Patent Application
20100016195
The present invention relates to a lubricating base oil, a lubricating oil composition for an internal combustion engine and a lubricating oil composition for a power train device.
In the field of lubricating oils, additives have been added to lubricating base oils such as highly refined mineral oils to improve the properties such as the viscosity-temperature characteristic or heat and oxidation stability of the lubricating oils (for example, see Patent documents 1-8).
For example, lubricating oils used in internal combustion engines such as automobile engines require heat and oxidation stability that allows them to withstand harsh conditions for prolonged periods. In order to ensure heat and oxidation stability of conventional lubricating oil for internal combustion engines, it is common to use highly refined base oils such as hycracked mineral oils or high performance base oils such as synthetic oils, with addition of peroxide-decomposable sulfur-containing compounds such as zinc dithiophosphate (ZDTP), molybdenum dithiocarbaminate (MoDTC), or ashless antioxidants such as phenol-based or amine-based antioxidants to the base oils (for example, see Patent documents 1 and 4-6).
With the recent emphasis on environmental issues such as reduction in carbon dioxide gas emissions, reduced energy consumption (increased fuel efficiency) of automobiles, construction equipment, agricultural machinery and the like has become a matter of urgency, and it is highly desirable for drive transmission devices such as gearboxes and final reduction gear boxes to help contribute to reduced energy consumption. Increased fuel efficiency for power train devices can be achieved by methods that lower the viscosity of the lubricating oil to reduce stirring resistance and friction resistance against sliding surfaces. For example, gearboxes used as automobile automatic transmissions or continously variable transmissions comprise a torque converter, wet clutch, gear bearing mechanism, oil pump, overpressure control mechanism and the like, while manual transmissions and final reduction gear boxs include a gear bearing mechanism, and by reducing the viscosity of the lubricating oils used therein to lower stirring resistance and friction resistance, it is possible to improve power transmission efficiency and achieve fuel savings.
However, reducing the viscosity of the lubricating oil also results in lower lubricity (antiwear property, anti-seizing properties, fatigue life, etc.), which is disadvantageous for gearboxes and the like. Also, phosphorus-based extreme-pressure agents that are added to guarantee antiwear property and the like for lubricating oils with reduced viscosity can significantly shorten the fatigue life. Sulfur-containing extreme-pressure agents are effective for improving fatigue life, but it is generally known that the effect of the lubricating base oil viscosity in low viscosity lubricating base oils is greater than that of the additives.
One strategy for ensuring lubricity when lowering the viscosity of lubricating oils for increased fuel efficiency has been to optimize the combinations of phosphorus-based extreme-pressure agents and sulfur-containing extreme-pressure agents added to lubricating base oils (for example, see Patent documents 7 and 8).
With the ever increasing demand for improved properties of lubricating oils in recent years, the conventional lubricating base oils described in Patent documents 1-8 are often less than satisfactory in terms of viscosity-temperature characteristic and heat and oxidation stability. Moreover, only limited improvement in properties can be achieved by addition of additives to conventional lubricating base oils.
Particularly from the viewpoint of increasingly harsher conditions for use of lubricating oils for internal combustion engines, as well as effective utilization of resources, waste oil reduction and cost reduction for lubricating oil user, the demand for superior long drain properties of lubricating oils continues to increase, and even the conventional lubricating oils for internal combustion engines described above are in need of improvement to meet such demands. Specifically, investigation by the present inventors suggests that lubricating base oils used in conventional lubricating oils for internal combustion engines, although referred to as “high performance base oils”, are not always adequate in terms of their heat and oxidation stability. Also, while it is possible to improve the heat and oxidation stability to some extent by increasing the content of antioxidants, this method has been limited in its improving effect on heat and oxidation stability.
Moreover, even the aforementioned conventional lubricating oils for power train devices are in need of improvement in order to meet the ever increasing demands for greater fuel efficiency. Specifically, investigation by the present inventors suggests that lubricating base oils used in conventional lubricating oils for power train devices, although referred to as “high performance base oils”, are not always adequate in terms of their lubricity and viscosity-temperature characteristics, or their heat and oxidation stability. The methods for optimizing additive formulations such as described in Patent documents 1 and 2 have therefore been limited in their ability to reduce viscosity within a range that does not impair properties such as antiwear property, prevention of seizure and fatigue life. In addition, conventional lubricating oils have not been satisfactory in terms of shear stability, and prolonged use of lubricating oils containing such lubricating base oils often causes them to have reduced viscosity and impaired lubricity.
The present invention has been accomplished in light of these circumstances, and one of its objects is to provide a lubricating base oil that exhibits excellent viscosity-temperature characteristics and heat and oxidation stability while also allowing additives to exhibit a higher level of function when additives are included.
It is another object of the invention to provide a lubricating oil composition for an internal combustion engine that has excellent heat and oxidation stability and a sufficient long drain property.
It is yet another object of the invention to provide a lubricating oil composition that can exhibit high levels of antiwear property, prevention of seizure and fatigue life for prolonged periods even with reduced viscosity, and that can achieve both fuel efficiency and durability in power train devices.
In order to solve the problems described above, the invention provides a lubricating base oil characterized by comprising 90% by mass or greater saturated components, wherein the proportion of cyclic saturated components among the saturated components is 10-40% by mass (hereinafter referred to as “first lubricating base oil” for convenience).
The first lubricating base oil, which satisfies the condition for the saturated component content and the proportion of cyclic saturated components among the saturated components, exhibits excellence in terms of viscosity-temperature characteristic and heat and oxidation stability. When additives are included in the first lubricating base oil, it is possible to achieve a high level of function for the additives while maintaining sufficiently stable dissolution of the additives in the lubricating base oil.
In addition, the first lubricating base oil can reduce viscosity resistance and stirring resistance in a practical temperature range due to its superior viscosity-temperature characteristic, and when friction modifiers or the like are added their effects are maximally exhibited. Consequently, the first lubricating base oil is highly useful for reducing energy loss and achieving energy savings in devices in which the lubricating base oil is applied.
The invention further provides a lubricating base oil characterized by satisfying the condition represented by the following formula (1) (hereinafter referred to as “second lubricating base oil” for convenience).
1.440≦n20−0.002×kv100≦1.453 (1)
[wherein n20 represents the 20° C. refractive index of the lubricating base oil, and kv100 represents the kinematic viscosity at 100° C. (mm2/s) of the lubricating base oil.]
A second lubricating base oil satisfying the condition represented by formula (1) above will allow excellence in viscosity-temperature characteristic and heat and oxidation stability to be achieved, while additives added to the second lubricating base oil will be kept in a sufficiently stable dissolved state in the lubricating base oil with an even higher level of function of the additives being exhibited.
This effect of the second lubricating base oil is based on knowledge acquired by the present inventors, that the middle expression in formula (1) above (n20−0.002×kv100) represents a satisfactory correlation between the content of saturated components in the lubricating base oil and the proportion of cyclic saturated components among the saturated components, and that restricting the value to the range of 1.440-1.453 can improve the aforementioned properties of the lubricating base oil.
The invention still further provides a lubricating oil composition for an internal combustion engine characterized by comprising the aforementioned first or second lubricating base oil, an ashless antioxidant containing essentially no sulfur as a constituent element, and at least one compound selected from among ashless antioxidants containing sulfur as a constituent element and organic molybdenum compounds.
When the lubricating oil composition for an internal combustion engine according to the invention contains the first lubricating base oil, the saturated component content and the proportion of cyclic saturated components among the saturated components in the first lubricating oil satisfy the condition specified above, and therefore excellent heat and oxidation stability and resistance to volatilization are exhibited. When the lubricating base oil includes additives, it can exhibit a high level of function for the additives while maintaining stable dissolution of the additives. Moreover, by adding both an ashless antioxidant containing essentially no sulfur as a constituent element (hereinafter also referred to as “component (A)”) and at least one compound selected from among ashless antioxidants containing sulfur as a constituent element and organic molybdenum compounds (hereinafter also referred to as “component (B)”) to the lubricating base oil having such excellent properties, it is possible to maximize the effect of improved heat and oxidation stability by synergistic action of components (A) and (B). The lubricating oil composition for an internal combustion engine according to the invention therefore allows a sufficient long drain property to be achieved.
In addition, since the first lubricating base oil satisfies the condition for the saturated component content and the proportion of cyclic saturated components among the saturated components, it exhibits excellence in terms of viscosity-temperature characteristic and frictional properties. Moreover, the first lubricating base oil whose additives have excellent solubility and efficacy as described above permits a high level of friction reducing effect to be obtained when a friction modifier is added. Consequently, a lubricating oil composition for an internal combustion engine according to the invention containing such an excellent first lubricating base oil results in reduced energy loss due to friction resistance or stirring resistance at sliding sections, and can therefore provide adequate energy savings.
It has been difficult to achieve both improvement in the low temperature viscosity characteristic while ensuring resistance to volatilization when using conventional lubricating base oils, but the first lubricating base oil can achieve a satisfactory balance with high levels of both the low temperature viscosity characteristic and resistance to volatilization. The lubricating oil composition for an internal combustion engine according to the invention is also useful for improving the cold startability, in addition to the long drain property and energy savings for internal combustion engines.
When the lubricating oil composition for an internal combustion engine according to the invention contains the second lubricating base oil, the second lubricating base oil also exhibits excellent heat and oxidation stability, as well as an excellent viscosity-temperature characteristic (including the low temperature viscosity characteristic) and superior frictional properties and resistance to volatilization, and allows included additives to exhibit a high level of function while maintaining the additives in a stable dissolved state. Therefore, a lubricating oil composition for an internal combustion engine comprising the second lubricating base oil, an ashless antioxidant containing essentially no sulfur as a constituent element, and at least one compound selected from among ashless antioxidants containing sulfur as a constituent element and organic molybdenum compounds, likewise makes it possible to achieve improvement in the long drain property, energy savings and the cold startability.
The invention yet further provides a lubricating oil composition for a power train device characterized by comprising the aforementioned first or second lubricating base oil, a poly(meth)acrylate-based viscosity index improver and a phosphorus-containing compound.
When the lubricating oil composition for a power train device according to the invention contains the first lubricating base oil, the first lubricating base oil satisfies the aforementioned condition for the saturated component content and the proportion of cyclic saturated components among the saturated components, and therefore the viscosity-temperature characteristic, heat and oxidation stability and frictional properties are superior to those of conventional lubricating base oils of the same viscosity grade. When the first lubricating base oil includes additives, it can exhibit a high level of function for the additives while maintaining stable dissolution of the additives. Furthermore, by adding a poly(meth)acrylate-based viscosity index improver (hereinafter also referred to as “component (C)”) and a phosphorus-containing compound (hereinafter also referred to as “component (D)”) to the first lubricating base oil having such superior properties, their synergistic action can maximize the effects of improved antiwear property, frictional properties, prevention of seizure and fatigue life, as well as the effect of improved shear stability, even when the viscosity is reduced. The lubricating oil composition for a power train device according to the invention can therefore provide power train devices with both increased fuel efficiency and durability.
It has been difficult to achieve both improvement in the low temperature viscosity characteristic while ensuring resistance to volatilization when using conventional lubricating base oils, but the first lubricating base oil can achieve a satisfactory balance with high levels of both the low temperature viscosity characteristic and resistance to volatilization. A lubricating oil composition for a drive unit according to the invention is therefore useful not only for achieving both fuel savings and durability for power train devices, but also for improving the cold startability.
When the lubricating oil composition for a power train device according to the invention contains the second lubricating base oil, the second lubricating base oil also exhibits excellence in terms of the viscosity-temperature characteristic, heat and oxidation stability and frictional properties, and allows included additives to exhibit a high level of function while maintaining the additives in a stable dissolved state. Therefore, a lubricating oil composition for a power train device comprising the second lubricating base oil and the specified poly(meth)acrylate-based viscosity index improver and phosphorus-containing compound can likewise provide both fuel efficiency and durability for power train devices, while also improving the cold startability.
According to the invention there is provided a lubricating base oil that exhibits excellent viscosity-temperature characteristics and heat and oxidation stability while also allowing additives to exhibit a higher level of function when additives are included. The lubricating base oil of the invention is suitable for use in various lubricating oil fields, and is especially useful for reducing energy loss and achieving energy savings in devices in which the lubricating base oil is applied.
The invention further realizes a lubricating oil composition for an internal combustion engine with superior heat and oxidation stability, and also excellence in terms of viscosity-temperature characteristic, frictional properties and resistance to volatilization. Moreover, when the lubricating oil composition for an internal combustion engine according to the invention is applied to an internal combustion engine, it provides a long drain property and increases energy efficiency while also improving the cold startability.
The invention still further realizes a lubricating oil composition for a power train device that can exhibit high levels of antiwear property, prevention of seizure and fatigue life for prolonged periods even with reduced viscosity. By using a lubricating oil composition for a power train device according to the invention it is possible to achieve both fuel savings and durability for power train devices, while also improving the cold startability.
Preferred embodiments of the invention will now be described in detail.
The lubricating base oil of the invention is characterized by satisfying at least one of the following conditions (a) or (b). The lubricating base oil of the invention may satisfy only of the conditions (a) or (b), but more preferably it satisfies both conditions (a) and condition (b). That is, the lubricating base oil of the invention comprises both the first and second lubricating base oils, with the first lubricating base oil preferably satisfying condition (b) and the second lubricating base oil preferably satisfying condition (a).
The lubricating base oil of the invention is not particularly restricted so long as it satisfies at least one of the aforementioned conditions (a) or (b). Specifically, there may be mentioned purified paraffinic mineral oils obtained by subjecting a lube-oil distillate obtained by atmospheric distillation and/or vacuum distillation of crude oil to a single treatment or two or more treatments from among refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid cleaning or white clay treatment, or normal paraffinic base oils, isoparaffinic base oils and the like, which satisfy at least one of the aforementioned conditions (a) or (b). Any of these lubricating base oils may be used alone or in combinations of two or more.
As a preferred example for the lubricating base oil of the invention there may be mentioned a base oil obtained by using one of the base oils (1)-(8) mentioned below as the raw material and purifying this feedstock oil and/or the lube-oil distillate recovered from the feedstock oil by a prescribed refining process, and recovering the lube-oil distillate.
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, the order is not particularly restricted and may be selected as appropriate.
The lubricating base oil of the invention is most preferably one of the following base oils (9) or (10) obtained by the prescribed treatment of a base oil selected from among base oils (1)-(8) above or a lube-oil distillate recovered from the base oil.
In 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 support 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 support 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 following production process A may be mentioned as a preferred example of a production process for the lubricating base oil of the invention.
Specifically, production process A according to the invention comprises a first step of preparing a hydrocracking catalyst comprising a support having an percentage of NH3 desorption amount at 300-800° C. of not greater than 80% with respect to the total NH3 desorption amount, based on NH3 desorption temperature dependence evaluation, and at least one metal from among metals of Group VIa and at least one metal from among metals of Group VIII of the Periodic Table supported on the support, a second step of hydrocracking of a feedfeedstock oil comprising 50% by volume or greater slack wax in the presence of the hydrocracking catalyst, at a hydrogen partial pressure of 0.1-14 MPa, a mean reaction temperature of 230-430° C., an LHSV of 0.3-3.0 hr−1 and a hydrogen/oil ratio of 50-14,000 scf/b, a third step of distilling separation of the cracked product oil obtained in the second step to obtain a lube-oil distillate, and a fourth step of dewaxing treatment of the lube-oil distillate obtained in third step. Production process A will now be explained in detail.
(Feedfeedstock Oil)
For production process A, a feedfeedstock oil comprising 50% by volume or greater slack wax is used. The phrase “feedstock oil comprising 50% by volume or greater slack wax” according to the invention refers to either a feedstock oil composed entirely of slack wax, or a feedstock oil that is a blended oil of slack wax and another feedstock oil and comprises 50% by volume or greater slack wax.
Slack wax is the wax-containing component obtained as a by-product of the solvent dewaxing step during production of a lubricating base oil from a paraffinic lube-oil distillate, and according to the invention the term includes slack wax obtained by further subjecting the wax-containing component to deoiling treatment. The major components of slack wax are n-paraffins and branched paraffins with few side chains (isoparaffins), and it has low naphthene and aromatic contents. The kinematic viscosity of the slack wax used for preparation of the feedstock oil may be selected as appropriate for the kinematic viscosity desired for the lubricating base oil, but for production of a low-viscosity base oil as a lubricating base oil for the invention, a relatively low viscosity slack wax is preferred, with a kinematic viscosity at 100° C. of about 2-25 mm2/s, preferably about 2.5-20 mm2/s and more preferably about 3-15 mm2/s. The other properties of the slack wax may be as desired, although the melting point is preferably 35-80° C., more preferably 45-70° C. and even more preferably 50-60° C. The oil content of the slack wax is preferably not greater than 60% by mass, more preferably not greater than 50% by mass, even more preferably not greater than 25% by mass and most preferably not greater than 10% by mass, and preferably 0.5% by mass or greater and more preferably 1% by mass or greater. The sulfur content of the slack wax is preferably not greater than 1% by mass and more preferably not greater than 0.5% by mass, and preferably 0.001% by mass or greater.
The oil content of the thoroughly deoiled slack wax (hereinafter referred to as “slack wax A”) is preferably 0.5-10% by mass and more preferably 1-8% by mass. The sulfur content of slack wax A is preferably 0.001-0.2% by mass, more preferably 0.01-0.15% by mass and even more preferably 0.05-0.12% by mass. However, the oil content of slack wax that has either not been subjected to deoiling treatment or has been subjected only to insufficient deoiling treatment (hereinafter, “slack wax B”) is preferably 10-60% by mass, more preferably 12-50% by mass and even more preferably 15-25% by mass. The sulfur content of slack wax B is preferably 0.05-1% by mass, more preferably 0.1-0.5% by mass and even more preferably 0.15-0.25% by mass.
By using slack wax A as the starting material for production process A described above, it is possible to satisfactorily obtain a lubricating base oil of the invention satisfying at least one of the aforementioned condition (a) or (b). Also, production process A can yield a lubricating base oil with high added value, a high viscosity index and excellent low-temperature characteristics and heat and oxidation stability, even when an inexpensive slack wax B with a relatively high oil or sulfur content and relatively inferior quality is used as the starting material.
When the feedstock oil is a blended oil comprising slack wax and another feedstock oil, the feedstock oils are not particularly restricted so long as the proportion of slack wax in the total blended oil is 50% by volume or greater, but it is preferred to use a blended oil comprising a heavy atmospheric distilled oil and/or vacuum distilled oil obtained from crude oil.
When the feedstock oil is a blended oil comprising slack wax and another feedstock oil, the proportion of slack wax in the blended oil is more preferably 70% by volume or greater and even more preferably 75% by volume or greater from the viewpoint of production of a base oil with a high viscosity index. If the proportion is less than 50% by volume, the oil content including the aromatic and naphthene contents of the obtained lubricating base oil will be increased, thus tending to lower the viscosity index of the lubricating base oil.
On the other hand, in order to maintain a high viscosity index of the lubricating base oil, the heavy atmospheric distilled oil and/or vacuum distilled oil from the crude oil, used in combination with the slack wax, is preferably a fraction with a run-off of 60% or greater by volume in a distillation temperature range of 300-570° C.
(Hydrocracking Catalyst)
The hydrocracking catalyst used in production process A described above comprises at least one metal from among metals of Group VIa and at least one metal from among metals of Group VIII of the Periodic Table, supported on a support with the percentage of an NH3 desorption amount at 300-800° C. with respect to the total NH3 desorption amount, based on NH3 desorption temperature dependence evaluation, of not greater than 80%.
