the water and if necessary the alcohol and diluting solvent. The specific reaction conditions may be appropriately selected according to the amounts of starting materials and reactants. Details regarding the production process are described, for example, in Japanese Unexamined Patent Application Publication SHO No. 60-116688 and Japanese Unexamined Patent Application Publication SHO No. 61-204298 . Since the particle size of an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate, produced by the method described above, is usually no greater than 0.1 µm and the total base value is usually 100 mgKOH/g or greater, it is preferred for use in the lubricating oil composition of this embodiment.
The content of the (C) first overbased metal salt in the lubricating oil composition of this embodiment is preferably 0.01-30% by mass and more preferably 0.05-5% by mass, based on the total mass of the lubricating oil composition. If the content is not at least 0.01% by mass the fuel efficiency effect may only last a short period of time, and if it exceeds 30% by mass no further effect commensurate with the content may be obtained, and therefore neither extreme is preferred.
The lubricating oil composition of this embodiment also preferably comprises (E) an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal carbonate (hereunder referred to as "(E) second overbased metal salt"), in addition to the (C) first overbased metal salt. The (E) second overbased metal salt may be, for example, an overbased alkaline earth metal sulfonate obtained by overbasing an alkaline earth metal sulfonate with an alkaline earth metal carbonate, an overbased alkaline earth metal phenate obtained by overbasing an alkaline earth metal phenate with an alkaline earth metal carbonate, or an overbased alkaline earth metal salicylate obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal carbonate. The alkaline earth metal may be magnesium, calcium or barium, but is preferably calcium. Most preferably, there is used in combination therewith, among these, an overbased calcium salicylate obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal carbonate.
The base value of the (E) second overbased metal salt, when the (C) first overbased metal salt is used in combination with a (E) second overbased metal salt in the lubricating oil composition of this embodiment, is preferably 50 mgKOH/g or greater, more preferably 100 mgKOH/g or greater, even more preferably 150 mgKOH/g or greater and most preferably 200 mgKOWg or greater. It is also preferably no greater than 500 mgKOH/g, more preferably no greater than 400 mgKOH/g and most preferably no greater than 300 mgKOH/g.
The lubricating oil composition of this embodiment may further contain any additives commonly used in lubricating oils, for the purpose of enhancing performance. Examples of such additives include additives such as metal cleaning agents other than the aforementioned first and second overbased metal salts, non-ash powders, antioxidants, anti-wear agents (or extreme-pressure agents), corrosion inhibitors, rust-preventive agents, demulsifiers, metal inactivating agents and antifoaming agents.
The metal cleaning agents other than the aforementioned first and second overbased metal salts include normal salts or basic salts such as alkali metal/alkaline earth metal sulfonates, alkali metal/alkaline earth metal phenates and alkali metal/alkaline earth metal salicylates. Alkali metals include sodium and potassium and alkaline earth metals include magnesium, calcium and barium, with magnesium and calcium being preferred, and calcium being especially preferred.
As non-ash powders there may be used any non-ash powders used in lubricating oils, examples of which include mono- or bis-succinic acid imides with at least one C40-400 straight-chain or branched alkyl group or alkenyl group in the molecule, benzylamines with at least one C40-400 alkyl group or alkenyl group in the molecule, polyamines with at least one C40-400 alkyl group or alkenyl group in the molecule, and modified forms of the foregoing with boron compounds, carboxylic acids, phosphoric acids and the like. One or more selected from among any of the above may be added for use.
As anti-wear agents (or extreme-pressure agents) there may be used any anti-wear agents and extreme-pressure agents that are utilized in lubricating oils. For example, sulfur-based, phosphorus-based and sulfur/phosphorus-based extreme-pressure agents may be used, specific examples of which include zinc dialkyldithiophosphates (ZnDTP), phosphorous acid esters, thiophosphorous acid esters, dithiophosphorous acid esters, trithiophosphorous acid esters, phosphoric acid esters, thiophosphoric acid esters, dithiophosphoric acid esters and trithiophosphoric acid esters, as well as their amine salts, metal salts and their derivatives, dithiocarbamates, zinc dithiocarbamate, MoDTC, disulfides, polysulfides, olefin sulfides, sulfurized fats and oils, and the like. Sulfur-based extreme-pressure agents, and especially sulfurized fats and oils, are preferably added.
As antioxidants there may be mentioned phenol-based and amine-based ash-free antioxidants, and copper-based or molybdenum-based metal antioxidants. Specific examples include phenol-based ash-free antioxidants such as 4,4'-methylenebis(2,6-di-tert-butylphenol) and 4,4'-bis(2,6-di-tert-butylphenol), and amine-based ash-free antioxidants such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine and dialkyldiphenylamine.
Examples of corrosion inhibitors include benzotriazole-based, tolyltriazole-based, thiadiazole-based and imidazole-based compounds.
Examples of rust-preventive agents include petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenylsuccinic acid esters and polyhydric alcohol esters.
Examples of demulsifiers include polyalkylene glycol-based nonionic surfactants such as polyoxyethylenealkyl ethers, polyoxyethylenealkylphenyl ethers and polyoxyethylenealkylnaphthyl ethers.