The “NH3 desorption temperature dependence evaluation” referred to here is the method described in the literature (Sawa M., Niwa M., Murakami Y., Zeolites 1990, 10, 532; Karge H. G., Dondur V., J. Phys. Chem. 1990, 94, 765 and elsewhere), and it is carried out as follows. First, the catalyst support is pretreated under a nitrogen stream for 30 minutes or longer at a temperature of 400° C. or higher to remove the adsorbed molecules, and then adsorption is carried out at 100° C. until the catalyst support is saturated by NH3. Next, the temperature of the catalyst support is raised to 100-800° C. at a temperature-elevating rate of than 10° C./min or less for NH3 desorption, and the NH3 separated by desorption is monitored at each prescribed temperature. The percentage of an NH3 desorption amount at 300-800° C. with respect to the total NH3 desorption amount (desorption amount at 100-800° C.) is then calculated.
The catalyst support used for production process A has the percentage of NH3 desorption amount at 300-800° C. of not greater than 80% with respect to the total NH3 desorption amount based on NH3 desorption temperature dependence evaluation, and it is preferably not greater than 70% and more preferably not greater than 60%. By using such a support to construct the hydrocracking catalyst, acidic substances that govern the cracking activity are sufficiently inhibited, so that it is possible to efficiently and reliably produce isoparaffins by decomposing isomerization of high-molecular-weight n-paraffins that derive from the slack wax in the feedstock oil by hydrocracking, and to satisfactorily inhibit excess cracking of the produced isoparaffin compounds. As a result, it is possible to obtain a sufficient amount of molecules with a high viscosity index having a suitably branched chemical structure, within a suitable molecular weight range.
As such supports there are preferred two-element oxides which are amorphous and acidic, and as examples there may be mentioned the two-element oxides cited in the literature (for example, “Metal Oxides and Their Catalytic Functions”, Shimizu, T., Kodansha, 1978).
Preferred among these are amorphous complex oxides that contain acidic two-element oxides obtained as complexes of two oxides of elements selected from among Al, B, Ba, Bi, Cd, Ga, La, Mg, Si, Ti, W, Y, Zn and Zr. The proportion of each oxide in such acidic two-element oxides can be adjusted to obtain an acidic support suitable for the purpose in the aforementioned NH3 adsorption/desorption evaluation. The acidic two-element oxide composing the support may be any one of the above, or a mixture of two or more thereof. The support may also be composed of the aforementioned acidic two-element oxide, or it may be a support obtained by binding the acidic two-element oxide with a binder.
The support is preferably one containing at least one acidic two-element oxide selected from among amorphous silica-alumina, amorphous silica-zirconia, amorphous silica-magnesia, amorphous silica-titania, amorphous silica-boria, amorphous alumina-zirconia, amorphous alumina-magnesia, amorphous alumina-titania, amorphous alumina-boria, amorphous zirconia-magnesia, amorphous zirconia-titania, amorphous zirconia-boria, amorphous magnesia-titania, amorphous magnesia-boria and amorphous titania-boria. The acidic two-element oxide composing the support may be any one of the above, or a mixture of two or more thereof. The support may also be composed of the aforementioned acidic two-element oxide, or it may be a support obtained by binding the acidic two-element oxide with a binder. The binder is not particularly restricted so long as it is one commonly used for catalyst preparation, but those selected from among silica, alumina, magnesia, titania, zirconia and clay, or mixtures thereof, are preferred.
For production process A, the hydrocracking catalyst has a structure wherein at least one metal of Group VIa of the Periodic Table (molybdenum, chromium, tungsten or the like) and at least one metal of Group VIII (nickel, cobalt, palladium, platinum or the like) are loaded on the aforementioned support. These metals have a hydrogenating function, and on the acidic support they complete a reaction which causes cracking or branching of the paraffin compounds, thus performing an important role for production of isoparaffins with a suitable molecular weight and branching structure.
As regards the loading amount of the metals in the hydrocracking catalyst, the loading amount of metals of Group VIa is preferably 5-30% by mass for each metal, and the loading amount of metals of Group VIII is preferably 0.2- 10% by mass for each metal.
The hydrocracking catalyst used for production process A more preferably comprises molybdenum in a range of 5-30% by mass as the one or more metals of Group VIa, and nickel in a range of 0.2-10% by mass as the one or more metals of Group VIII.
The hydrocracking catalyst composed of the support, at least one metal of Group VIa and at least one metal of Group VIII is preferably used in a sulfidized state for hydrocracking. The sulfidizing treatment may be carried out by a publicly known method.
(Hydrocracking Step)
For production process A, the feedstock oil containing 50% by volume or greater slack wax is hydrocracked in the presence of the hydrocracking catalyst, at a hydrogen partial pressure of 0.1-14 MPa, preferably 1-14 MPa and more preferably 2-7 MPa; a mean reaction temperature of 230-430° C., preferably 330-400° C. and more preferably 350-390° C.; an LHSV of 0.3-3.0 hr−1 and preferably 0.5-2.0 hr−1 and a hydrogen/oil ratio of 50-14,000 scf/b and preferably 100-5000 scf/b.
In the hydrocracking step, the n-paraffins derived from the slack wax in the feedstock oil are isomerized to isoparaffins during cracking, producing isoparaffin components with a low pour point and a high viscosity index, but it is possible to simultaneously decompose the aromatic compounds in the feedstock oil, which inhibit rise in the viscosity index, to monocyclic aromatic compounds, naphthene compounds and paraffin compounds, and to decompose the polycyclic naphthene compounds, which also inhibit rise in the viscosity index, to monocyclic naphthene compounds or paraffin compounds. From the viewpoint of increasing the viscosity index, it is preferred to minimize the high boiling point and low viscosity index compounds in the feedstock oil.
If the cracking rate as an evaluation of the extent of reaction is defined by the following formula:
(cracking rate (% by volume))=100−(proportion (% by volume) of fraction with boiling point of 360° C. or higher in product)
then the cracking rate is preferably 3-90% by volume. A cracking rate of less than 3% by volume is not preferred because it will result in insufficient production of isoparaffins by decomposing isomerization of high-molecular-weight n-paraffins with a high pour point in the feedstock oil and insufficient hydrocracking of the aromatic or polycyclic naphthene components with an inferior viscosity index, while a cracking rate of greater than 90% by volume is not preferred because it will reduce the lube-oil distillate yield.
(Distilling Separation Step)
The lube-oil distillate is then subjected to distilling separation from the cracked product oil obtained from the hydrocracking step described above. A fuel oil fraction is also sometimes obtained as the light fraction.
The fuel oil fraction is the fraction obtained as a result of thorough desulfurization and denitrification, and thorough hydrogenation of the aromatic components. The naphtha fraction with a high isoparaffin content, the kerosene fraction with a high smoke point and the gas oil fraction with a high cetane number are all high quality products suitable as fuel oils.
On the other hand, even with insufficient hydrocracking of the lube-oil distillate, a portion thereof may be supplied for repeat of the hydrocracking step. In order to obtain a lube-oil distillate with the desired kinematic viscosity, the lube-oil distillate may also be subjected to vacuum distillation. The vacuum distillation separation may be carried out after the dewaxing treatment described below.
In the evaporating separation step, the cracked product oil obtained from the hydrocracking step may be subjected to vacuum distillation to satisfactorily obtain a lubricating base oil such as 70 Pale, SAE10 or SAE20.
A system using a lower viscosity slack wax as the feedstock oil is suitable for producing an increased 70 Pale or SAE10 fraction, while a system using a high viscosity slack wax in the range mentioned above as the feedstock oil is suitable for obtaining more SAE20. Even with high viscosity slack wax, however, conditions for producing significant amounts of 70 Pale and SAE10 may be selected depending on the extent of the cracking reaction.
(Dewaxing Step)
The lube-oil distillate obtained by fractional distillation from the cracked product oil in the distilling separation step has a high pour point, and therefore dewaxing is carried out to obtain a lubricating base oil with the desired pour point. The dewaxing treatment may be carried out by an ordinary method such as a solvent dewaxing method or catalytic dewaxing method. Solvent dewaxing methods generally employ MEK and toluene mixed solvents, but solvents such as benzene, acetone or MIBK may also be used. In order to limit the pour point of the dewaxing oil to not higher than −10° C., such methods are preferably carried out under conditions with a solvent/oil ratio of 1-6 and a filtration temperature of −5 to −45° C. and preferably −10 to −40° C. The wax removed by filtration may be supplied again as slack wax to a hydrocracking step.
The production process described above may also include solvent refining treatment and/or hydrorefining treatment in addition to the dewaxing treatment. Such additional treatment is performed to improve the ultraviolet stability or oxidation stability of the lubricating base oil, and may be carried out by methods ordinarily used for lubricating oil refining steps.
The solvent used for solvent refining will usually be furfural, phenol, N-methylpyrrolidone or the like, in order to remove the small amounts of aromatic compounds and especially polycyclic aromatic compounds, remaining in the lube-oil distillate.
The hydrorefining is carried out for hydrogenation of the olefin compounds and aromatic compounds, and the catalyst therefor is not particularly restricted; there may be used alumina catalysts supporting at least one metal from among Group VIa metals such as molybdenum and at least one metal from among Group VIII metals such as cobalt and nickel, under conditions with a reaction pressure (hydrogen partial pressure) of 7-16 MPa, a mean reaction temperature of 300-390° C. and an LHSV of 0.5-4.0 hr−1.
The following production process B may be mentioned as another preferred example of a production process for the lubricating base oil of the invention.
Specifically, production process B according to the invention comprises a fifth step of hydrocracking and/or hydroisomerization of a feedstock oil containing paraffinic hydrocarbons in the presence of a catalyst, and a sixth step of dewaxing treatment of the product obtained from the fifth step or of the lube-oil distillate collected by distillation or the like from the product.
Production process B will now be explained in detail.
(Feedstock Oil)
For production process B there is used a feedstock oil containing paraffinic hydrocarbons. The term “paraffinic hydrocarbons” according to the invention refers to hydrocarbons with a paraffin molecule content of 70% by mass or greater. The number of carbons of the paraffinic hydrocarbons is not particularly restricted but will normally be about 10-100. The method for producing the paraffinic hydrocarbons is not particularly restricted, and various petroleum-based and synthetic paraffinic hydrocarbons may be used, but as especially preferred paraffinic hydrocarbons there may be mentioned synthetic waxes (Fischer-Tropsch wax (FT wax), GTL wax, etc.) obtained by gas-to-liquid (GTL) processes, among which FT wax is preferred. Synthetic wax is preferably wax composed mainly of normal paraffins with 15-80 and more preferably 20-50 carbon atoms.
The kinematic viscosity of the paraffinic hydrocarbons used for preparation of the feedstock oil may be appropriately selected according to the desired kinematic viscosity of the lubricating base oil, but for production of a low-viscosity base oil as a lubricating base oil of the invention, relatively low viscosity paraffinic hydrocarbons with a kinematic viscosity at 100° C. of about 2-25 mm2/s, preferably about 2.5-20 mm2/s and more preferably about 3-15 mm2/s, are preferred. The other properties of the paraffinic hydrocarbons may be as desired, but when the paraffinic hydrocarbons are synthetic wax such as FT wax, the melting point is preferably 35-80° C., more preferably 50-80° C. and even more preferably 60-80° C. The oil content of the synthetic wax is preferably not greater than 10% by mass, more preferably not greater than 5% by mass and even more preferably not greater than 2% by mass. The sulfur content of the synthetic wax is preferably not greater than 0.01% by mass, more preferably not greater than 0.001% by mass and even more preferably not greater than 0.0001% by mass.
When the feedstock oil is a blended oil comprising the aforementioned synthetic wax and another feedstock oil, the feedstock oils are not particularly restricted so long as the proportion of synthetic wax in the total blended oil is 50% by volume or greater, but it is preferred to use a blended oil comprising a heavy atmospheric distilled oil and/or vacuum distilled oil obtained from crude oil.
Also, when the feedstock oil is a blended oil comprising the aforementioned synthetic wax and another feedstock oil, the proportion of synthetic wax in the blended oil is more preferably at least 70% by volume and even more preferably at least 75% by volume from the viewpoint of production of a base oil with a high viscosity index. If the proportion is less than 70% by volume, the oil content including the aromatic and naphthene contents of the obtained lubricating base oil will be increased, thus tending to lower the viscosity index of the lubricating base oil.
On the other hand, in order to maintain a high viscosity index of the lubricating base oil, the heavy atmospheric distilled oil and/or vacuum distilled oil from the crude oil, used in combination with the synthetic wax, is preferably a fraction with a run-off of at least 60% by volume in a distillation temperature range of 300-570° C.
(Catalyst)
There are no particular restrictions on the catalyst used for production process B, but it is preferably a catalyst comprising at least one metal selected from metals of Group VIb and Group VIII of the Periodic Table as an active metal component supported on a support containing an aluminosilicate.
An aluminosilicate is a metal oxide composed of the three elements aluminum, silicon and oxygen. Other metal elements may also be included in ranges that do not interfere with the effect of the invention. In this case, the amount of other metal elements is preferably not greater than 5% by mass and more preferably not greater than 3% by mass of the total of alumina and silica in terms of their oxides. As examples of metal elements that may be included there may be mentioned titanium, lanthanum and manganese.
The crystallinity of the aluminosilicate can be estimated by the proportion of tetracoordinated aluminum atoms among the aluminum atoms, and this proportion can be measured by 27Al solid NMR. The aluminosilicate used for the invention has a tetracoordinated aluminum proportion of preferably at least 50% by mass, more preferably at least 70% by mass and even more preferably at least 80% by mass of the total aluminum. Aluminosilicates with tetracoordinated aluminum contents of greater than 50% by mass of the total aluminum are known as “crystalline aluminosilicates”.
Zeolite may be used as a crystalline aluminosilicate. As preferred examples there may be mentioned Y-zeolite, ultrastabilized Y-zeolite (USY zeolite), β-zeolite, mordenite and ZSM-5, among which USY zeolite is particularly preferred. According to the invention, one type of crystalline aluminosilicate may be used alone, or two or more may be used in combination.
The method of preparing the support containing the crystalline aluminosilicate may be a method in which a mixture of the crystalline aluminosilicate and binder is shaped and the shaped body is fired. There are no particular restrictions on the binder used, but alumina, silica, silica-alumina, titania and magnesia are preferred, and alumina is particularly preferred. There are also no particular restrictions on the proportion of binder used, but normally it will be preferably 5-99% by mass and more preferably 20-99% by mass based on the total amount of the shaped body. The firing temperature for the shaped body comprising the crystalline aluminosilicate and binder is preferably 430-470° C., more preferably 440-460° C. and even more preferably 445-455° C. The firing time is not particularly restricted but will normally be 1 minute to 24 hours, preferably 10 minutes to 20 hours and more preferably 30 minutes-10 hours. The firing may be carried out in an atmosphere of air, but is preferably carried out in an oxygen-free atmosphere such as a nitrogen atmosphere.
The Group VIb metal supported on the support may be chromium, molybdenum, tungsten or the like, and the Group VIII metal may be, specifically, cobalt, nickel, rhodium, palladium, iridium, platinum or the like. These metals may be used as single metals alone, or two or more thereof may be used in combination. For a combination of two or more metals, precious metals such as platinum and palladium may be combined, base metals such as nickel, cobalt, tungsten and molybdenum may be combined, or a precious metal and a base metal may be combined.
The metal may be loaded onto the support by impregnation of the support with a solution containing the metal, or by a usual method such as ion exchange. The loading amount of the metal may be selected as appropriate, but it will usually be 0.05-2% by mass and preferably 0.1-1% by mass based on the total amount of the catalyst.
(Hydrocracking/Hydroisomerization Step)
Production process B includes hydrocracking/hydroisomerization of a feedstock oil containing paraffinic hydrocarbons, in the presence of the aforementioned catalyst. The hydrocracking/hydroisomerization step may be carried out using a fixed bed reactor. The conditions for the hydrocracking/hydroisomerization are preferably, for example, a temperature of 250-400° C., a hydrogen pressure of 0.5-10 MPa and a feedstock oil liquid space velocity (LHSV) of 0.5-10 h−1.
(Distilling Separation Step)
The lube-oil distillate is then subjected to distilling separation from the cracked product oil obtained from the hydrocracking/hydroisomerization step described above. The distilling separation step in production process B is the same as the distilling separation step in production process A and will not be explained again here.
(Dewaxing Step)
The lube-oil distillate obtained by fractional distillation from the cracked product oil in the distilling separation step described above is then subjected to dewaxing. The dewaxing step may be carried out by a conventionally known dewaxing process such as solvent dewaxing or catalytic dewaxing. When the substances with a boiling point of 370° C. or lower in the cracking/isomerization product oil have not been separated from the high-boiling-point substances before dewaxing, the entire hydroisomerization product may be dewaxed, or the fraction with a boiling point of 370° C. or higher may be dewaxed, depending on the intended purpose of the cracking/isomerization product oil.
For solvent dewaxing, the hydroisomerization product is contacted with cold ketone and acetone and another solvent such as MEK or MIBK, and then cooled for precipitation of the high pour point substances as solid wax, and the precipitate separated from the solvent-containing lube-oil distillate (raffinate). The raffinate is then cooled with a scraped surface chiller for removal of the solid wax. Low molecular hydrocarbons such as propane can also be used for the dewaxing, in which case the cracking/isomerization product oil and low molecular hydrocarbons are mixed and at least a portion thereof is gasified to further cool the cracking/isomerization product oil and precipitate the wax. The wax is separated from the raffinate by filtration, membrane separation or centrifugal separation. The solvent is then removed from the raffinate and the raffinate is subjected to fractional distillation to obtain the target lubricating base oil.
In the case of catalytic dewaxing (catalyst dewaxing), the cracking/isomerization product oil is reacted with hydrogen in the presence of a suitable dewaxing catalyst under conditions effective for lowering the pour point. For catalytic dewaxing, some of the high-boiling-point substances in the cracking/isomerization product are converted to low-boiling-point substances, and then the low-boiling-point substances are separated from the heavier base oil fraction and the base oil fraction is subjected to fractional distillation to obtain two or more lubricating base oils. The low-boiling-point substances may be separated either before obtaining the target lubricating base oil or during the fractional distillation.
The dewaxing catalyst is not particularly restricted so long as it can lower the pour point of the cracking/isomerization product oil, and it is preferably one that yields the target lubricating base oil at high yield from the cracking/isomerization product oil. As such dewaxing catalysts there are preferred shape-selective molecular sieves, and specifically there may be mentioned ferrierite, mordenite, ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-22 (also known as Theta-1 or TON), silicoaluminophosphates (SAPO) and the like. These molecular sieves are preferably used in combination with catalyst metal components and more preferably in combination with precious metals. An example of a preferred combination is a complex of platinum and H-mordenite.
The dewaxing conditions are not particularly restricted, but the temperature is preferably 200-500° C. and the hydrogen pressure is preferably 10-200 bar (1 MPa-20 MPa). For a flow-through reactor, the H2 treatment speed is preferably 0.1-10 kg/l/hr and the LHSV is preferably 0.1-10−1 and more preferably 0.2-2.0 h-−1. The dewaxing is preferably carried out in such a manner that substances with initial boiling points of 350-400° C., normally present at not greater than 40% by mass and preferably not greater than 30% by mass in the cracking/isomerization product oil, are converted to substances with boiling points of below their initial boiling points.