Examples of metal inactivating agents include imidazolines, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazole and its derivatives, 1,3,4-thiadiazolepolysulfide, 1,3,4-thiadiazolyl-2,5-bisdialkyl dithiocarbamate, 2-(alkyldithio)benzimidazole and β-(o-carboxybenzylthio)propionitrile.
Examples of antifoaming agents include silicone oils, alkenylsuccinic acid derivatives, polyhydroxyaliphatic alcohols and long-chain fatty acid esters, methyl salicylate and o-hydroxybenzyl alcohols, which have 25°C kinematic viscosities of 1000-100,000 mm²/s.
When such additives are added to the lubricating oil composition of this embodiment, their contents are 0.01-10% by mass based on the total mass of the lubricating oil composition.
The 100°C kinematic viscosity of the lubricating oil composition of this embodiment is preferably 4-12 mm²/s, and it is preferably no greater than 9 mm²/s, more preferably no greater than 8 mm²/s, even more preferably no greater than 7.8 mm²/s and most preferably no greater than 7.6 mm²/s. The 100°C kinematic viscosity of the lubricating oil composition of this embodiment is preferably 5 mm²/s or greater, more preferably 6 mm²/s or greater, even more preferably 6.5 mm²/s or greater and most preferably 7 mm²/s or greater. The 100°C kinematic viscosity according to the invention is the 100°C kinematic viscosity measured according to ASTM D-445. If the 100°C kinematic viscosity is less than 4 mm²/s, insufficient lubricity may result, and if it is greater than 12 mm²/s it may not be possible to obtain the necessary low-temperature viscosity and sufficient fuel efficiency performance.
The 40°C kinematic viscosity of the lubricating oil composition of this embodiment is preferably 4-50 mm²/s, more preferably no greater than 40 mm²/s, even more preferably no greater than 35 mm²/s, yet more preferably no greater than 32 mm²/s and most preferably no greater than 30 mm²/s. The 40°C kinematic viscosity of the lubricating oil composition of this embodiment is preferably 10 mm²/s or greater, more preferably 20 mm²/s or greater, even more preferably 25 mm²/s or greater and most preferably 27 mm²/s or greater. The 40°C kinematic viscosity according to the invention is the kinematic viscosity at 40°C measured according to ASTM D-445. If the 40°C kinematic viscosity is less than 4 mm²/s, insufficient lubricity may result, and if it is greater than 50 mm²/s it may not be possible to obtain the necessary low-temperature viscosity and sufficient fuel efficiency performance.
The viscosity index of the lubricating oil composition of this embodiment is preferably in the range of 140-400, and it is preferably 190 or greater, more preferably 200 or greater, even more preferably 210 or greater and most preferably 220 or greater. If the viscosity index of the lubricating oil composition of this embodiment is less than 140 it may be difficult to maintain the 150°C HTHS viscosity while improving fuel efficiency, and it may also be difficult to lower the -35°C low-temperature viscosity. If the viscosity index of the lubricating oil composition of this embodiment is greater than 400 the evaporation property may be poor, and problems may occur due to solubility of the additives or lack of compatibility with the sealant material.
The 100°C HTHS viscosity of the lubricating oil composition of this embodiment is preferably no greater than 5.5 mPa·s, more preferably no greater than 5.0 mPa·s, even more preferably no greater than 4.8 mPa·s and most preferably no greater than 4.7 mPa·s. It is also preferably 3.0 mPa·s or greater, even more preferably 3.5 mPa·s or greater, yet more preferably 4.0 mPa·s or greater and most preferably 4.2 mPa·s or greater. The 100°C HTHS viscosity, according to the invention, is the high-temperature high-shear viscosity at 100°C according to ASTM D4683. If the 100°C HTHS viscosity is less than 3.0 mPa·s, insufficient lubricity may result, and if it is greater than 5.5 mPa·s it may not be possible to obtain the necessary low-temperature viscosity and sufficient fuel efficiency performance.
The 150°C HTHS viscosity of the lubricating oil composition of this embodiment is preferably no greater than 3.5 mPa·s, more preferably no greater than 3.0 mPa·s, even more preferably no greater than 2.8 mPa·s and most preferably no greater than 2.7 mPa·s. It is also preferably 2.0 mPa·s or greater, more preferably 2.3 mPa·s or greater, even more preferably 2.4 mPa·s or greater, yet more preferably 2.5 mPa·s or greater and most preferably 2.6 mPa·s or greater. The 150°C HTHS viscosity, according to the invention, is the high-temperature high-shear viscosity at 150°C according to ASTM D4683. If the 150°C HTHS viscosity is less than 2.0 mPa·s, insufficient lubricity may result, and if it is greater than 3.5 mPa·s it may not be possible to obtain the necessary low-temperature viscosity and sufficient fuel efficiency performance.
Also, the ratio of the 150°C HTHS viscosity and the 100°C HTHS viscosity of the lubricating oil composition of this embodiment (150°C HTHS viscosity/100°C HTHS viscosity) is preferably 0.50 or greater, more preferably 0.52 or greater, even more preferably 0.54, yet more preferably 0.55 or greater and most preferably 0.56 or greater. If the ratio is less than 0.50, it may not be possible to obtain the necessary low-temperature viscosity and sufficient fuel efficiency performance.
The lubricating oil composition of this embodiment has excellent fuel efficiency and lubricity, and is effective for improving fuel efficiency while maintaining a constant level for the 150°C HTHS viscosity, even without using a synthetic oil such as a poly-α-olefinic base oil or ester-based base oil or a low-viscosity mineral base oil, because it reduces the 40°C and 100°C kinematic viscosity and the 100°C HTHS viscosity of lubricating oils. The lubricating oil composition of this embodiment having such superior properties can be suitably employed as a fuel efficient engine oil, such as a fuel efficient gasoline engine oil or fuel efficient diesel engine oil.