Production process A and production process B were explained above as preferred production processes for lubricating base oils of the invention, but the production process for a lubricating base oil of the invention is not limited to those described. For example, in production process A, a synthetic wax such as FT wax or GTL wax may be used instead of slack wax. Also, a feedstock oil comprising slack wax (preferably slack wax A or B) may be used in production process B. In addition, production processes A and B may employ both slack wax (preferably slack wax A or B) and synthetic wax (preferably FT wax or GTL wax).
When the feedstock oil used for production of the lubricating base oil of the invention is a blended oil comprising the aforementioned slack wax and/or synthetic wax and a feedstock oil except for these waxes, the content of the slack wax and/or synthetic wax is preferably 50% by mass or greater based on the total amount of the feedstock oil.
For production of a lubricating base oil satisfying condition (a) above, the feedstock oil is preferably a feedstock oil comprising slack wax and/or synthetic wax wherein the oil content is 0-60% by mass and preferably 10-50% by mass; more preferably a feedstock oil comprising slack wax A and/or slack wax B wherein the oil content is 0.5-60% by mass and preferably 10-50; and most preferably a feedstock oil comprising slack wax B wherein the oil content is 5-60% by mass and preferably 10-50% by mass.
When the lubricating base oil of the invention satisfies condition (a) above, the saturated component content of the lubricating base oil is 90% by mass or greater as mentioned above, and it is preferably 95% by mass or greater, more preferably 96% by mass or greater and even more preferably 97% by mass or greater, based on the total amount of the lubricating base oil. The proportion of cyclic saturated components among the saturated components is 10-40% by mass as mentioned above, but it is preferably 10.5-30% by mass, more preferably 11-25% by mass and even more preferably 12-21% by mass. 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 achieve adequate levels for 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. In addition, a saturated component content and proportion of cyclic saturated components among the saturated components satisfying the aforementioned conditions can improve the frictional properties of the lubricating base oil itself, resulting in a greater friction reducing effect and thus increased energy savings.
If the saturated component content is less than 90% by mass, the viscosity-temperature characteristic, heat and oxidation stability and frictional properties will be inadequate. If the proportion of cyclic saturated components among the saturated components is less than 10% by mass, the solubility of the additives included in the lubricating base oil may be insufficient and the effective amount of additives kept dissolved in the lubricating base oil will be reduced, making it impossible to effectively achieve the function of the additives. If the proportion of cyclic saturated components among the saturated components is greater than 40% by mass, the efficacy of additives included in the lubricating base oil will be reduced. The saturated component content may be 100% by mass, but from the viewpoint of reducing production cost and improving the solubility of the additives, it is preferably not greater than 99.9% by mass, more preferably not greater than 99.5% by mass, even more preferably not greater than 99% by mass and most preferably not greater than 98.5% by mass.
When the lubricating base oil of the invention satisfies condition (a) above, a proportion of cyclic saturated components of 10-40% by mass among the saturated components is equivalent to an acyclic saturated component content of 60-90% by mass among the saturated components. The term “acyclic saturated components” includes both straight-chain paraffins and branched paraffins. There are no particular restrictions on the proportion of each paraffin component in the lubricating base oil of the invention, but the branched paraffin component content is preferably 55-99% by mass, more preferably 57.5-95% by mass, even more preferably 60-95% by mass, yet more preferably 70-90% by mass and most preferably 80-90% by mass based on the total amount of the lubricating base oil. If the proportion of branched paraffin components in the lubricating base oil satisfies the aforementioned conditions it will be possible to further 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 an even higher level.
The saturated component content for the purpose of the invention is the value measured according to ASTM D 2007-93 (units: % by mass).
The proportions of the cyclic saturated components and acyclic saturated components among the saturated components for the purpose of the invention are the naphthene portion (measurement of monocyclic-hexacyclic naphthenes, units: % by mass) and alkane portion (units: % by mass), respectively, both measured according to ASTM D 2786-91.
The straight-chain paraffin content of the lubricating base oil for the purpose of the invention is the value obtained by subjecting the saturated portion that has been separated and fractionated by the method described in ASTM D 2007-93 mentioned above, to gas chromatography under the conditions described below, in order to identify and quantify the straight-chain paraffins among the saturated components, and expressing the measured value with respect to the total amount of the lubricating base oil. For identification and quantitation, a C5-50 straight-chain paraffin mixture sample is used as the reference sample, and the straight-chain paraffin content among the saturated components is determined as the proportion of the total of the peak areas corresponding to each straight-chain paraffin, with respect to the total peak area of the chromatogram (subtracting the peak area for the diluent).
The proportion of branched paraffins in the lubricating base oil is the difference between the acyclic saturated component content among the saturated components and the straight-chain paraffin content among the saturated components, and it is a value expressed with respect to the total amount of the lubricating base oil.
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. As examples of other methods there may be mentioned 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.
When the lubricating base oil of the invention satisfies condition (b), n20−0.002×kv100 is 1.440-1.453 as mentioned above, but it is preferably 1.441-1.453, more preferably 1.443-1.452 and even more preferably 1.444-1.450. If n20−0.002×kv100 is within the range specified above it will be possible to achieve an excellent 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 an even higher level. An n20−0.002×kv100 value within the aforementioned range can also improve the frictional properties of the lubricating base oil itself, resulting in a greater friction reducing effect and thus increased energy savings.
If the n20−0.002×kv100 value exceeds the aforementioned upper limit, the viscosity-temperature characteristic, heat and oxidation stability and frictional properties will tend to be insufficient, and the efficacy of additives when added to the lubricating base oil will be reduced. If the n20−0.002×kv100 value is less than the aforementioned lower limit, the solubility of the additives included in the lubricating base oil will be insufficient and the effective amount of additives kept dissolved in the lubricating base oil will be reduced, making it impossible to effectively achieve the function of the additives.
The 20° C. refractive index (n20) for the purpose of the invention is the refractive index measured at 20° C. according to ASTM D1218-92. The kinematic viscosity at 100° C. (kv100) for the purpose of the invention is the kinematic viscosity measured at 100° C. according to JIS K 2283-1993.
The aromatic content of the lubricating base oil of the invention is not particularly restricted so long as the lubricating base oil satisfies at least one of conditions (a) and (b) above, but it is preferably not greater than 10% by mass, more preferably 0.1-5% by mass, even more preferably 0.2-4.5% by mass and most preferably 0.3-3% by mass based on the total amount 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 the invention 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 in this case 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.
The % CP of the lubricating base oil of the invention is not particularly restricted so long as the lubricating base oil satisfies at least one of conditions (a) and (b), but it is preferably 80 or greater, more preferably 82-99, even more preferably 85-95 and most preferably 87-93. If the % Cp 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 % Cp 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 % CN of the lubricating base oil of the invention is not particularly restricted so long as the lubricating base oil satisfies at least one of the aforementioned conditions (a) and (b), but it is preferably not greater than 19, more preferably 5-15, even more preferably 7-13 and most preferably 8-12. If the % CN 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 the % CN is less than the aforementioned lower limit, the additive solubility will tend to be lower.
The % CA of the lubricating base oil of the invention is not particularly restricted so long as the lubricating base oil satisfies at least one of conditions (a) and (b), but it is preferably not greater than 5, more preferably not greater than 2, even more preferably not greater than 1.5 and most preferably not greater than 1. If the % CA 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. The % CA value of the lubricating base oil of the invention may be zero, but the solubility of additives can be further increased with a % CA value of 0.1 or greater.
There are no particular restrictions on the ratio of % CP and % CN in the lubricating base oil of the invention so long as the lubricating base oil satisfies at least one of the aforementioned conditions (a) and (b), but % CP/% CN is preferably 5 or more, more preferably 6 or more and even more preferably 7 or more. If the % CP/% CN ratio 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. The % CP/% CN ratio is preferably not greater than 35, more preferably not greater than 20, even more preferably not greater than 14 and most preferably not greater than 13. The additive solubility can be further increased if the % CP/% CN ratio is not greater than the aforementioned upper limit.
The % CP, % CN and % CA 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 methods of ASTM D 3238-85 (n-d-M ring analysis). That is, the preferred ranges for % CP, % CN and % CA are based on the values determined by these methods, and for example, % CN may be a value exceeding 0 according to these methods even if the lubricating base oil contains no naphthene portion.
The sulfur content in the lubricating base oil of the invention 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. The lubricating base oil of the invention preferably has a sulfur content of not greater than 100 ppm by mass, more preferably not greater than 50 ppm by mass, even more preferably not greater than 10 ppm by mass and most preferably not greater than 5 ppm by mass, from the viewpoint of further improving the heat and oxidation stability and achieving low sulfurization.
From the viewpoint of cost reduction it is preferred to use a slack wax or the like as the starting material, in which case the sulfur content of the obtained lubricating base oil is preferably not greater than 50 ppm by mass and more preferably not greater than 10 ppm by mass. The sulfur content for the purpose of the invention is the sulfur content measured according to JIS K 2541-1996.
The nitrogen content in the lubricating base oil of the invention is not particularly restricted, but is preferably not greater than 5 ppm by mass, more preferably not greater than 3 ppm by mass and even more preferably not greater than 1 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 kinematic viscosity of the lubricating base oil of the invention is not particularly restricted so long as the lubricating base oil satisfies at least one of the aforementioned conditions (a) and (b), but the kinematic viscosity at 100° C. is preferably 1.5-20 mm2/s and more preferably 2.0-11 mm2/s. A kinematic viscosity at 100° C. of lower than 1.5 mm2/s for the lubricating base oil is not preferred from the standpoint of evaporation loss. If it is attempted to obtain a lubricating base oil having a kinematic viscosity at 100° C. of greater than 20 mm2/s, the yield will be reduced and it will be difficult to increase the cracking rate even when using a heavy wax as the starting material.
According to the invention, a lubricating base oil having a kinematic viscosity at 100° C. in one of the following ranges is preferably used after fractionation by distillation or the like.
The kinematic viscosity at 40° C. of the lubricating base oil of the invention is preferably 6.0-80 mm2/s and more preferably 8.0-50 mm2/s. According to the invention, a lube-oil distillate having a kinematic viscosity at 40° C. in one of the following ranges is preferably used after fractionation by distillation or the like.
By satisfying at least one of the aforementioned conditions (a) and (b), the aforementioned lubricating base oils (I) and (IV) can provide a superior low temperature viscosity characteristic and notably lower the viscosity resistance and stirring resistance compared to conventional lubricating base oils of the same viscosity grade. Moreover, by including a pour point depressant it is possible to lower the —BF viscosity at −40° C. to below 2000 mPa·s. The —BF viscosity at −40° C. is the viscosity measured according to JPI-5S-26-99.
Also, by satisfying at least one of the aforementioned conditions (a) and (b), the aforementioned lubricating base oils (II) and (V) can provide a superior low temperature viscosity characteristic and superior resistance to volatilization and lubricity, compared to conventional lubricating base oils of the same viscosity grade. For example, with lubricating base oils (II) and (V) it is possible to lower the −35° C. CCS viscosity to 3000 mPa·s or less.
Also, by satisfying at least one of the aforementioned conditions (a) and (b), the aforementioned lubricating base oils (III) and (VI) can provide a superior low temperature viscosity characteristic, as well as superior resistance to volatilization, heat and oxidation stability and lubricity, compared to conventional lubricating base oils of the same viscosity grade.
The viscosity index of the lubricating base oil of the invention will depend on the viscosity grade of the lubricating base oil, and for example, the viscosity index for the lubricating oils (I) and (IV) is preferably 105-130, more preferably 110-125 and even more preferably 120-125. The viscosity index for the lubricating base oils (II) and (V) is preferably 125-160, more preferably 130-150 and even more preferably 135-150. Also, the viscosity index for the lubricating base oils (III) and (VI) is preferably 135-180 and more preferably 140-160. If the viscosity index is less than the aforementioned lower limit, the viscosity-temperature characteristic, heat and oxidation stability and resistance to volatilization will tend to be reduced. 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 20° C. refractive index of the lubricating base oil of the invention will depend on the viscosity grade of the lubricating base oil, but the 20° C. refractive indexes of the lubricating base oils (I) and (IV) mentioned above is preferably 1.440-1.460, more preferably 1.442-1.458 and even more preferably 1.445-1.455. The 20° C. refractive index of the lubricating base oils (II) and (V) is preferably 1.450-1.465, more preferably 1.452-1.460 and even more preferably 1.453-1.458. The 20° C. refractive index of the lubricating base oils (III) and (VI) is preferably 1.455-1.468, more preferably 1.458-1.466 and even more preferably 1.459-1.465. If the refractive index exceeds the aforementioned upper limit, 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 pour point of the lubricating base oil of the invention 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 not higher than −10° C., more preferably not higher than −12.5° C. and even more preferably not higher than −15° C. The pour point for the lubricating base oils (II) and (V) is preferably not higher than −10° C., more preferably not higher than −15° C. and even more preferably not higher than −17.5° C. The pour point for the lubricating base oils (III) and (VI) is preferably not higher than −10° C., more preferably not higher than −12.5° C. and even more preferably not 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 −35° C. CCS viscosity of the lubricating base oil of the invention will depend on the viscosity grade of the lubricating base oil, and the −35° C. CCS viscosities of the lubricating base oils (I) and (IV) are preferably not greater than 1000 mPa·s. The −35° C. CCS viscosity for the lubricating base oils (II) and (V) is preferably not greater than 3000 mPa·s, more preferably not greater than 2400 mPa·s, even more preferably not greater than 2200 mPa·s and most preferably not greater than 2000 mPa·s. The −35° C. CCS viscosity for the lubricating base oils (III) and (VI) is preferably not greater than 15,000 mPa·s, more preferably not greater than 10,000 mPa·s and even more preferably not greater than 8000 mPa·s. If the −35° C. CCS viscosity 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 −35° C. CCS viscosity for the purpose of the invention is the viscosity measured according to JIS K 2010-1993.
The 15° C. density (ρ15, units: g/cm3) of the lubricating base oil of the invention will also depend on the viscosity grade of the lubricating base oil, but it is preferably not greater than the value of ρ as represented by the following formula (2), i.e., ρ15≦ρ.
ρ=0.0025×kv100+0.820 (2)
[In this equation, kv100 represents the kinematic viscosity at 100° C. (mm2/s) of the lubricating base oil.]
If ρ15>ρ, 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.
For example, the value of ρ15 for lubricating base oils (I) and (IV) is preferably not greater than 0.830 g/cm3, more preferably not greater than 0.825 g/cm3 and even more preferably not greater than 0.820 g/cm3. The value of ρ15 for lubricating base oils (II) and (V) is preferably not greater than 0.835 g/cm3 and more preferably not greater than 0.830 g/cm3. The value of ρ15 for lubricating base oils (III) and (VI) is preferably not greater than 0.840 g/cm3 and more preferably not greater than 0.835 g/cm3.
The 15° C. density for the purpose of the invention is the density measured at 15° C. according to JIS K 2249-1995.
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 (3), i.e., AP≧A.
A=4.1×kv100+97 (3)
[In this equation, kv100 represents the kinematic viscosity at 100° C. (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 value of AP for the lubricating base oils (I) and (IV) is preferably 108° C. or higher, more preferably 110° C. or higher and even more preferably 112° C. or higher. The value of AP for the lubricating base oils (II) and (V) is preferably 113° C. or higher, more preferably 116° C. or higher, even more preferably 118° C. or higher and most preferably 120° C. or higher. The value of AP for the lubricating base oils (III) and (VI) is preferably 125° C. or higher, more preferably 127° C. or higher and even 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 NOACK evaporation amount of the lubricating base oil of the invention is not particularly restricted, and for example, the NOACK evaporation amount for lubricating base oils (I) and (IV) it is preferably 20% by mass or greater, more preferably 25% by mass or greater and even more preferably 30 or greater, and preferably not greater than 50% by mass, more preferably not greater than 45% by mass and even more preferably not greater than 42% by mass. The NOACK evaporation amount for lubricating base oils (II) and (V) is preferably 6% by mass or greater, more preferably 8% by mass or greater and even more preferably 10% by mass or greater, and preferably not greater than 20% by mass, more preferably not greater than 16% by mass, even more preferably not greater than 15% by mass and most preferably not greater than 14% by mass. The NOACK evaporation amount for lubricating base oils (III) and (VI) is preferably 1% by mass or greater and more preferably 2% by mass or greater, and preferably not greater than 8% by mass, more preferably not greater than 6% by mass and even more preferably not greater than 4% by mass. If the NOACK evaporation amounts are below the aforementioned lower limits it will tend to be difficult to improve the low temperature viscosity characteristic. If the NOACK evaporation amounts are above the respective upper limits, the evaporation loss of the lubricating oils will be increased when they are used as lubricating oils for an internal combustion engine, and catalyst poisoning will be undesirably accelerated as a result. The NOACK evaporation amount for the purpose of the invention is the evaporation loss as measured according to ASTM D 5800-95.
The distillation properties of the lubricating base oil of the invention are preferably an initial boiling point (IBP) of 290-440° C. and a final boiling point (FBP) of 430-580° C. in gas chromatography distillation, and rectification of one or more fractions selected from among fractions in this distillation range can yield lubricating base oils (I)-(III) and (IV)-(VI) having the aforementioned preferred viscosity ranges.
For example, for the distillation properties of the lubricating base oils (I) and (IV), the initial boiling point (IBP) is preferably 260-360° C., more preferably 300-350° C. and even more preferably 310-350° C. The 10% distillation temperature (T10) is preferably 320-400° C., more preferably 340-390° C. and even more preferably 350-380° C. The 50% distillation temperature (T50) is preferably 350-430° C., more preferably 360-410° C. and even more preferably 370-400° C. The 90% distillation temperature (T90) is preferably 380-460° C., more preferably 390-450° C. and even more preferably 400-440° C. The final boiling point (FBP) is preferably 420-520° C., more preferably 430-500° C. and even more preferably 440-480° C. T90-T10 is preferably 50-100° C., more preferably 55-85° C. and even more preferably 60-70° C. FBP-IBP is preferably 100-250° C., more preferably 110-220° C. and even more preferably 120-200° C. T10-IBP is preferably 10-80° C., more preferably 15-60° C. and even more preferably 20-50° C. FBP-T90 is preferably 10-80° C., more preferably 15-70° C. and even more preferably 20-60° C.
For the distillation properties of the lubricating base oils (II) and (V), the initial boiling point (IBP) is preferably 300-380° C., more preferably 320-370° C. and even more preferably 330-360° C. The 10% distillation temperature (T10) is preferably 340-420° C., more preferably 350-410° C. and even more preferably 360-400° C. The 50% distillation temperature (T50) is preferably 380-460° C., more preferably 390-450° C. and even more preferably 400-460° C. The 90% distillation temperature (T90) is preferably 440-500° C., more preferably 450-490° C. and even more preferably 460-480° C. The final boiling point (FBP) is preferably 460-540° C., more preferably 470-530° C. and even more preferably 480-520° C. T90-T10 is preferably 50-100° C., more preferably 60-95° C. and even more preferably 80-90° C. FBP-IBP is preferably 100-250° C., more preferably 120-180° C. and even more preferably 130-160° C. T10-IBP is preferably 10-70° C., more preferably 15-60° C. and even more preferably 20-50° C. FBP-T90 is preferably 10-50° C., more preferably 20-40° C. and even more preferably 25-35° C.
For the distillation properties of the lubricating base oils (III) and (VI), the initial boiling point (IBP) is preferably 320-480° C., more preferably 350-460° C. and even more preferably 380-440° C. The 10% distillation temperature (T10) is preferably 420-500° C., more preferably 430-480° C. and even more preferably 440-460° C. The 50% distillation temperature (T50) is preferably 440-520° C., more preferably 450-510° C. and even more preferably 460-490° C. The 90% distillation temperature (T90) is preferably 470-550° C., more preferably 480-540° C. and even more preferably 490-520° C. The final boiling point (FBP) is preferably 500-580° C., more preferably 510-570° C. and even more preferably 520-560° C. T90-T10 is preferably 50-120° C., more preferably 55-100° C. and even more preferably 55-90° C. FBP-IBP is preferably 100-250° C., more preferably 110-220° C. and even more preferably 115-200° C. T10-IBP is preferably 10-100° C., more preferably 15-90° C. and even more preferably 20-50° C. FBP-T90 is preferably 10-50° C., more preferably 20-40° C. and even more preferably 25-35° C.
By setting IBP, T10, T50, T90, FBP, T90-T10, FBP-IBP, T10-IBP and FBP-T90 within the preferred ranges specified above for lubricating base oils (I)-(VI), it is possible to further improve the low temperature viscosity and further reduce the evaporation loss. If the distillation ranges for T90-T10, FBP-IBP, T10-IBP and FBP-T90 are too narrow, the lubricating base oil yield will be poor resulting in low economy.
The IBP, T10, T50, T90 and FBP values for the purpose of the invention are the running points measured according to ASTM D 2887-97.
The residual metal content in the lubricating base oil of the invention derives from metals in the catalyst or starting materials that have become unavoidable contaminants during the production process, and it is preferred to thoroughly remove such residual metal contents. For example, the Al, Mo and Ni contents are preferably not greater than 1 ppm by mass respectively. If the metal contents exceed the aforementioned upper limit, the functions of additives in the lubricating base oil will tend to be inhibited.
The residual metal content for the purpose of the invention is the metal content as measured according to JPI-5S-38-2003.
The lubricating base oil of the invention can exhibit excellent heat and oxidation stability if at least one of the aforementioned conditions (a) and (b) are satisfied, but it preferably also exhibits a RBOT life as described hereunder, according to its kinematic viscosity. For example, the RBOT life for the lubricating base oils (I) and (IV) is preferably 290 min or longer, more preferably 300 min or longer and even more preferably 310 min or longer. The RBOT life for the lubricating base oils (II) and (V) is preferably 350 min or longer, more preferably 360 min or longer and even more preferably 370 min or longer. Also, the RBOT life for the lubricating base oils (III) and (VI) is preferably 400 min or longer, more preferably 410 min or longer and even more preferably 420 min or longer. If the RBOT life of the lubricating base oil is less than the specified lower limit, the viscosity-temperature characteristic and heat and oxidation stability 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 RBOT life for the purpose of the invention is the RBOT value as measured according to JIS K 2514-1996, for a composition obtained by adding a phenol-based antioxidant (2,6-di-tert-butyl-p-cresol: DBPC) at 0.2% by mass to the lubricating base oil.
The lubricating base oil of the invention having the composition described above exhibits an excellent viscosity-temperature characteristic heat and oxidation stability, as well as improved frictional properties of the lubricating base oil itself, making it possible to achieve an increased friction reducing effect and thus improved energy savings. When additives are included in the lubricating base oil of the invention, the functions of the additives (improved heat and oxidation stability by antioxidants, increased friction reducing effect by friction modifiers, improved antiwear property by anti-wear agents, etc.) are exhibited at a higher level. The lubricating base oil of the invention can be applied as a base oil for a variety of lubricating oils. The specific use of the lubricating base oil of the invention may be as a lubricating oil for an internal combustion engine such as a passenger vehicle gasoline engine, two-wheel vehicle gasoline engine, diesel engine, gas engine, gas heat pump engine, ship engine, electric power engine or the like (lubricating oils for internal combustion engines), as a lubricating oil for a power train device such as an automatic transmission, manual transmission, continously variable transmission, final reduction gear box or the like (oil for power train device), as a hydraulic oil for a hydraulic power unit such as a damper, construction machine or the like, or as a compressor oil, turbine oil, industrial gear oil, refrigerator oil, rust preventing oil, heating medium oil, gas holder seal oil, bearing oil, paper machine oil, machine tool oil, sliding guide surface oil, electrical insulation oil, shaving oil, press oil, rolling oil, heat treatment oil or the like, and using the lubricating base oil of the invention for these purposes will allow the improved characteristics of the lubricating oil including the viscosity-temperature characteristic, heat and oxidation stability, energy savings and fuel efficiency to be exhibited at a high level, together with a longer lubricating oil life and lower levels of environmentally unfriendly substances.
When the lubricating base oil of the invention is used as the base oil for a lubricating oil, the lubricating base oil of the invention may be used alone or the lubricating base oil of the invention may be combined with one or more other base oils. When the lubricating base oil of the invention is combined with another base oil, the proportion of the lubricating base oil of the invention of 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 the invention, and as examples of mineral oil base oils there may be mentioned solvent refined mineral oils, hydrocracked mineral oils, hydrorefined mineral oils and solvent dewaxed base oils having kinematic viscosities at 100° C. of 1-100 mm2/s.
As synthetic base oils there may be mentioned poly-α-olefins and their hydrides; isobutene oligomers and their hydrides; 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-ethyl hexanoate, pentaerythritol pelargonate and the like), polyoxyalkylene glycols, dialkyldiphenyl ethers and polyphenyl ethers, 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 oligomer, decene oligomer, ethylene-propylene co-oligomers and the like), and their hydrides.
There are no particular restrictions on the process for producing poly-α-olefins, and as examples 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 additives included in the lubricating base oil of the invention are not particularly restricted, and any additives that are commonly employed in the field of lubricating oils may be used. As specific lubricating oil additives there may be mentioned antioxidants, ashless dispersants, metal-based detergents, extreme-pressure agents, anti-wear agents, viscosity index improvers, pour point depressants, friction modifiers, oil agents, corrosion inhibitors, rust-preventive agents, demulsifiers, metal inactivating agents, seal swelling agents, antifoaming agents, coloring agents, and the like. These additives may be used alone or in combinations of two or more.
(Lubricating Oil Composition for Internal Combustion Engine)
The lubricating oil composition for an internal combustion engine according to the invention comprises the aforementioned lubricating base oil of the invention, an ashless antioxidant containing essentially no sulfur as a constituent element, and at least one compound selected from among ashless antioxidants containing sulfur as a constituent element and organic molybdenum compounds.
The modes for the lubricating oil of the invention in the lubricating oil composition for an internal combustion engine according to the invention, and the process for its production, are as described above and will not be repeated here. The lubricating base oil of the invention may be used as a single type or a combination of two or more types.
The lubricating base oil of the invention may also be used in combination with one or more other base oils in the lubricating oil composition for an internal combustion engine according to the invention. As other base oils there may be used the mineral oil base oils and/or synthetic base oils mentioned as examples for the lubricating base oil of the invention. When the lubricating base oil of the invention is combined with another base oil, the proportion of the lubricating base oil of the invention in the total the mixed base oil is preferably 30% by mass or greater, more preferably 50% by mass or greater and even more preferably 70% by mass or greater.
The lubricating oil composition for an internal combustion engine according to the invention comprises, as component (A), an ashless antioxidant containing essentially no sulfur as a constituent element. Component (A) is preferably a phenol-based or amine-based ashless antioxidant containing no sulfur as a constituent element.
As specific examples of phenol-based ashless antioxidants containing no sulfur as a constituent element there may be mentioned 4,4′-methylenebis(2,6-di-tert-butylphenol), 4,4′-bis(2,6-di-tert-butylphenol), 4,4′-bis(2-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-nonylphenol), 2,2′-isobutylidenebis(4,6-dimethylphenol), 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4 (N,N′-dimethylaminomethylphenol), octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tridecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionate, and mixtures of the foregoing. Among these there are preferred hydroxyphenyl group-substituted esteric antioxidants that are esters of hydroxyphenyl group-substituted fatty acids and C4-12 alcohols ((octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionate and the like) and bisphenol-based antioxidants, with hydroxyphenyl group-substituted esteric antioxidants being more preferred. Phenol-based compounds with a molecular weight of 240 or greater are preferred for their high decomposition temperatures which allow them to exhibit their effects even under high-temperature conditions.
As specific amine-based ashless antioxidants containing no sulfur as a constituent element there may be mentioned phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, alkyldiphenylamine, dialkyldiphenylamine, N,N′-diphenyl-p-phenylenediamine, and mixtures of the foregoing. The alkyl groups in these amine-based ashless antioxidants are preferably C1-20 straight-chain or branched alkyl groups, and more preferably C4-12 straight-chain or branched alkyl groups.
There are no particular restrictions on the content of component (A) according to the invention, but it is preferably 0.01% by mass or greater, more preferably 0.1% by mass or greater, even more preferably 0.5% by mass or greater and most preferably 1.0% by mass or greater, and preferably not greater than 5% by mass, more preferably not greater than 3% by mass and most preferably not greater than 2% by mass, based on the total amount of the composition. If the content is less than 0.01% by mass the heat and oxidation stability of the lubricating oil composition will be insufficient, and it may not be possible to maintain superior cleanability for prolonged periods. On the other hand, a content of component (A) exceeding 5% by mass will tend to reduce the storage stability of the lubricating oil composition.
According the invention, a combination of 0.4-2% by mass of a phenol-based ashless antioxidant and 0.4-2% by mass of an amine-based ashless antioxidant, based on the total amount of the composition, may be used in combination as component (A), or as is most preferable, an amine-based antioxidant may be used alone at 0.5-2% by mass and even more preferably 0.6-1.5% by mass, which will allow excellent cleanability to be maintained for long periods.
The lubricating oil composition for an internal combustion engine according to the invention comprises, as component (B): (B-1) an ashless antioxidant containing sulfur as a constituent element and (B-2) an organic molybdenum compound.
As (B-1) the ashless antioxidant containing sulfur as a constituent element there may be suitably used sulfurized fats and oils, dihydrocarbyl polysulfide, dithiocarbamates, thiadiazoles and phenol-based ashless antioxidants containing sulfur as a constituent element.
As examples of sulfurized fats and oils there may be mentioned oils such as sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil and sulfurized rice bran oil; disulfide fatty acids such as oleic sulfide; and sulfurized esters such as sulfurized methyl oleate.
As examples of sulfurized olefins there may be mentioned compounds represented by the following general formula (4).
R11—Sx—R12 (4)
In general formula (4), R11 represents a C2-15 alkenyl group, R12 represents a C2-15 alkyl group or alkenyl group and x represents an integer of 1-8.
The compounds represented by general formula (4) above may be obtained by reacting a C2-15 olefin or its 2-4 mer with a sulfidizing agent such as sulfur or sulfur chloride. Examples of olefins that are preferred for use include propylene, isobutene and diisobutene.
Dihydrocarbyl polysulfides are compounds represented by the following general formula (5).
R13—Sy—R14 (5)
In general formula (5), R13 and R14 each separately represent a C1-20 alkyl group (including cycloalkyl groups), C6-20 aryl or C7-20 arylalkyl group, which may be the same or different, and y represents an integer of 2-8.
As specific examples for R13 and R14 there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyls, hexyls, heptyls, octyls, nonyls, decyls, dodecyls, cyclohexyl, phenyl, naphthyl, tolyl, xylyl, benzyl and phenethyl.
As specific preferred examples of dihydrocarbyl polysulfides there may be mentioned dibenzyl polysulfide, di-tert-nonyl polysulfide, didodecyl polysulfide, di-tert-butyl polysulfide, dioctyl polysulfide, diphenyl polysulfide and dicyclohexyl polysulfide.
As dithiocarbamates there may be mentioned, as preferred examples, compounds represented by the following general formula (6) or (7).
In general formulas (6) and (7), R15, R16, R17, R18, R19 and R20 each separately represent a C1-30 and preferably 1-20 hydrocarbon group, R21 represents hydrogen or a C1-30 hydrocarbon group and preferably hydrogen or a C1-20 hydrocarbon group, e represents an integer of 0-4, and f represents an integer of 0-6.
As examples of C1-30 hydrocarbon groups there may be mentioned alkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aryl, alkylaryl and arylalkyl groups.
As examples of thiadiazoles there may be mentioned 1,3,4-thiadiazole compounds represented by the following general formula (8), 1,2,4-thiadiazole compounds represented by general formula (9), and 1,4,5-thiadiazole compounds represented by general formula (10).
In general formulas (8)-(10), R22, R23, R24, R25, R26 and R27 may be the same or different and each separately represents hydrogen or a C1-30 hydrocarbon group, and g, h, i, j, k and l each separately represent an integer of 0-8.
As examples of C1-30 hydrocarbon groups there may be mentioned alkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aryl, alkylaryl and arylalkyl groups.
As phenol-based ashless antioxidants containing sulfur as a constituent element there may be mentioned 4,4′-thiobis(2-methyl-6-tert-butylphenol), 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 2,2′-thio-diethylenebis[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the like.
Dihydrocarbyl polysulfides, dithiocarbamates and thiadiazoles are preferably used as component (B-1) from the viewpoint of achieving more excellent heat and oxidation stability.
When (B-1) an ashless antioxidant containing sulfur as a constituent element is used as component (B) according to the invention, 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 and even more preferably 0.01% by mass or greater, and preferably not greater than 0.2% by mass, more preferably not greater than 0.1% by mass and most preferably not greater than 0.04% by mass, in terms of sulfur element based on the total amount of the composition. If the content is less than the aforementioned lower limit, the heat and oxidation stability of the lubricating oil composition will be insufficient, and it may not be possible to maintain superior cleanability for prolonged periods. On the other hand, if it exceeds the aforementioned upper limit the adverse effects on exhaust gas purification apparatuses by the high sulfur content of the lubricating oil composition will tend to be increased.
As the (B-2) organic molybdenum compound as component (B) there may be used (B-2-1) organic molybdenum compounds containing sulfur as a constituent element and (B-2-2) organic molybdenum compounds containing no sulfur as a constituent element.
As examples of (B-2-1) organic molybdenum compounds containing sulfur as a constituent element there may be mentioned organic molybdenum complexes such as molybdenum dithiophosphates and molybdenum dithiocarbamates.
As specific examples of molybdenum dithiophosphates there may be mentioned compounds represented by the following general formula (11).
In general formula (11), R28, R29, R30 and R31 may be the same or different and each represents a hydrocarbon group such as a C2-30, preferably C5-18 and more preferably C5-12 alkyl group or a C6-18 and preferably C10-15 (alkyl)aryl group. Y1, Y2, Y3 and Y4 each represent a sulfur atom or oxygen atom.
As preferred examples of alkyl groups there may be mentioned ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, which may be primary alkyl, secondary alkyl or tertiary alkyl groups, and either straight-chain or branched.
As preferred examples of (alkyl)aryl groups there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl, where the alkyl groups may be primary alkyl, secondary alkyl or tertiary alkyl groups, and either straight-chain or branched. These (alkyl)aryl groups include all substituted isomers with different substitution positions of the alkyl groups on the aryl groups.
Preferred examples of molybdenum dithiophosphates include, specifically, molybdenum sulfide-diethyl dithiophosphate, molybdenum sulfide-dipropyl dithiophosphate, molybdenum sulfide-dibutyl dithiophosphate, molybdenum sulfide-dipentyl dithiophosphate, molybdenum sulfide dihexyl dithiophosphate, molybdenum sulfide-dioctyl dithiophosphate, molybdenum sulfide-didecyl dithiophosphate, molybdenum sulfide-didodecyl dithiophosphate, molybdenum sulfide-di(butylphenyl)dithiophosphate, molybdenum sulfide-di(nonylphenyl)dithiophosphate, oxymolybdenum sulfide-diethyl dithiophosphate, oxymolybdenum sulfide-dipropyl dithiophosphate, oxymolybdenum sulfide-dibutyl dithiophosphate, oxymolybdenum sulfide-dipentyl dithiophosphate, oxymolybdenum sulfide-dihexyl dithiophosphate, oxymolybdenum sulfide-dioctyl dithiophosphate, oxymolybdenum sulfide-didecyl dithiophosphate, oxymolybdenum sulfide-didodecyl dithiophosphate, oxymolybdenum sulfide-di(butylphenyl)dithiophosphate, oxymolybdenum sulfide-di(nonylphenyl)dithiophosphate (where the alkyl groups may be straight-chain or branched, and the alkylphenyl groups may be bonded at any position of the alkyl groups), as well as mixtures of the foregoing. Also preferred as molybdenum dithiophosphates are compounds with different numbers of carbon atoms or structural hydrocarbon groups in the molecule.
As specific examples of molybdenum dithiocarbamates there may be used compounds represented by the following general formula (12).
In general formula (12), R32, R33, R34 and R35 may be the same or different and each represents a hydrocarbon group such as a C2-24 and preferably C4-13 alkyl group, or a C6-24 and preferably C10-15 (alkyl)aryl. Y5, Y6, Y7 and Y8 each represent a sulfur atom or oxygen atom.
As preferred examples of alkyl groups there may be mentioned ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, which may be primary alkyl, secondary alkyl or tertiary alkyl groups, and either straight-chain or branched.
As preferred examples of (alkyl)aryl groups there may be mentioned phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl, where the alkyl groups may be primary alkyl, secondary alkyl or tertiary alkyl groups, and either straight-chain or branched. These (alkyl)aryl groups include all substituted isomers with different substitution positions of the alkyl groups on the aryl groups. As molybdenum dithiocarbamates having structures other than those described above there may be mentioned compounds with structures in which dithiocarbamate groups are coordinated with thio- or polythio-trimeric molybdenum, as disclosed in WO98/26030 and WO99/31113.
Preferred examples of molybdenum dithiocarbamates include, specifically, molybdenum sulfide-diethyl dithiocarbamate, molybdenum sulfide-dipropyl dithiocarbamate, molybdenum sulfide-dibutyl dithiocarbamate, molybdenum sulfide-dipentyl dithiocarbamate, molybdenum sulfide-dihexyl dithiocarbamate, molybdenum sulfide-dioctyl dithiocarbamate, molybdenum sulfide-didecyl dithiocarbamate, molybdenum sulfide-didodecyl dithiocarbamate, molybdenum sulfide-di(butylphenyl)dithiocarbamate, molybdenum sulfide-di(nonylphenyl)dithiocarbamate, oxymolybdenum sulfide-diethyl dithiocarbamate, oxymolybdenum sulfide-dipropyl dithiocarbamate, oxymolybdenum sulfide-dibutyl dithiocarbamate, oxymolybdenum sulfide-dipentyl dithiocarbamate, oxymolybdenum sulfide-dihexyl dithiocarbamate, oxymolybdenum sulfide-dioctyl dithiocarbamate, oxymolybdenum sulfide-didecyl dithiocarbamate, oxymolybdenum sulfide-didodecyl dithiocarbamate, oxymolybdenum sulfide-di(butylphenyl)dithiocarbamate, oxymolybdenum sulfide-di(nonylphenyl)dithiocarbamate (where the alkyl groups may be straight-chain or branched and the alkylphenyl groups may be bonded at any position of the alkyl groups. Also preferred as molybdenum dithiocarbamates are compounds with different numbers of carbon atoms or structural hydrocarbon groups in the molecule.
As other sulfur-containing organic molybdenum complexes there may be mentioned 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, halogenated molybdenum compounds such as molybdenum chloride, and the like), with sulfur-containing organic compounds (for example, alkyl(thio)xanthate, thiadiazole, mercaptothiadiazole, thio carbonate, tetrahydrocarbylthiuram disulfide, bis(di(thio)hydrocarbyldithio phosphonate)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 alkenylsucciniimides.