Examples

The present invention will now be explained in greater detail based on examples and comparative examples, with the understanding that these examples are in no way limitative on the invention.

[Examples 1-5, Comparative Examples 1-3]

For Examples 1 to 5 and Comparative Examples 1 to 3 there were prepared lubricating oil compositions having the compositions shown in Table 2, using the base oils and additives listed below. The properties of base oils O-1, O-2 and O-3 are shown in Table 1.

(Base oils)

O-1 (Base oil 1): Mineral oil obtained by hydrotreatment/hydroisomerization of n-paraffin-containing oil
O-2 (Base oil 2): Mineral oil obtained by hydrotreatment/hydroisomerization of n-paraffin-containing oil
O-3 (Base oil 3): Hydrocracked mineral oil

(Additives)

A-1: Polymethacrylate (M1 = 1.45, M2 = 3.99, M1/M2 = 0.48, ΔKV40/ΔKV100 = 1.9, ΔHTHS100/ΔHTHS150 = 1.48, MW = 400,000, PSSI = 12, Mw/Mn = 3.1, Mw/PSSI = 33,333)
A-2: Polymethacrylate (M1 = 0.60, M2 = 0.95, M1/M2 = 0.64, ΔKV40/ΔKV100 = 2.2, ΔHTHS100/ΔHTHS150 = 1.51, MW = 400,000, PSSI = 20, Mw/Mn = 2.2, Mw/PSSI = 20,000)
a-1: Dispersed polymethacrylate (M1 = 0.46, M2 = 3.52, M1/M2 = 0.13, ΔKV40/ΔKV100 = 3.3, ΔHTHS100/ΔHTHS150 = 1.79, MW = 300,000, PSSI = 40, Mw/Mn = 4.0, Mw/PSSI = 7500)
B-1: MoDTC (Mo content = 10% by mass)
C-1: Overbased calcium borate salicylate obtained by overbasing calcium salicylate with calcium borate (base value: 190 mgKOH/g, Ca content = 6.8% by mass, B content = 2.7% by mass)
c-1: Overbased calcium salicylate (base value: 170 mgKOH/g, Ca content = 6.3%)
d-1: Imide-based succinate dispersing agent (Mw = 13,000)
e-1: ZnDTP (sec-type, P content = 6.2% by mass)
f-1: Other additives (antioxidants, anti-wear agents, pour point depressants, antifoaming agents, etc.).

[Table 1]

			Base oil 1	Base oil 2	Base oil 3
Density	(15°C)	g/cm³	0.820	0.825	0.8388
Kinematic viscosity	(40°C)	mm²/s	15.8	17.75	18.72
	(100°C)	mm²/s	3.854	4.073	4.092
Viscosity index			141	132	120
Flow point		°C	-22.5	-22.5	-22.5
Aniline point		°C	118.5	119.1	111.6
Iodine value			0.06	0.1	0.79
Sulfur content		ppm by mass	<1	<1	2
Nitrogen content		ppm by mass	<3	<3	<3
n-d-M analysis		% C_P	93.3	87.3	78
		% C_N	6.7	12.7	20.7
		% C_A	0	0	1.3
Chromatographic separation mass%		Saturated content	99.6	99.6	95.1
		Aromatic content	0.2	0.2	4.7
		Resin content	0.1	0.2	0.2
		Yield	99.9	100	100
Paraffin content based on saturated components		mass%	87.1		50.6
Naphthene content based on saturated components		mass%	12.9		49.4