Component (B) according to the invention is preferably the (B-2-1) organic molybdenum compound containing sulfur as a constituent element in order to obtain a friction reducing effect in addition to improving the heat and oxidation stability, with molybdenum dithiocarbamates being particularly preferred.
As the (B-2-2) organic molybdenum compounds containing no sulfur as a constituent element there may be mentioned, specifically, molybdenum-amine complexes, molybdenum-succiniimide 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.
As molybdenum compounds in the aforementioned molybdenum-amine complexes there may be mentioned sulfur-free molybdenum compounds such as molybdenum trioxide or its hydrate (MoO3.nH2O), molybdic acid (H2 MoO4), alkali metal salts of molybdic acid (M2MoO4; where M represents an alkali metal), ammonium molybdate ((NH4)2MoO4 or (NH4)6[Mo7O24].4H2O), MoCl5, MoOCl4, MoO2Cl2, MoO2Br2, Mo2O3Cl6 or the like. Of these molybdenum compounds, hexavalent molybdenum compounds are preferred from the viewpoint of yield of the molybdenum-amine complex. From the viewpoint of availability, the preferred hexavalent molybdenum compounds are molybdenum trioxide or its hydrate, molybdic acid, molybdic acid alkali metal salts and ammonium molybdate.
There are no particular restrictions on nitrogen compounds for the molybdenum-amine complex, but as specific nitrogen compounds there may be mentioned ammonia, monoamines, diamines, polyamines, and the like. As more specific examples there may be mentioned alkylamines with C1-30 alkyl groups (where the alkyl groups may be straight-chain or branched) such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, methylethylamine, methylpropylamine, methylbutylamine, ethylpropylamine, ethylbutylamine and propylbutylamine; alkenylamines with C2-30 alkenyl groups (where the alkenyl groups may be straight-chain or branched) such as ethenylamine, propenylamine, butenylamine, octenylamine and oleylamine; alkanolamines with C1-30 alkanol groups (where the alkanol groups may be straight-chain or branched) such as methanolamine, ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine, nonanolamine, methanolethanolamine, methanolpropanolamine, methanolbutanolamine, ethanolpropanolamine, ethanolbutanolamine and propanolbutanolamine; alkylenediamines with C1-30 alkylene groups such as methylenediamine, ethylenediamine, propylenediamine and butylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; compounds with C8-20 alkyl or alkenyl groups on the aforementioned monoamines, diamines or polyamines such as undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine, oleyldiethanolamine, oleylpropylenediamine and stearyltetraethylenepentamine; heterocyclic compounds such as N-hydroxyethyloleylimidazoline; alkylene oxide addition products of the foregoing, and mixtures of the foregoing. Primary amines, secondary amines and alkanolamines are preferred among those mentioned above.
The number of carbon atoms in the hydrocarbon group of the amine compound composing the molybdenum-amine complex is preferably 4 or greater, more preferably 4-30 and most preferably 8-18. If the hydrocarbon group of the amine compound has less than 4 carbon atoms, the solubility will tend to be poor. Limiting the number of carbon atoms in the amine compound to not greater than 30 will allow the molybdenum content in the molybdenum-amine complex to be relatively increased, so that the effect of the invention can be enhanced with a small amount of addition.
As molybdenum-succiniimide complexes there may be mentioned complexes of the sulfur-free molybdenum compounds mentioned above for the molybdenum-amine complexes, and succiniimides with C4 or greater alkyl or alkenyl groups. As succiniimides there may be mentioned succinimides having at least one C40-400 alkyl or alkenyl group in the molecule, or their derivatives, and preferably succinimides with C4-39 and more preferably C8-18 alkyl or alkenyl groups. If the number of carbon atoms of the alkyl or alkenyl group of the succinimide is less than 4, the solubility will tend to be impaired. Although a succinimide with an alkyl or alkenyl group having more than 30 and 400 or less carbon atoms may be used, the number of carbon atoms of the alkyl or alkenyl group is preferably not greater than 30 in order to obtain a relatively higher molybdenum content in the molybdenum-succinimide complex, and allow a greater effect according to the invention to be achieved with a smaller amount of addition.
As molybdenum salts of organic acids there may be mentioned salts of organic acids with molybdenum bases such as molybdenum oxides or molybdenum hydroxides, molybdenum carbonate or molybdenum chloride, mentioned above as examples for the molybdenum-amine complexes. As organic acids there are preferred the phosphorus compounds and carboxylic acids represented by the following general formula (P-1) or (P-2).
[In formula (P-1), R57 represents a C1-30 hydrocarbon group, R58 and R59 may be the same or different and each represents hydrogen or a C1-30 hydrocarbon group, and n represents 0 or 1.]
[In formula (P-2), R60, R61 and R62 may be the same or different and each represents hydrogen or a C1-30 hydrocarbon group, and n represents 0 or 1.]
The carboxylic acid in a molybdenum salt of a carboxylic acid may be either a monobasic acid or polybasic acid.
As monobasic acids there may be used C2-30 and preferably C4-24 fatty acids, which may be straight-chain or branched and saturated or unsaturated. As specific examples there may be mentioned saturated fatty acids such as acetic acid, propionic acid, straight-chain or branched butanoic acid, straight-chain or branched pentanoic acid, straight-chain or branched hexanoic acid, straight-chain or branched heptanoic acid, straight-chain or branched octanoic acid, straight-chain or branched nonanoic acid, straight-chain or branched decanoic acid, straight-chain or branched undecanoic acid, straight-chain or branched dodecanoic acid, straight-chain or branched tridecanoic acid, straight-chain or branched tetradecanoic acid, straight-chain or branched pentadecanoic acid, straight-chain or branched hexadecanoic acid, straight-chain or branched heptadecanoic acid, straight-chain or branched octadecanoic acid, straight-chain or branched hydroxyoctadecanoic acid, straight-chain or branched nonadecanoic acid, straight-chain or branched eicosanoic acid, straight-chain or branched heneicosanoic acid, straight-chain or branched docosanoic acid, straight-chain or branched tricosanoic acid and straight-chain or branched tetracosanoic acid, and unsaturated fatty acids such as acrylic acid, straight-chain or branched butenoic acid, straight-chain or branched pentenoic acid, straight-chain or branched hexenoic acid, straight-chain or branched heptenoic acid, straight-chain or branched octenoic acid, straight-chain or branched nonenoic acid, straight-chain or branched decenoic acid, straight-chain or branched undecenoic acid, straight-chain or branched dodecenoic acid, straight-chain or branched tridecenoic acid, straight-chain or branched tetradecenoic acid, straight-chain or branched pentadecenoic acid, straight-chain or branched hexadecenoic acid, straight-chain or branched heptadecenoic acid, straight-chain or branched octadecenoic acid, straight-chain or branched hydroxyoctadecenoic acid, straight-chain or branched nonadecenoic acid, straight-chain or branched eicosenoic acid, straight-chain or branched heneicosenoic acid, straight-chain or branched docosenoic acid, straight-chain or branched tricosenoic acid and straight-chain or branched tetracosenoic acid, as well as mixtures of the foregoing.
The monobasic acid may be a monocyclic or polycyclic carboxylic acid (optionally with hydroxyl groups) in addition to any of the aforementioned fatty acids, and the number of carbon atoms is preferably 4-30 and more preferably 7-30. As monocyclic or polycyclic carboxylic acids there may be mentioned aromatic carboxylic acids or cycloalkylcarboxylic acids with 0-3 and preferably 1-2 straight-chain or branched alkyl groups having 1-30 carbon atoms and preferably 1-20 carbon atoms, and more specifically, (alkyl)benzenecarboxylic acid, (alkyl)naphthalenecarboxylic acid, (alkyl)cycloalkylcarboxylic acid and the like. As preferred examples of monocyclic or polycyclic carboxylic acids there may be mentioned benzoic acid, salicylic acid, alkylbenzoic acid, alkylsalicylic acid, cyclohexanecarboxylic acid and the like.
As polybasic acids there may be mentioned dibasic acids, tribasic acids and tetrabasic acids. The polybasic acids may be straight-chain polybasic acids or cyclic polybasic acids. In the case of a linear polybasic acid, it may be straight-chain or branched and either saturated or unsaturated. As straight-chain polybasic acids there are preferred C2-16 straight-chain dibasic acids, and as specific examples there may be mentioned ethanedioic acid, propanedioic acid, straight-chain or branched butanedioic acid, straight-chain or branched pentanedioic acid, straight-chain or branched hexanedioic acid, straight-chain or branched heptanedioic acid, straight-chain or branched octanedioic acid, straight-chain or branched nonanedioic acid, straight-chain or branched decanedioic acid, straight-chain or branched undecanedioic acid, straight-chain or branched dodecanedioic acid, straight-chain or branched tridecanedioic acid, straight-chain or branched tetradecanedioic acid, straight-chain or branched heptadecanedioic acid, straight-chain or branched hexadecanedioic acid, straight-chain or branched hexenedioic acid, straight-chain or branched heptenedioic acid, straight-chain or branched octenedioic acid, straight-chain or branched nonenedioic acid, straight-chain or branched decenedioic acid, straight-chain or branched undecenedioic acid, straight-chain or branched dodecenedioic acid, straight-chain or branched tridecenedioic acid, straight-chain or branched tetradecenedioic acid, straight-chain or branched heptadecenedioic acid, straight-chain or branched hexadecenedioic acid, alkenylsuccinic acid, and mixtures of the foregoing. As cyclic polybasic acids there may be mentioned alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, aromatic tricarboxylic acids such as trimellitic acid and aromatic tetracarboxylic acids such as pyromellitic acid.
As molybdenum salts of alcohols there may be mentioned salts of alcohols with the sulfur-free molybdenum compounds mentioned above for the molybdenum-amine complexes, and the alcohols may be monohydric alcohols, polyhydric alcohols, polyhydric alcohol partial esters or partial ester compounds or hydroxyl group-containing nitrogen compounds (alkanolamines and the like). Molybdic acid is a strong acid and forms esters by reaction with alcohols, and esters of molybdic acid with alcohols are also included within the molybdenum salts of alcohols according to the invention.
As monohydric alcohols there may be used C1-24, preferably C1-12 and more preferably C1-8 monohydric alcohols, and such alcohols may be straight-chain or branched, and either saturated or unsaturated. As specific examples of C1-24 alcohols there may be mentioned methanol, ethanol, straight-chain or branched propanol, straight-chain or branched butanol, straight-chain or branched pentanol, straight-chain or branched hexanol, straight-chain or branched heptanol, straight-chain or branched octanol, straight-chain or branched nonanol, straight-chain or branched decanol, straight-chain or branched undecanol, straight-chain or branched dodecanol, straight-chain or branched tridecanol, straight-chain or branched tetradecanol, straight-chain or branched pentadecanol, straight-chain or branched hexadecanol, straight-chain or branched heptadecanol, straight-chain or branched octadecanol, straight-chain or branched nonadecanol, straight-chain or branched eicosanol, straight-chain or branched heneicosanol, straight-chain or branched tricosanol, straight-chain or branched tetracosanol, and mixtures of the foregoing.
As polyhydric alcohols there may be used polyhydric alcohols with 2-10 hydroxy groups and preferably polyhydric alcohols with C2-6 hydroxy groups. As specific examples of polyhydric alcohols with 2-10 hydroxy groups there may be mentioned dihydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycols (3-15 mers of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycols (3-15 mers of propylene glycol), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol and neopentyl glycol; polyhydric alcohols such as glycerin, polyglycerins (2-8 mers of glycerin such as diglycerin, triglycerin and tetraglycerin), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their 2-8 mers, pentaerythritols and their 2-4 mers, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol-glycerin condensation product, adonitol, arabitol, xylitol and mannitol; saccharides such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose and sucrose, and mixtures of the foregoing.
As partial esters of polyhydric alcohols there may be mentioned the polyhydric alcohols mentioned above as polyhydric alcohols having some of the hydroxyl groups hydrocarbylesterified, among which glycerin monooleate, glycerin dioleate, sorbitan monooleate, sorbitan dioleate, pentaerythritol monooleate, polyethyleneglycol monooleate and polyglycerin monooleate are preferred.
As partial ethers of polyhydric alcohols there may be mentioned the polyhydric alcohols mentioned above as polyhydric alcohols having some of the hydroxyl groups hydrocarbyletherified, and compounds having ether bonds formed by condensation between polyhydric alcohols (sorbitan condensation products and the like), among which 3-octadecyloxy-1,2-propanediol, 3-octadecenyloxy-1,2-propanediol, polyethyleneglycol alkyl ethers are preferred.
As hydroxyl group-containing nitrogen compounds there may be mentioned the examples of alkanolamines for the molybdenum-amine complexes referred to above, as well as alkanolamides wherein the amino groups on the alkanols are amidated (diethanolamide and the like), among which stearyldiethanolamine, polyethyleneglycolstearylamine, polyethyleneglycoldioleylamine, hydroxyethyllaurylamine, diethanolamide oleate and the like are preferred.
When a (B-2-2) organic molybdenum compound containing sulfur as a constituent element is used as component (B) according to the invention it is possible to increase the high-temperature cleanability and base number retention rate of the lubricating oil composition, and this is preferred for maintaining the initial friction reducing effect for longer periods, while molybdenum-amine complexes are especially preferred among such compounds.
The (B-2-1) organic molybdenum compound containing sulfur as a constituent element and (B-2-2) organic molybdenum compound containing no sulfur as a constituent element may also be used in combination for the invention.
When (B-2) an organic molybdenum compound is used as component (B) according to the invention, 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 and even more preferably 0.01% by mass or greater, and preferably not greater than 0.2% by mass, more preferably not greater than 0.1% by mass and most preferably not greater than 0.04% by mass, in terms of molybdenum element based on the total amount of the 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 it may not be possible to maintain superior cleanability for prolonged periods. On the other hand, if the content of component (B-1) 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.
The lubricating oil composition for an internal combustion engine according to the invention may consist entirely of the lubricating base oil and components (A) and (B) described above, but it may further contain the additives described below as necessary for further enhancement of function.
The lubricating oil composition for an internal combustion engine according to the invention preferably also further contains an anti-wear agent from the viewpoint of greater enhancement of the antiwear property. As extreme-pressure agents there are preferably used phosphorus-based extreme-pressure agents and phosphorus/sulfur-containing extreme-pressure agents.
As phosphorus-based extreme-pressure agents there may be mentioned phosphoric acid, phosphorous acid, phosphoric acid esters (including phosphoric acid monoesters, phosphoric acid diesters and phosphoric acid triesters), phosphorous acid esters (including phosphorous acid monoesters, phosphorous acid diesters and phosphorous acid triesters), and salts of the foregoing (such as amine salts or metal salts). As phosphoric acid esters and phosphorous acid esters there may generally be used those with 2-30 carbon atoms and preferably 3-20 carbon atoms hydrocarbon groups.
As phosphorus/sulfur-containing extreme-pressure agents there may be mentioned thiophosphoric acid, thiophosphorous acid, thiophosphoric acid esters (including thiophosphoric acid monoesters, thiophosphoric acid diesters and thiophosphoric acid triesters), thiophosphorous acid esters (including thiophosphorous acid monoesters, thiophosphorous acid diesters and thiophosphorous acid triesters), salts of the foregoing, and zinc dithiophosphate. As thiophosphoric acid esters and thiophosphorous acid esters there may generally be used those with C2-30 and preferably C3-20 hydrocarbon groups.
There are no particular restrictions on the extreme-pressure agent content, but it is preferably 0.01-5% by mass and more preferably 0.1-3% by mass based on the total amount of the composition.
Among the extreme-pressure agents mentioned above, zinc dithiophosphates are especially preferred for the lubricating oil composition for an internal combustion engine according to the invention. As examples of zinc dithiophosphates there may be mentioned compounds represented by the following general formula (13).
R36, R37, R38 and R39 in general formula (13) each separately represent a C1-24 hydrocarbon group. The hydrocarbon groups are preferably C1-24 straight-chain or branched alkyl, C3-24 straight-chain or branched alkenyl, C5-13 cycloalkyl or straight-chain or branched alkylcycloalkyl, C6-18 aryl or straight-chain or branched alkylaryl, and C7-19 arylalkyl groups. The alkyl groups or alkenyl groups may be primary, secondary or tertiary.
Specific examples for R36, R37, R38 and R39 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl and tetracosyl; alkenyl groups such as propenyl, isopropenyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl (such as oleyl), nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl and tetracosenyl; cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; alkylcycloalkyl groups such as methylcyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, ethylmethylcyclopentyl, trimethylcyclopentyl, diethylcyclopentyl, ethyldimethylcyclopentyl, propylmethylcyclopentyl, propylethylcyclopentyl, dipropylcyclopentyl, propylethylmethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, ethylmethylcyclohexyl, trimethylcyclohexyl, diethylcyclohexyl, ethyldimethylcyclohexyl, propylmethylcyclohexyl, propylethylcyclohexyl, di-propylcyclohexyl, propylethylmethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, ethylcycloheptyl, propylcycloheptyl, ethylmethylcycloheptyl, trimethylcycloheptyl, diethylcycloheptyl, ethyldimethylcycloheptyl, propylmethylcycloheptyl, propylethylcycloheptyl, di-propylcycloheptyl and propylethylmethylcycloheptyl; aryl groups such as phenyl and naphthyl; alkylaryl groups such as tolyl, xylyl, ethylphenyl, propylphenyl, ethylmethylphenyl, trimethylphenyl, butylphenyl, propylmethylphenyl, diethylphenyl, ethyldimethylphenyl, tetramethylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl; and arylalkyl groups such as benzyl, methylbenzyl, dimethylbenzyl, phenethyl, methylphenethyl and dimethylphenethyl. The aforementioned hydrocarbon groups include all possible straight-chain and branched structures, and the positions of the double bonds of the alkenyl groups, the bonding positions of the alkyl groups on the cycloalkyl groups, the bonding positions of the alkyl groups on the aryl groups and the bonding positions of the aryl groups on the alkyl groups may be as desired.
As specific preferred examples of zinc dithiophosphates there may be mentioned zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-sec-butyldithiophosphate, zinc di-sec-pentyldithiophosphate, zinc di-n-hexyldithiophosphate, zinc di-sec-hexyldithiophosphate, zinc di-octyldithiophosphate, zinc di-2-ethylhexyldithiophosphate, zinc di-n-decyldithiophosphate, zinc di-n-dodecyldithiophosphate, zinc diisotridecyldithiophosphate, and any desired combinations of the foregoing.
The process for production of the zinc dithiophosphate is not particularly restricted, and it may be produced by any desired conventional method. Specifically, it may be synthesized, for example, by reacting an alcohol or phenol containing hydrocarbon groups corresponding to R36, R37, R38 and R39 in formula (13) above with diphosphorus pentasulfide to produce a dithiophosphoric acid, and neutralizing it with zinc oxide. The structure of the zinc dithiophosphate will differ depending on the starting alcohol used.
The content of the zinc dithiophosphate is not particularly restricted, but from the viewpoint of inhibiting catalyst poisoning of the exhaust gas purification device, it is preferably not greater than 0.2% by mass, more preferably not greater than 0.1% by mass, even more preferably not greater than 0.08% by mass and most preferably not greater than 0.06% by mass as phosphorus element based on the total amount of the composition. From the viewpoint of forming a metal salt of phosphoric acid that will exhibit a function and effect as an anti-wear additive, the content of the zinc dithiophosphate is preferably 0.01% by mass or greater, more preferably 0.02% by mass or greater and even more preferably 0.04% by mass or greater as phosphorus element based on the total amount of the composition. If the zinc dithiophosphate content is less than the aforementioned lower limit, the antiwear property improving effect of its addition will tend to be insufficient.
The lubricating oil composition for an internal combustion engine according to the invention preferably further contains an ashless dispersant from the viewpoint of cleanability and sludge dispersibility. As such ashless dispersants there may be mentioned alkenylsuccinimides and alkylsuccinimides derived from polyolefins, and their derivatives. A typical succinimide can be obtained by reacting succinic anhydride substituted with a high molecular weight alkenyl group or alkyl group, with a polyalkylenepolyamine containing an average of 4-10 (and preferably 5-7) nitrogen atoms per a molecule. The high molecular weight alkenyl group or alkyl group is preferably polybutene (polyisobutene) with a number-average molecular weight of 700-5000, and more preferably polybutene (polyisobutene) with a number-average molecular weight of 900-3000.
As examples of preferred polybutenylsuccinimides to be used in the lubricating oil composition for an internal combustion engine according to the invention there may be mentioned compounds represented by the following general formulas (14) and (15).
The PIB in general formulas (14) and (15) represent polybutenyl groups, which are obtained from polybutene produced by polymerizing high purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride-based catalyst or aluminum chloride-based catalyst, and the polybutene mixture will usually include 5-100% by mole molecules with vinylidene structures at the ends. Also, from the viewpoint of obtaining a sludge-inhibiting effect, n is an integer of 2-5 and preferably an integer of 3-4.
There are no particular restrictions on the method of producing the succinimide represented by general formula (14) or (15), and for example, polybutenylsuccinic acid obtained by reacting a chlorinated product of the aforementioned polybutene, preferably highly reactive polybutene(polyisobutene) obtained by polymerization of the aforementioned high purity isobutene with a boron fluoride-based catalyst, and more preferably polybutene that has been thoroughly depleted of chlorine or fluorine, with maleic anhydride at 100-200° C., may be reacted with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine. The polybutenylsuccinic acid may be reacted with a two-fold (molar ratio) amount of polyamine for production of bissuccinimide, or the polybutenylsuccinic acid may be reacted with an equivalent (molar ratio) amount of polyamine for production of a monosuccinimide. From the viewpoint of achieving excellent sludge dispersibility, a polybutenylbissuccinimide is preferred.
Since trace amounts of fluorine or chlorine can remain in the polybutene used in the production process described above as a result of the catalyst used in the process, it is preferred to use polybutene that has been thoroughly depleted of fluorine or chlorine by an appropriate method such as adsorption or thorough washing with water. The fluorine or chlorine content is preferably not greater than 50 ppm by mass, more preferably not greater than 10 ppm by mass, even more preferably not greater than 5 ppm by mass and most preferably not greater than I ppm by mass.
In processes where polybutene is reacted with maleic anhydride to obtain polybutenylsuccinic anhydride, it has been the common practice to employ chlorination using chlorine. However, such methods result in significant chlorine residue (for example, approximately 2000-3000 ppm) in the final succinimide product. On the other hand, methods that employ no chlorine, such as methods using highly reactive polybutene and/or thermal reaction processes, can limit residual chlorine in the final product to extremely low levels (for example, 0-30 ppm). In order to reduce the chlorine content in the lubricating oil composition to within a range of 0-30 ppm by mass, therefore, it is preferred to use polybutenylsuccinic anhydride obtained not by a chlorination method but by a method using the aforementioned highly reactive polybutene and/or a thermal reaction process.
As polybutenylsuccinimide derivatives there may be used “modified” succinimides obtained by reacting boron compounds such as boric acid or oxygen-containing organic compounds such as alcohols, aldehydes, ketones, alkylphenols, cyclic carbonates, organic acids and the like with compounds represented by general formula (14) or (15) above, and neutralizing or amidating all or a portion of the residual amino groups and/or imino groups. Particularly advantageous from the viewpoint of heat and oxidation stability are boron-containing alkenyl (or alkyl) succinimides obtained by reaction with boron compounds such as boric acid.
As boron compounds to be reacted with the compound represented by general formula (14) or (15) there may be mentioned boric acid, boric acid salts, boric acid esters and the like. As specific examples of boric acids there may be mentioned orthoboric acid, metaboric acid and tetraboric acid. As boric acid salts there may be mentioned alkali metal salts, alkaline earth metal salts and ammonium salts of boric acid, and as more specific examples there may be mentioned lithium borates such as lithium metaborate, lithium tetraborate, lithium pentaborate and lithium perborate; sodium borates such as sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate and sodium octaborate; potassium borates such as potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate and potassium octaborate; calcium borates such as calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate and calcium hexaborate; magnesium borates such as magnesium metaborate, magnesium diborate, trimagnesium tetraborate, pentamagnesium tetraborate and magnesium hexaborate; and ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate. As boric acid esters there may be mentioned esters of boric acid and preferably C1-6 alkyl alcohols, and as more specific examples there may be mentioned monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, tributyl borate and the like. Succinimide derivatives reacted with such boron compounds are preferred for superior heat resistance and oxidation stability.
As examples of oxygen-containing organic compounds to be reacted with the compound represented by general formula (14) or (15) there may be mentioned, specifically, C1-30 monocarboxylic acids such as formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid and eicosanoic acid, C2-30 polycarboxylic acids such as oxalic acid, phthalic acid, trimellitic acid and pyromellitic acid or their anhydrides or ester compounds, and C2-6 alkylene oxides, hydroxy(poly)oxyalkylene carbonates and the like. Presumably, reaction of such oxygen-containing organic compounds produces a compound wherein all or a portion of the amino groups or imino groups in the compound represented by general formula (14) or (15) have the structure represented by general formula (16) below.
R40 in general formula (16) represents hydrogen, C1-24 alkyl, C1-24 alkenyl, C1-24 alkoxy or a hydroxy(poly)oxyalkylene group represented by —O—(R41O)mH, R41 represents C1-4 alkylene, and m represents an integer of 1-5. Preferred among these from the viewpoint of excellent sludge dispersibility are polybutenylbissuccinimides, composed mainly of product from reaction of these oxygen-containing organic compounds with all of the amino groups or imino groups. Such compounds can be obtained by reacting, for example, (n-1) moles of oxygen-containing organic compound with 1 mol of the compound of formula (11), for example. Succinimide derivatives obtained by reaction with such oxygen-containing organic compounds have excellent sludge dispersibility, and those reacted with hydroxy(poly)oxyalkylene carbonate are especially preferred.
The weight-average molecular weight of the polybutenylsuccinimide and/or its derivative as an ashless dispersant used for the invention is preferably 5000 or greater, more preferably 6500 or greater, even more preferably 7000 or greater and most preferably 8000 or greater. With a weight-average molecular weight of less than 5000, the molecular weight of the non-polar polybutenyl groups will be low and the sludge dispersibility will be poor, while the oxidation stability will be inferior due to a higher proportion of amine portions of the polar groups, which can act as active sites for oxidative degradation, such that the usable life-lengthening effect of the invention may not be achieved. On the other hand, from the viewpoint of preventing reduction of the low temperature viscosity characteristic, the weight-average molecular weight of the polybutenylsuccinimide and/or its derivative is preferably not greater than 20,000 and most preferably not greater than 15,000. The weight-average molecular weight referred to here is the weight-average molecular weight based on polystyrene, as measured using a 150-CALC/GPC by Japan Waters Co., equipped with two GMHHR-M (7.8 mmID×30 cm) columns by Tosoh Corp. in series, with tetrahydrofuran as the solvent, a temperature of 23° C., a flow rate of 1 mL/min, a sample concentration of 1% by mass, a sample injection rate of 75 μL and a differential refractometer (RI) as the detector.
According to the invention, the ashless dispersant used may be, in addition to the aforementioned succinimide and/or its derivative, an alkyl or alkenylpolyamine, alkyl or alkenylbenzylamine, alkyl or alkenylsuccinic acid ester, Mannich base, or a derivative thereof.
The ashless dispersant content of the lubricating oil composition for an internal combustion engine according to the invention is preferably 0.005% by mass or greater, more preferably 0.01% by mass or greater and even more preferably 0.05% by mass or greater, and preferably not greater than 0.3% by mass, more preferably not greater than 0.2% by mass and even more preferably not greater than 0.15% by mass, in terms of nitrogen element, based on the total amount of the composition. If the ashless dispersant content is not above the aforementioned lower limit a sufficient effect on cleanability will not be exhibited, while the content preferably does not exceed the aforementioned upper limit in order to avoid impairing the low temperature viscosity characteristic and demulsifying property. When using an imide-based succinate ashless dispersant with a weight-average molecular weight of 6500 or greater, the content is preferably 0.005-0.05% by mass and more preferably 0.01-0.04% by mass, in terms of nitrogen element, based on the total amount of the composition, from the viewpoint of exhibiting sufficient sludge dispersibility and achieving an excellent low temperature viscosity characteristic.
When a high molecular weight ashless dispersant is used, the content is preferably 0.005% by mass or greater and more preferably 0.01% by mass or greater, and preferably not greater than 0.1% by mass and more preferably not greater than 0.05% by mass, in terms of nitrogen element, based on the total amount of the composition. If the high molecular weight ashless dispersant content is not above the aforementioned lower limit a sufficient effect on cleanability will not be exhibited, while the content preferably does not exceed the aforementioned upper limit in order to avoid impairing the low temperature viscosity characteristic and demulsifying property.
When a boron compound-modified ashless dispersant is used, the content is preferably 0.005% by mass or greater, more preferably 0.01% by mass or greater and even more preferably 0.02% by mass or greater, and preferably not greater than 0.2% by mass and more preferably not greater than 0.1% by mass, in terms of boron element, based on the total amount of the composition. If the ashless dispersant modified by the boron compound content is not above the aforementioned lower limit a sufficient effect on cleanability will not be exhibited, while the content preferably does not exceed the aforementioned upper limit in order to avoid impairing the low temperature viscosity characteristic and demulsifying property.
The lubricating oil composition for an internal combustion engine according to the invention preferably contains an ashless friction modifier to allow further improvement in the frictional properties. The ashless friction modifier used may be any compound ordinarily used as a friction modifier for lubricating oils, and as examples there may be mentioned ashless friction modifiers that are amine compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic ethers, hydrazide (such as oleyl hydrazide), semicarbazides, ureas, ureidos, biurets and the like having one or more C6-30 alkyl or alkenyl and especially C6-30 straight-chain alkyl or straight-chain alkenyl groups in the molecule.
The friction modifier content of the lubricating oil composition for an internal combustion engine according to the invention 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 not greater than 3% by mass, more preferably not greater than 2% by mass and even more preferably not greater than 1% by mass, based on the total amount of the composition. If the friction modifier content is less than the aforementioned lower limit the friction reducing effect by the addition will tend to be insufficient, while if it is greater than the aforementioned upper limit, the effects of the anti-wear additives may be inhibited, or the solubility of the additives may be reduced.
The lubricating oil composition for an internal combustion engine according to the invention preferably further contains a metal-based detergent from the viewpoint of cleanability. The metal-based detergent used is preferably at least one alkaline earth metal-based detergent selected from among alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates.
As alkaline earth metal sulfonates there may be mentioned alkaline earth metal salts, especially magnesium salts and/or calcium salts, and preferably calcium salts, of alkylaromatic sulfonic acids obtained by sulfonation of alkyl aromatic compounds with a molecular weight of 300-1,500 and preferably 400-700. As such alkylaromatic sulfonic acids there may be mentioned, specifically, petroleum sulfonic acids and synthetic sulfonic acids. As petroleum sulfonic acids there may be used the sulfonated alkyl aromatic compounds obtained from lube-oil distillates of a mineral oil, or “mahogany acids” that are by-products of white oil production. Examples of synthetic sulfonic acids that may be used include sulfonated products of alkylbenzenes with straight-chain or branched alkyl groups, either as by-products of alkylbenzene production plants that are used as starting materials for detergents or obtained by alkylation of polyolefins onto benzene, or sulfonated alkylnaphthalenes such as sulfonated dinonylnaphthalenes. There are no particular restrictions on the sulfonating agent used for sulfonation of these alkyl aromatic compounds, but for most purposes fuming sulfuric acid or sulfuric anhydride may be used.
As alkaline earth metal phenates there may be mentioned alkaline earth metal salts, and especially magnesium salts and/or calcium salts, of alkylphenols, alkylphenol sulfides and alkylphenol Mannich reaction products, examples of which include compounds represented by the following general formulas (17)-(19).
In general formulas (17)-(19), R41, R42, R43, R44, R45 and R46 may be the same or different and each represents a C4-30 and preferably C6-18 straight-chain or branched alkyl group, M1, M2 and M3 each represent an alkaline earth metal and preferably calcium and/or magnesium, and x represents 1 or 2. As specific examples for R41, R42, R43, R44, R45 and R46 in the above formulas there may be mentioned butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontyl, which may be straight-chain or branched. These may be primary alkyl, secondary alkyl or tertiary alkyl groups.
As alkaline earth metal salicylates there may be mentioned alkaline earth metal salts, and especially magnesium salts and/or calcium salts, of alkylsalicylic acids, examples of which include compounds represented by the following general formula (20).
In general formula (20), R47 represents a C1-30 and preferably C6-18 straight-chain or branched alkyl group, n represents an integer of 1-4 and preferably 1 or 2, and M4 represents an alkaline earth metal and preferably calcium and/or magnesium. As specific examples for R47 there may be mentioned butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontyl, which may be straight-chain or branched. These may be primary alkyl, secondary alkyl or tertiary alkyl groups.
Alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates include not only neutral (normal salt) alkaline earth metal sulfonates, neutral (normal salt) alkaline earth metal phenates and neutral (normal salt) alkaline earth metal salicylates obtained by reacting the aforementioned alkylaromatic sulfonic acids, alkylphenols, alkylphenol sulfides, alkylphenol Mannich reaction products and alkylsalicylic acids directly with alkaline earth metal bases such as oxides or hydroxides of alkaline earth metals such as magnesium and/or calcium, or by first forming alkali metal salts such as sodium salts or potassium salts and then replacing them with alkaline earth metal salts, but also basic alkaline earth metal sulfonates, basic alkaline earth metal phenates and basic alkaline earth metal salicylates obtained by heating neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates with an excess of alkaline earth metal salts or alkaline earth metal bases in the presence of water, and overbased(superbased) alkaline earth metal sulfonates, overbased(superbased) alkaline earth metal phenates and overbased(superbased) alkaline earth metal salicylates obtained by reacting alkaline earth metal hydroxides with carbon dioxide gas or boric acid in the presence of neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates.
According to the invention, the aforementioned neutral alkaline earth metal salts, basic alkaline earth metal salts, overbased(superbased) alkaline earth metal salts or mixtures thereof may be used. Of these, combinations of overbased calcium sulfonate and overbased calcium phenate, or overbased calcium salicylate, are preferably used and overbased calcium salicylate is most preferably used, from the viewpoint of maintaining cleanability for prolonged periods. Metal-based detergents are generally marketed or otherwise available in forms diluted with light lubricating base oils, and for most purposes the metal content will be 1.0-20% by mass and preferably 2.0-16% by mass. The alkaline earth metal-based detergent used for the invention may have any total base number, but for most purposes the total base number is not greater than 500 mgKOH/g and preferably 150-450 mgKOH/g. The total base number referred to here is the 5 total base number determined by the perchloric acid method, as measured according to JIS K2501(1992): “Petroleum Product And Lubricating Oils-Neutralization Value Test Method”, Section 7.
The metal-based detergent content of the lubricating oil composition for an internal combustion engine according to the invention may be as desired, but it is preferably 0.1-10% by mass, more preferably 0.5-8% by mass and most preferably 1-5% by mass based on the total amount of the composition. The content is preferably not greater than 10% by mass because no commensurate effect will be obtained with the increased addition.
The lubricating oil composition for an internal combustion engine according to the invention preferably contains a viscosity index improver to allow further improvement in the viscosity-temperature characteristic. As viscosity index improvers there may be mentioned non-dispersant or dispersant polymethacrylates, dispersed ethylene-α-olefin copolymers and their hydrides, polyisobutylene and its hydride, styrene-diene hydrogenated copolymers, styrene-maleic anhydride ester copolymers and polyalkylstyrenes, among which non-dispersant viscosity index improvers and/or dispersed viscosity index improvers with weight-average molecular weights of 10,000-1,000,000, preferably 100,000-900,000, more preferably 150,000-500,000 and even more preferably 180,000-400,000 are preferred.
As specific examples of non-dispersant viscosity index improvers there may be mentioned homopolymers of a monomer (hereinafter referred to as “monomer (M-1)”) selected from among compounds represented by the following general formulas (21), (22) and (23), and copolymers of two or more of monomer (M-1), or hydrides thereof. As specific examples of dispersed viscosity index improvers, on the other hand, there may be mentioned compounds obtained by introducing an oxygen-containing group into a copolymer of two or more monomers (hereinafter referred to as “monomer (M-2)”) selected from among compounds represented by general formulas (24) and (25) or their hydrides, and copolymers of one or more of monomer (M-1) selected from among compounds represented by general formulas (21)-(23) with one or more of monomer (M-2) selected from among compounds represented by general formulas (24) and (25), or hydrides thereof.
In general formula (21), R48 represents hydrogen or methyl and R49 represents hydrogen or a C1-18 alkyl group. Specific examples of C1-18 alkyl groups represented by R49 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl (where the alkyl groups may be straight-chain or branched).
In general formula (22), R50 represents hydrogen or methyl and R51 represents hydrogen or a C1-12 hydrocarbon group. Specific examples of C1-12 hydrocarbon groups represented by R51 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl (which alkyl groups may be straight-chain or branched); C5-7 cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; C6-11 alkylcycloalkyl groups such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl (where the alkyl groups may be substituted at any position on the cycloalkyl groups); alkenyl groups such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl (where the alkenyl groups may be straight-chain or branched, and the double bonds may be at any position); aryl groups such as phenyl and naphthyl; C7-12 alkylaryl groups such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl and hexylphenyl (where the alkyl groups may be straight-chain or branched, and substituted at any position of the aryl groups); and C7-12 arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl (where the alkyl groups may be straight-chain or branched).
In general formula (23), X1 and X2 each separately represent hydrogen, a C1-18 alkoxy group (—OR52: R52═C1-1 8 alkyl group) or a C1-18 monoalkylamino group (—NHR53: R53═C1-18 alkyl group).
In general formula (23), R54 represents hydrogen or methyl, R55 represents a C1-18 alkylene group, Y1 represents an amine residue or heterocyclic residue containing 1-2 nitrogen atoms and 0-2 oxygen atoms, and m is 0 or 1. Specific examples of C1-18 alkylene groups represented by R55 include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene and octadecylene (which alkylene groups may be straight-chain or branched). Specific examples of groups represented by Y1 include dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoylamino, morpholino, pyrolyl, pyrrolino, pyridyl, methylpyridyl, pyrrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino and pyrazino.
In general formula (25), R56 represents hydrogen or methyl and Y2 represents an amine residue or heterocyclic residue containing 1-2 nitrogen atoms and 0-2 oxygen atoms. Specific examples of groups represented by Y2 include dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoylamino, morpholino, pyrolyl, pyrrolino, pyridyl, methylpyridyl, pyrrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino and pyrazino.