[Evaluation of lubricating oil compositions]

Each of the lubricating oil compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was measured for 40°C or 100°C kinematic viscosity, viscosity index and 100°C or 150°C HTHS viscosity. The fuel efficiency was measured by measuring the engine friction. The physical property values and fuel efficiency were measured by the following evaluation methods. 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 D-4683
(4) Engine friction test: Using a 2 L engine, the average value for friction at different measuring points at oil temperatures of 60°C-100°C and rotational speeds of 500-1500 rpm was calculated, and the friction improvement rate was calculated with respect to Comparative Example 1 as the reference oil.

[Table 2]

		Units	Example 1	Example 2	Example 3	Example 4	Example 5	Comp Ex 1	Comp. Ex 2	Comp Ex 3
Base oil	Based on total
O-1	base oil	mass%		100
O-2	Base oil 1	mass%	100		100	100	100	100		100
O-3	Base oil 2	mass%							100
	Base oil 3
Additives	Based on total composition
A-1	Polymethacrylate	mass%					13
A-2	Polymethacrylate	mass%	13	153	13	13		14		13
a-1	Polymethacrylate	mass%							4.5
B-1	MoDTC	mass%	0.8	0.8	0.8	0.8	0.8	0.8	0.8
C-1	Overbased borate Ca salicylate	mass%	2.9	2.9	1.5	0.8	1.5			2.9
c-1	Overbased Ca salicylate	mass%			1.5	2.3	1.5	3.1	3.1
d-1	Succinic acid imide	mass%	5	5	5	5	5	5	5	5
e-1	ZnDTP	mass%	1.1	1.1	1.1	1.1	1.1	1.1	1.1	1.1
f-1	Other additives	mass%	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Evaluation results
Kinematic viscosity	40°C	mm²/s	30.3	29.0	30.4	30.6	29.6	31.9	40.8	29.8
Kinematic viscosity	100°C	mm²/s	7.5	7.5	7.5	7.5	7.4	7.9	8.8	7.4
Viscosity index			231	247	231	230	233	233	202	231
HTHS viscosity	100°C	mPa·s	4.6	4.5	4.6	4.6	4.8	4.7	53	4.5
	150°C	mPa·s	2.6	2.6	2.6	2.6	2.6	2.6	2.6	2.5
Motoring friction improvement rate		%	1.3	1.5	1.6	1.2	1.6	0.0	-1.7	-4.3

As shown in Table 2, the lubricating oil compositions of Examples 1-5, which employed polymethacrylates with specific structures and included added overbased metal salts obtained by overbasing oil-soluble metal salts with alkaline earth metal borates, exhibited high motoring friction improvement rates (friction reduction rates) and excellent fuel efficiency. In contrast, the lubricating oil composition of Comparative Example 1, which did not contain an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate, had an approximately the same 150°C HTHS viscosity but exhibited high motoring friction (a low improvement rate). The lubricating oil composition of Comparative Example 2, which did not contain an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate, and did not contain a polymethacrylate as specified in the present application, also had high motoring friction (a low improvement rate). The lubricating oil composition of Comparative Example 3, which did not contain a friction modifier, also had high motoring friction (a low improvement rate). The lubricating oil composition of the invention can lower the 100°C HTHS viscosity while maintaining high-temperature high-shear viscosity at 150°C, even without using a synthetic oil such as a poly-α-olefinic base oil or ester-based base oil, or a low-viscosity mineral base oil, and also exhibits notably superior fuel efficiency by addition of a friction modifier and a specific metal cleaning agent.

Claims

A lubricating oil composition comprising:
a lubricating base oil with a 100°C kinematic viscosity of 1-20 mm²/s,

a viscosity index improver having a ratio M1/M2 of 0.20 or greater, between the total area of the peaks between chemical shifts of 36-38 ppm M1 and the total area of the peaks between chemical shifts of 64-66 ppm M2, with respect to the total area of all of the peaks, in the spectrum obtained by ¹³C-NMR,

a friction modifier, and

an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate.
A lubricating oil composition according to claim 1, wherein the viscosity index improver is a poly(meth)acrylate-based viscosity index improver.
A lubricating oil composition according to claim 1 or 2, wherein the second viscosity index improver has a PSSI of no greater than 40 and a weight-average molecular weight/PSSI ratio of at least 1 × 10⁴.
A lubricating oil composition according to any one of claims 1 to 3, wherein the friction modifier is an organic molybdenum compound.
A lubricating oil composition according to any one of claims 1 to 4, wherein the overbased metal salt obtained by overbasing the oil-soluble metal salt with the alkaline earth metal borate is an alkaline earth metal salicylate obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal borate.