Specific preferred examples for monomer (M-1) include C1-18 alkyl acrylates, C1-18 alkyl methacrylates, C2-20 olefins, styrenes, methylstyrene, maleic anhydride esters, maleic anhydride amides and mixtures of the foregoing.
Specific preferred examples for monomer (M-2) include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures of the foregoing.
The molar ratio of copolymerization for the copolymer of the one or more monomers selected from among (M-1) compounds and one or more monomers selected from among (M-2) compounds will generally be, approximately, monomer (M-1):monomer (M-2)=80:20-95:5. Any production process may be employed, but usually a copolymer can be easily obtained by radical solution polymerization of the monomer (M-1) and monomer (M-2) in the presence of a polymerization initiator such as benzoyl peroxide.
Of the viscosity index improvers mentioned above, polymethacrylate-based viscosity index improvers are preferred from the viewpoint of a superior cold flow property.
The viscosity index improver content of the lubricating oil composition for an internal combustion engine according to the invention is preferably 0.1-15% by mass and more preferably 0.5-5% by mass based on the total amount of the composition. If the viscosity index improver content is less than 0.1% by mass, the improving effect on the viscosity-temperature characteristic by its addition will tend to be insufficient, while if it exceeds 15% by mass it will tend to be difficult to maintain the initial extreme-pressure property for long periods.
If necessary in order to improve performance, other additives in addition to those mentioned above may be added to the lubricating oil composition for an internal combustion engine according to the invention, and such additives may include corrosion inhibitors, rust-preventive agents, demulsifiers, metal inactivating agents, pour point depressants, rubber swelling agents, antifoaming agents, coloring agents and the like, either alone or in combinations of two or more.
As examples of corrosion inhibitors there may be mentioned benzotriazole-based, tolyltriazole-based, thiadiazole-based and imidazole-based compounds.
As examples of rust-preventive agents there may be mentioned petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenylsuccinic acid esters and polyhydric alcohol esters.
As examples of demulsifiers there may be mentioned polyalkylene glycol-based nonionic surfactants such as polyoxyethylenealkyl ether, polyoxyethylenealkylphenyl ether and polyoxyethylenealkylnaphthyl ether.
As examples of metal inactivating agents there may be mentioned imidazolines, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazole or its derivatives, 1,3,4-thiadiazolepolysulfides, 1,3,4-thiadiazolyl-2,5-bisdialkyl dithiocarbamates, 2-(alkyldithio)benzimidazoles and β-(o-carboxybenzylthio)propionitrile.
Any publicly known pour point depressants may be selected as pour point depressants depending on the properties of the lubricating base oil, but preferred are polymethacrylates with a weight-average molecular weight of greater than 50,000 and not greater than 150,000, and preferably 80,000-120,000.
As antifoaming agents there may be used any compounds commonly employed as antifoaming agents for lubricating oils, and as examples there may be mentioned silicones such as dimethylsilicone and fluorosilicone. Any one or more selected from these compounds may be added in any desired amount.
As coloring agents there may be used any normally employed compounds and in any desired amounts, although the contents will usually be 0.001-1.0% by mass based on the total amount of the composition.
When such additives are added to a lubricating oil composition of the invention, the contents will normally be selected in ranges of 0.005-5% by mass for corrosion inhibitors, rust-preventive agents and demulsifiers, 0.005-1% by mass for metal inactivating agents, 0.05-1% by mass for pour point depressants, 0.0005-1% by mass for antifoaming agents and 0.001-1.0% by mass for coloring agents, based on the total amount of the composition.
The lubricating oil composition for an internal combustion engine according to the invention may include additives containing sulfur as a constituent element as mentioned above, but the total sulfur content of the lubricating oil composition (the total of sulfur from the lubricating base oil and additives) is preferably 0.05-0.3% by mass, more preferably 0.08-0.25% by mass, even more preferably 0.1-0.2% by mass and most preferably 0.12-0.18% by mass from the viewpoint of solubility of the additives and of exhausting the base number that results from production of sulfur oxides under high-temperature oxidizing conditions.
The kinematic viscosity at 100° C. of the lubricating oil composition for an internal combustion engine according to the invention will normally be 4-24 mm2/s, but from the viewpoint of maintaining the oil film thickness which prevents seizing and wear and the viewpoint of inhibiting increase in stirring resistance, it is preferably 5-18 mm2/s, more preferably 6-15 mm2/s and even more preferably 7-12 mm2/s.
The lubricating oil composition for an internal combustion engine according to the invention having the construction described above has excellent heat and oxidation stability, as well as superiority in terms of viscosity-temperature characteristic, frictional property and resistance to volatilization, and therefore exhibits an adequate long drain property and energy savings when used as a lubricating oil for an internal combustion engine, such as a gasoline engine, diesel engine, oxygen-containing compound-containing fuel engine or gas engine for two-wheel vehicles, four-wheel vehicles, electric power generation, ships and the like.
(Lubricating oil composition for power train device) A lubricating oil composition for a power train device according to the invention comprises the lubricating base oil of the invention described above, a poly(meth)acrylate-based viscosity index improver and a phosphorus-containing compound.
The modes for the lubricating oil of the invention in the lubricating oil composition for a power train device according to the invention, and the process for its production, are as described above and will not be repeated here. The lubricating base oil of the invention may be used as a single type or a combination of two or more types.
The lubricating base oil of the invention may also be used in combination with one or more other base oils in the lubricating oil composition for a power train device according to the invention. As other base oils there may be used the mineral oil base oils and/or synthetic base oils mentioned as examples for the lubricating base oil of the invention. When the lubricating base oil of the invention is combined with another base oil, the proportion of the lubricating base oil of the invention of the total mixed base oil is preferably 30% by mass or greater, more preferably 50% by mass or greater and even more preferably 70% by mass or greater.
The lubricating oil composition for a power train device according to the invention also comprises a poly(meth)acrylate-based viscosity index improver as component (C). By combining the poly(meth)acrylate-based viscosity index improver with the lubricating base oil of the invention as described above, it is possible to effectively exhibit a viscosity index-improving effect, a viscosity-suppressing effect at low temperatures and a pour point-lowering effect, in addition to the original excellent viscosity-temperature characteristic of the lubricating base oil, and thus to achieve a high level of low-temperature characteristics.
There are no particular restrictions on the poly(meth)acrylate-based viscosity index improver used for the invention, and non-dispersant or dispersed poly(meth)acrylate compounds commonly employed as viscosity index improvers for lubricating oils may be used. Polymers of compounds represented by the following general formula (26) may be mentioned as non-dispersant poly(meth)acrylate-based viscosity index improvers.
In general formula (26), R57 represents a C1-30 alkyl group. The alkyl group represented by R57 may be either straight-chain or branched. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triacontyl (which alkyl groups may be either straight-chain or branched).
As preferred examples of dispersed poly(meth)acrylate-based viscosity index improvers there may be mentioned, specifically, copolymers obtained by copolymerizing one or more monomers selected from among compounds represented by general formula (26) above, with one or more nitrogen-containing monomers selected from among compounds represented by general formula (27) or (28) below.
In general formulas (27) and (28), R58 and R60 each separately represent hydrogen or methyl. R59 represents a C1-30 alkylene group, of which specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene and triacontylene (where the alkylene groups may be either straight-chain or branched). The letter “a” represents an integer of 0 or 1, and X3 and X4 each separately represent an amine residue or heterocyclic residue containing 1-2 nitrogen atoms and 0-2 oxygen atoms. Specific preferred examples for X3 and X4 include dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoylamino, morpholino, pyrolyl, pyrrolino, pyridyl, methylpyridyl, pyrrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino and pyrazino.
Specific preferred examples of nitrogen-containing monomers represented by general formula (27) or (28) include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures thereof.
A poly(meth)acrylate-based viscosity index improver used for the invention may be either dispersant or non-dispersant as mentioned above, but preferably a non-dispersant poly(meth)acrylate-based viscosity index improver is used, and more preferably one of the following (C-1)-(C-3).
Of polymers (C-1)-(C-3) above, polymers (C-2) and (C-3) are especially preferred from the viewpoint of improving the fatigue life. Polymer (C-3) preferably contains a monomer of general formula (26) wherein R57 is a C22-28 branched alkyl group (more preferably 2-decyltetradecyl group) as a structural unit.
The weight-average molecular weight of the poly(meth)acrylate-based viscosity index improver used for the invention is not particularly restricted but is preferably 5,000-100,000, more preferably 10,000-60,000 and even more preferably 15,000-24,000. If the weight-average molecular weight of the poly(meth)acrylate-based viscosity index improver is less than 5,000 the viscosity increase effect due to addition of the viscosity index improver will be insufficient, while if it is greater than 100,000 the fatigue life, antiwear property and shear stability will be inadequate. The weight-average molecular weight referred to here is the weight-average molecular weight based on polystyrene, as measured using a 150-CALC/GPC by Japan Waters Co., equipped with two GMHHR-M (7.8 mmID×30 cm) columns by Tosoh Corp. set in series, with tetrahydrofuran as the solvent and a differential refractometer (RI) as the detector, and with a temperature of 23° C., a flow rate of 1 mL/min, a sample concentration of 1% by mass, a sample injection rate of 75 μL.
The poly(meth)acrylate-based viscosity index improver content in the lubricating oil composition for a power train device according to the invention is preferably 0.1-20% by mass and more preferably 1-15% by mass based on the total amount of the composition. If the poly(meth)acrylate-based viscosity index improver content is less than 0.1% by mass the viscosity-increasing effect and the cold flow property-improving effect of the addition will tend to be insufficient, while if it is greater than 20% by mass the viscosity of the lubricating oil composition will be increased, making it difficult to achieve fuel savings and tending to lower the shear stability. When a poly(meth)acrylate-based viscosity index improver is added to the lubricating base oil, the poly(meth)acrylate-based viscosity index improver will generally be dissolved in 5-95% by mass of a diluent and the mixture added to the lubricating base oil, for improved lubricity and handleability, and the poly(meth)acrylate-based viscosity index improver content in this case refers to the total amount of the poly(meth)acrylate-based viscosity index improver and the diluent.
The lubricating oil composition for a power train device according to the invention further contains a phosphorus-containing compound as component (D). As phosphorus-containing compounds there are preferably used phosphorus-based extreme-pressure agents and phosphorus/sulfur-containing extreme-pressure agents.
As phosphorus-based extreme-pressure agents there may be mentioned phosphoric acid, phosphorous acid, phosphoric acid esters and phosphorous acid esters with C1-30 and preferably C3-20 hydrocarbon groups, and salts of the foregoing. As phosphorus/sulfur-containing extreme-pressure agents there may be mentioned thiophosphoric acid, thiophosphorous acid, thiophosphoric acid esters and thiophosphorous acid esters with C1-30 and preferably C3-20 hydrocarbon groups, salts of the foregoing, and zinc dithiophosphate.
As examples of C1-30 hydrocarbon groups there may be mentioned alkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aryl, alkylaryl and arylalkyl groups.
As examples of alkyl groups there may be mentioned alkyl groups such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl (which alkyl groups may be straight-chain or branched).
As cycloalkyl groups there may be mentioned C5-7 cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl.
As examples of alkylcycloalkyl groups there may be mentioned C6-11 alkylcycloalkyl groups such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl, (where the alkyl groups may be substituted at any position on the cycloalkyl groups).
As examples of the alkenyl groups there may be mentioned alkenyl groups such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl (where the alkenyl groups may be straight-chain or branched, and the double bonds may be at any positions).
As examples of aryl groups there may be mentioned aryl groups such as phenyl and naphthyl.
As examples of alkylaryl groups there may be mentioned C7-18 alkylaryl groups such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecylphenyl (where the alkyl groups may be straight-chain or branched and substituted at any positions on the aryl groups).
As examples of arylalkyl groups there may be mentioned C7-12 arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl (where the alkyl groups may be either straight-chain or branched).
According to the invention it is preferred to use at least one phosphorus-based extreme-pressure agent selected from among phosphorous acid, phosphorous acid monoesters, phosphorous acid diesters, phosphorous acid triesters, and salts of the foregoing. As phosphorus/sulfur-containing extreme-pressure agents there are preferably used at least one selected from among thiophosphorous acid, thiophosphorous acid monoesters, thiophosphorous acid diesters, thiophosphorous acid triesters, dithiophosphorous acid, dithiophosphorous acid monoesters, dithiophosphorous acid diesters, dithiophosphorous acid triesters, trithiophosphorous acid, trithiophosphorous acid monoesters, trithiophosphorous acid diesters, trithiophosphorous acid triesters, and salts of the foregoing.
As specific preferred examples of phosphorus-based extreme-pressure agents there may be mentioned monobutyl phosphate, monooctyl phosphate, monolauryl phosphate, dibutyl phosphate, dioctyl phosphate, dilauryl phosphate, diphenyl phosphate, tributyl phosphate, trioctyl phosphate, trilauryl phosphate, triphenyl phosphate, monobutyl phosphite, monooctyl phosphite, monolauryl phosphite, dibutyl phosphite, dioctyl phosphite, dilauryl phosphite, diphenyl phosphite, tributyl phosphite, trioctyl phosphite, trilauryl phosphite, triphenyl phosphite, and salts of the foregoing, among which phosphorous acid ester-based extreme-pressure agents and especially phosphorous acid diester-based extreme-pressure agents are preferred.
As specific preferred examples of phosphorus/sulfur-containing extreme-pressure agents there may be mentioned monobutyl thiophosphate, monooctyl thiophosphate, monolauryl thiophosphate, dibutyl thiophosphate, dioctyl thiophosphate, dilauryl thiophosphate, diphenyl thiophosphate, tributyl thiophosphate, trioctyl thiophosphate, triphenyl thiophosphate, trilauryl thiophosphate, monobutyl thiophosphite, monooctyl thiophosphite, monolauryl thiophosphite, dibutyl thiophosphite, dioctyl thiophosphite, dilauryl thiophosphite, diphenyl thiophosphate, tributyl thiophosphite, trioctyl thiophosphite, triphenyl thiophosphite and trilauryl thiophosphite having 1-3, preferably 2 or 3 and especially 3 sulfur atoms in the molecule, as well as salts of the foregoing, among which thiophosphorous acid ester-based extreme-pressure agents and especially trithiophosphorous acid ester-based extreme-pressure agents are preferred.
As examples of salts of (thio)phosphoric acid esters and (thio)phosphorous acid esters there may be mentioned salts obtained by reacting (thio)phosphoric acid monoesters, (thio)phosphoric acid diesters, (thio)phosphorous acid monoesters, (thio)phosphorous acid diesters and the like with nitrogen compounds such as ammonia or amine compounds containing only C1-8 hydrocarbon or hydroxyl-containing hydrocarbon groups in the molecule, or metal bases such as zinc oxide or zinc chloride, and neutralizing all or a portion of the remaining acidic hydrogens.
As specific nitrogen compounds there may be mentioned ammonia; alkylamines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine and dioctylamine (where the alkyl groups may be straight-chain or branched); alkanolamines such as monomethanolamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, monoheptanolamine, monooctanolamine, monononanolamine, dimethanolamine, methanolethanolamine, diethanolamine, methanolpropanolamine, ethanolpropanolamine, dipropanolamine, methanolbutanolamine, ethanolbutanolamine, propanolbutanolamine, dibutanolamine, dipentanolamine, dihexanolamine, diheptanolamine and dioctanolamine (where the alkanol groups may be straight-chain or branched); and mixtures of the foregoing.
As phosphorus-containing compounds to be used for the invention there are preferred phosphorous acid diester-based extreme-pressure agents such as di-2-ethylhexyl phosphite from the viewpoint of improving the fatigue life and heat and oxidation stability, trithiophosphorous acid triester-based extreme-pressure agents such as trilauryl trithiophosphite from the viewpoint of improving the fatigue life, and zinc dialkyldithiophosphate from the viewpoint of improving the antiwear property.
There are no particular restrictions on the phosphorus-containing compound content of the lubricating oil composition for a power train device according to the invention, but from the viewpoint of the fatigue life, extreme-pressure property, antiwear property and oxidation stability, it is preferably 0.01-0.2% by mass and more preferably 0.02-0.15% by mass as phosphorus element based on the total amount of the composition. If the phosphorus-containing compound content is below the aforementioned lower limit, the lubricity will tend to be insufficient. Also, when the lubricating oil composition is used as a lubricating oil for a manual transmission, the synchro property (lubrication which allows gears with different reduction gear ratios to engage smoothly for function) will tend to be insufficient. On the other hand, if the phosphorus-containing compound content is greater than the aforementioned upper limit the fatigue life will tend to be inadequate. Also, when the lubricating oil composition is used as a lubricating oil for a manual transmission, the heat and oxidation stability will tend to be insufficient.
The lubricating oil composition for a power train device according to the invention may consist only of the lubricating base oil, the poly(meth)acrylate-based viscosity index improver and the phosphorus-containing compound described above, but it may further contain the various additives mentioned below as necessary.
The lubricating oil composition for a power train device according to the invention also preferably comprises a sulfur-containing extreme-pressure agent in addition to the aforementioned phosphorus/sulfur-containing extreme-pressure agent, from the viewpoint of yet further improving the fatigue life, extreme-pressure property and antiwear property. As sulfur-containing extreme-pressure agents there may be used the sulfurized fats and oils, olefin sulfides, dihydrocarbyl polysulfides, dithiocarbamates, thiadiazoles and benzothiazoles mentioned as examples for the (B-1) ashless antioxidant containing sulfur as a constituent element in the explanation given above regarding the lubricating oil composition for an internal combustion engine according to the invention, and they will not be repeated here.
There are no particular restrictions on the sulfur-containing extreme-pressure agent content of the lubricating oil composition for a power train device according to the invention, but from the viewpoint of fatigue life, extreme-pressure property, antiwear property and oxidation stability, it is preferably 0.01-3% by mass, more preferably 0.1-3% by mass, even more preferably 0.5-2.5% by mass and most preferably 1.5-2.5% by mass ,in terms of sulfur element, based on the total amount of the composition. If the sulfur-containing extreme-pressure agent content is below the aforementioned lower limit, the lubricity will tend to be insufficient. Also, when the lubricating oil composition is used as a lubricating oil for a manual transmission, the synchro property (lubrication which allows gears with different reduction gear ratios to engage smoothly for function) will tend to be insufficient. On the other hand, if the sulfur-containing extreme-pressure agent content is above the aforementioned upper limit, the fatigue life will tend to be inadequate. Also, when the lubricating oil composition is used as a lubricating oil for a manual transmission, the heat and oxidation stability will tend to be insufficient. When the lubricating oil composition for a power train device according to the invention is to be used as a lubricating oil for a final reduction gear box it will be necessary to ensure an even superior extreme-pressure property, and therefore the sulfur-containing extreme-pressure agent content is preferably 0.5-3% by mass and more preferably 1.5-2.5% by mass, in terms of sulfur element, based on the total amount of the composition.
As mentioned above, the lubricating oil composition for a power train device according to the invention comprises a poly(meth)acrylate-based viscosity index improver, but it may also comprise a viscosity index improver other than the poly(meth)acrylate-based viscosity index improver. As such viscosity index improvers there may be mentioned dispersed ethylene-α-olefin copolymers and their hydrides, polyisobutylene or its hydrides, styrene-diene hydrogenated copolymers, styrene-maleic anhydride ester copolymers and polyalkylstyrenes.
When using such viscosity index improvers, the content thereof will normally be selected within a range of 0.1-10% by mass based on the total amount of the composition.
The lubricating oil composition for a power train device according to the invention also preferably comprises an ashless dispersant from the viewpoint of yet further improving the antiwear property, heat and oxidation stability and frictional properties. As examples of ashless dispersants there may be mentioned the following nitrogen compounds (E-1)-(E-3). These may be used alone or in combinations of two or more.
More specifically, examples of the (F-1) succinimides include compounds represented by the following general formula (29) or (30).
In general formula (29), R61 represents a C40-400 and preferably C60-350 alkyl or alkenyl group, and j represents an integer of 1-5 and preferably 2-4.
In general formula (30), R62 and R63 each separately represent a C40-400 and preferably C60-350 alkyl or alkenyl group, and k represents an integer of 0-4 and preferably 1-3.
The aforementioned succinimides include “mono type” succinimides represented by general formula (29), in a form with succinic anhydride added to one end of a polyamine by imidation, and “bis type” succinimides represented by general formula (30), in a form with succinic anhydride added to both ends of a polyamine, and either or mixtures of both of these may be used for the lubricating oil composition for a power train device according to the invention.
Specific examples of the (F-2) benzylamines include compounds represented by the following general formula (31).
In general formula (31), R64 represents a C40-400 and preferably C60-350 alkyl or alkenyl group, and m represents an integer of 1-5 and preferably 2-4.
The benzylamine may be obtained, for example, by reacting a polyolefin (for example, a propylene oligomer, polybutene or ethylene-α-olefin copolymer) with a phenol to produce an alkylphenol, and then reacting this with formaldehyde and a polyamine (for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine) by Mannich reaction.
Specific examples of the (F-3) polyamines include compounds represented by the following general formula (32).
R65—NH—(CH2CH2NH)n—H (32)
In general formula (32), R65 represents a C40-400 and preferably C60-350 alkyl or alkenyl group, and m represents an integer of 1-5 and preferably 2-4.
The polyamine may be obtained, for example, by chlorination of a polyolefin (for example, a propylene oligomer, polybutene or ethylene-α-olefin copolymer) followed by reaction with ammonia or a polyamine (for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or the like).
The nitrogen compound may have any nitrogen content, but from the viewpoint of antiwear property, oxidation stability and frictional properties, the nitrogen content is usually preferred to be 0.01-10% by mass and more preferably 0.1-10% by mass.
As examples of derivatives of the aforementioned nitrogen compounds there may be mentioned “acid-modified compounds” obtained by reacting the aforementioned nitrogen compounds with C2-30 monocarboxylic acids (fatty acids and the like) or C2-30 polycarboxylic acids such as oxalic acid, phthalic acid, trimellitic acid or pyromellitic acid, and neutralizing all or a portion of the remaining amino and/or imino groups for amidation; “boron-modified compounds” obtained by reacting the aforementioned nitrogen compounds with boric acid and neutralizing all or a portion of the remaining amino and/or imino groups for amidation; sulfur-modified compounds obtained by reacting the aforementioned nitrogen compounds with sulfur compounds; and modified compounds obtained by combining two or more types of modification, selected from among acid modification, boron modification and sulfur modification, of the aforementioned nitrogen compounds.
When the lubricating oil composition for a power train device according to the invention contains an ashless dispersant, there are no particular restrictions on its content but it is preferably 0.5-10.0% by mass and more preferably 1-8.0% by mass based on the total amount of the composition. If the ashless dispersant content is less than 0.5% by mass the effect of improving the fatigue life and extreme-pressure property will tend to be insufficient, while if it is greater than 10.0% by mass the cold flow property of the composition will be excessively impaired. Particularly when the lubricating oil composition for a power train device according to the invention is used as a lubricating oil for an automatic transmission or continously variable transmission, the content of the ashless dispersant is preferably 1-6% by mass based on the total amount of the composition. When the lubricating oil composition for a power train device according to the invention is used as a lubricating oil for a manual transmission, the content of the ashless dispersant is preferably 0.5-6% by mass and more preferably 0.5-2% by mass based on the total amount of the composition.
The lubricating oil composition for a power train device according to the invention also preferably comprises a metal-based detergent from the viewpoint of yet further improving the frictional properties. As specific examples of metal-based detergents there may be mentioned alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates, and any one or combination of two or more metal-based detergents selected from among these may be used.
More specifically, as alkaline earth metal sulfonates there may be mentioned alkaline earth metal salts of alkylaromatic sulfonic acids obtained by sulfonation of alkyl aromatic compounds with molecular weights of 100-1500 and preferably 200-700. Magnesium salts and/or calcium salts are especially preferred. As such alkylaromatic sulfonic acids there may be mentioned, specifically, petroleum sulfonic acids and synthetic sulfonic acids.
As petroleum sulfonic acids there may be used sulfonated alkyl aromatic compounds from mineral oil lube-oil distillates, or “mahogany acids” that are by-products of white oil production. Examples of synthetic sulfonic acids that may be used include sulfonated products of alkylbenzenes with straight-chain or branched alkyl groups, either as by-products of alkylbenzene production plants that are used as starting materials for detergents or obtained by alkylation of polyolefins onto benzene, or sulfonated dinonylnaphthalenes. The sulfonating agent used for these alkyl aromatic compounds may be, for example, fuming sulfuric acid or sulfuric acid.
As specific alkaline earth metal phenates there may be mentioned alkylphenols with at least one C4-30 and preferably 6-18 straight-chain or branched alkyl group, and alkylphenol sulfides obtained by reacting these alkylphenols with sulfur or alkaline earth metal salts of Mannich reaction products of alkylphenols obtained by reacting the alkylphenols with formaldehyde. Magnesium salts and/or calcium salts are especially preferred.
As specific alkaline earth metal salicylates there may be mentioned alkaline earth metal salts of alkylsalicylic acids with at least one C4-30 and preferably 6-18 straight-chain or branched alkyl group. Magnesium salts and/or calcium salts are especially preferred.
The aforementioned alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates may also contain, so long as the total base number is in a range of 20-450 mgKOH/g, not only neutral salts (normal salts) obtained by reacting an alkylaromatic sulfonic acid, alkylphenol, alkylphenol sulfide, alkylphenol Mannich reaction product, alkylsalicylic acid or the like directly with an alkaline earth metal base such as an oxide or hydroxide of an alkaline earth metal such as magnesium and/or calcium, or by first forming an alkali metal salt such as a sodium salt or potassium salt and then substituting it with an alkaline earth metal salt, but also basic salts obtained by heating such neutral salts (normal salts) with an excess of alkaline earth metal salts or alkaline earth metal bases ((hydroxides or oxides of alkaline earth metals) in the presence of water, or overbased(superbased) salts obtained by reacting neutral salts (normal salts) with alkaline earth metal bases in the presence of carbon dioxide gas. These reactions are usually carried out in solvents (aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as xylene or light lubricating base oils). Also, metal-based detergents are generally marketed or otherwise available in forms diluted with light lubricating base oils, and for most purposes the metal content will be 1.0-20% by mass and preferably 2.0-16% by mass.
When the lubricating oil composition for a power train device according to the invention contains a metal-based detergent, there are no particular restrictions on its content, but it is preferably 0.005-0.5% by mass, more preferably 0.008-0.3% by mass and even more preferably 0.01-0.2% by mass as metal element based on the total amount of the composition. If the metal-based detergent content is less than 0.005% by mass as metal element the improving effect on the frictional property will be insufficient, and if it exceeds 0.5% by mass an adverse effect may be exhibited on the wet clutch friction material. When the lubricating oil composition for a power train device according to the invention is to be used as a lubricating oil for an automatic transmission or continuously variable transmission, the metal-based detergent content is preferably 0.005-0.2% by mass and more preferably 0.008-0.02% by mass as metal element based on the total amount of the composition. Particularly when the lubricating oil composition for a power train device according to the invention is to be used as a lubricating oil for a manual transmission, the metal-based detergent content is preferably 0.05-0.5% by mass, more preferably 0.1-0.4% by mass and even more preferably 0.2-0.35% by mass as metal element based on the total amount of the composition.
The lubricating oil composition for a power train device according to the invention also preferably comprises an antioxidant from the viewpoint of yet further improving the heat and oxidation stability. As antioxidants there may be used any ones commonly employed in the field of lubricating oils, but particularly preferred ones are phenol-based antioxidants and/or amine-based antioxidants, and especially combinations of phenol-based antioxidants and amine-based antioxidants.
As specific examples of antioxidants there may be mentioned alkylphenols such as 2-6-di-tert-butyl-4-methylphenol, bisphenols such as methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol), naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, and esters of (3,5-di-tert-butyl-4-hydroxyphenyl) fatty acids (propionic acid and the like) or (3-methyl-5-tertbutyl-4-hydroxyphenyl) fatty acids (propionic acid or the like) with monohydric or polyhydric alcohols such as methanol, octanol, octadecanol, 1,6-hexadiol, neopentyl glycol, thiodiethylene glycol, triethylene glycol and pentaerythritol. Dialkylzinc dithiophosphates such as di-2-ethylhexylzinc dithiophosphate may also be used as antioxidants.
According to the invention, the one or more compounds selected from among the antioxidants mentioned above may be used in any desired amounts. There are no particular restrictions on the antioxidant content, but it is preferably 0.01-5.0% by mass based on the total amount of the composition.
The lubricating oil composition for a power train device according to the invention also preferably comprises a friction modifier from the viewpoint of yet further improving the wet clutch frictional properties for gearboxes. As friction modifiers there may be used any compounds commonly employed as friction modifiers in the field of lubricating oils, but preferred for use are amine compounds, imide compounds, fatty acid esters, fatty acid amides, fatty acid metal salts and the like having at least one C6-30 alkyl or alkenyl and especially C6-30 straight-chain alkyl or straight-chain alkenyl group in the molecule.
Examples of amine compounds include C6-30 straight-chain or branched and preferably straight-chain aliphatic monoamines, straight-chain or branched and preferably straight-chain aliphatic polyamines, and alkylene oxide addition products of these aliphatic amines. As imide compounds there may be mentioned succinimides with C6-30 straight-chain or branched alkyl or alkenyl groups, or the same modified with a carboxylic acid, boric acid, phosphoric acid, sulfuric acid or the like. Examples of fatty acid esters include esters of C7-31 straight-chain or branched and preferably straight-chain fatty acids with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of fatty acid amides include amides of C7-31 straight-chain or branched and preferably straight-chain fatty acids with aliphatic monoamines alcohols or aliphatic polyamines. As fatty acid metal salts there may be mentioned alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of C7-31 straight-chain or branched and preferably straight-chain fatty acids.
Preferred among these according to the invention are ones containing one or more selected from among amine-based friction modifiers, ester-based friction modifiers, amide-based friction modifiers and fatty acid friction modifiers, and most preferred from the viewpoint of further improving the fatigue life are ones containing one or more selected from among amine-based friction modifiers, fatty acid friction modifiers and amide-based friction modifiers. From the viewpoint of notably improving the anti-shudder life when the lubricating oil composition for a power train device according to the invention is to be used as a lubricating oil for an automatic transmission or continuously variable transmission, it is most preferred to include an imide-based friction modifier.
According to the invention, the one or more compounds selected from among the friction modifiers mentioned above may be used in any desired amounts. There are no particular restrictions on the friction modifier content, but it is preferably 0.01-5.0% by mass and more preferably 0.03-3.0% by mass based on the total amount of the composition. When the lubricating oil composition for a power train device according to the invention is to be used as a lubricating oil for an automatic transmission or continuously variable transmission, the friction modifier content is preferably 0.5-5% by mass and more preferably 2-4% by mass based on the total amount of the composition, since it will be necessary to further improve the frictional properties. Especially when the lubricating oil composition for a power train device according to the invention is to be used as a lubricating oil composition for a manual transmission, the content of the friction modifier is preferably 0.1-3% by mass and more preferably 0.5-1.5% by mass based on the total amount of the composition.
If necessary in order to improve performance, other additives in addition to those mentioned above may be added to the lubricating oil composition for a power train device according to the invention, and such additives may include corrosion inhibitors, rust-preventive agents, demulsifiers, metal inactivating agents, pour point depressants, rubber swelling agents, antifoaming agents, coloring agents and the like, either alone or in combinations of two or more. Specific examples of such additives are the same as for the lubricating oil composition for an internal combustion engine according to the invention described above and will not be repeated here.
When the lubricating oil composition for a power train device according to the invention contains a pour point depressant, it is preferred to use a poly(meth)acrylate-based pour point depressant with a weight-average molecular weight of 50,000-300,000, preferably 60,000-300,000 and most preferably 100,000-250,000, as the pour point depressant.
A lubricating oil composition for a power train device according to the invention having the construction described above can exhibit high levels of antiwear property, prevention of seizure and fatigue life for prolonged periods even with reduced viscosity, and can achieve both fuel efficiency and durability in power train devices while also improving the cold startability. There are no particular restrictions on driving force transmisstting devices to which the lubricating oil composition for a power train device according to the invention may be applied, and specifically there may be mentioned gearboxes such as automatic transmissions, continuously variable transmission s and manual transmissions, as well as final reduction gear boxes, power distribution/regulating mechanisms and the like. The following preferred modes of the invention will now be described: (I) a lubricating oil composition for an automatic transmission or continuously variable transmission, (II) a lubricating oil for a manual transmission composition and (III) a lubricating oil composition for a final reduction gear box.
The kinematic viscosity at 100° C. of the lubricating base oil in the (I) lubricating oil composition for an automatic transmission or continuously variable transmission is preferably 2-8 mm2/s, more preferably 2.6-4.5 mm2/s, even more preferably 2.8-4.3 mm2/s and most preferably 3.3-3.8 mm2/s. If the kinematic viscosity is below this lower limit the lubricity will tend to be insufficient, while if it is greater than the upper limit the cold flow property will tend to be insufficient.
The kinematic viscosity at 40° C. of the lubricating base oil in the (I) lubricating oil composition for an automatic transmission or continuously variable transmission is preferably 15-50 mm2/s, more preferably 20-40 mm2/s and even more preferably 25-35 mm2/s. If the kinematic viscosity is below this lower limit the lubricity will tend to be insufficient, while if it is greater than the upper limit the fuel savings will tend to be insufficient due to increased stirring resistance.
The viscosity index of the lubricating base oil of the invention in the (I) lubricating oil composition for an automatic transmission or continuously variable transmission is preferably 120-160, more preferably 125-150 and even more preferably 130-145. A viscosity index within this range will allow the viscosity-temperature characteristic to be further improved.
The phosphorus-containing compounds in the (I) lubricating oil composition for an automatic transmission or continuously variable transmission are preferably one or more selected from among phosphoric acid, phosphoric acid esters, phosphorous acid, phosphorous acid esters, thiophosphoric acid, thiophosphoric acid esters, thiophosphorous acid, thiophosphorous acid esters, and salts of the foregoing, more preferably one or more selected from among phosphoric acid, phosphoric acid esters, phosphorous acid, phosphorous acid esters, and salts of the foregoing, and even more preferably one or more selected from among phosphoric acid esters, phosphorous acid esters and salts of the foregoing.
The phosphorus-containing compound content of the (I) lubricating oil composition for an automatic transmission or continuously variable transmission is preferably 0.005-0.1% by mass, more preferably 0.01-0.05% by mass and even more preferably 0.02-0.04% by mass, in terms of phosphorus element, based on the total amount of the composition. If the phosphorus-containing compound content is below the aforementioned lower limit the lubricity will tend to be insufficient, while if it is greater than the aforementioned upper limit the wet frictional properties and fatigue life will tend to be insufficient.
The —BF viscosity at −40° C. of the (I) lubricating oil composition for an automatic transmission or continuously variable transmission is preferably not greater than 20,000 mPa·s, more preferably not greater than 15,000 mPa·s, even more preferably not greater than 10,000 mPa·s, yet more preferably not greater than 8,000 mPa·s and most preferably not greater than 7,000 mPa·s. If the BF viscosity exceeds the aforementioned upper limit, the cold startability will tend to be insufficient.
The viscosity index of the (I) lubricating oil composition for an automatic transmission or continuously variable transmission is preferably 100-250, more preferably 150-250 and even more preferably 170-250. If the viscosity index is below the aforementioned lower limit, the fuel savings will tend to be insufficient. A composition wherein the aforementioned upper limit is exceeded will have an excessive poly(meth)acrylate-based viscosity index improver content, and the shear stability will tend to be insufficient.
The kinematic viscosity at 100° C. of the lubricating base oil of the invention in the (II) lubricating oil composition for a manual transmission is preferably 3.0-20 mm2/s, more preferably 3.3-15 mm2/s, even more preferably 3.3-8 mm2/s, yet more preferably 3.8-6 mm2/s and most preferably 4.3-5.5 mm2/s. If the kinematic viscosity is below this lower limit the lubricity will tend to be insufficient, while if it is greater than the upper limit the cold flow property will tend to be insufficient.
The kinematic viscosity at 40° C. of the lubricating base oil of the invention in the (II) lubricating oil composition for a manual transmission is preferably 10-200 mm2/s, more preferably 15-80 mm2/s, even more preferably 20-70 mm2/s and most preferably 23-60 mm2/s. If the kinematic viscosity is below this lower limit the lubricity will tend to be insufficient, while if it is greater than the upper limit the fuel savings will tend to be insufficient due to increased stirring resistance.
The viscosity index of the lubricating base oil of the invention in the (II) lubricating oil composition for a manual transmission is preferably 130-170, more preferably 135-165 and even more preferably 140-160. A viscosity index within this range will allow the viscosity-temperature characteristic to be further improved.
As phosphorus-containing compounds to be added to the (II) lubricating oil composition for a manual transmission, there are preferred one or more selected from among thiophosphoric acid, thiophosphoric acid esters, thiophosphorous acid and thiophosphorous acid esters, there are more preferred one or more selected from among thiophosphoric acid esters and thiophosphorous acid esters, and especially preferred is zinc dithiophosphate.
The phosphorus-containing compound content of the (II) lubricating oil composition for a manual transmission is preferably 0.01-0.2% by mass, more preferably 0.05-0.15% by mass and even more preferably 0.09-0.14% by mass, in terms of phosphorus element, based on the total amount of the composition. If the phosphorus-containing compound content is below the aforementioned lower limit the lubricity and synchro property will tend to be insufficient, while if it is greater than the aforementioned upper limit the heat and oxidation stability and fatigue life will tend to be insufficient.
The —BF viscosity at −40° C. of the (II) lubricating oil composition for a manual transmission is preferably not greater than 20,000 mPa·s, more preferably not greater than 15,000 mPa·s, even more preferably not greater than 10,000 mPa·s, yet more preferably not greater than 9,000 mPa·s and most preferably not greater than 8,000 mPa·s. If the BF viscosity exceeds the aforementioned upper limit, the cold startability will tend to be insufficient.
The viscosity index of the (II) lubricating oil composition for a manual transmission is preferably 100-250, more preferably 140-250 and even more preferably 150-250. If the viscosity index is below the aforementioned lower limit, the fuel savings will tend to be insufficient. A composition wherein the aforementioned upper limit is exceeded will have an excessive poly(meth)acrylate-based viscosity index improver content, and the shear stability will tend to be insufficient.
The kinematic viscosity at 100° C. of the lubricating base oil of the invention in the (III) lubricating oil composition for a final reduction gearbox is preferably 3.0-20 mm2/s, more preferably 3.3-15 mm2/s, even more preferably 3.3-8 mm2/s, yet more preferably 3.8-6 mm2/s and most preferably 4.3-5.5 mm2/s. If the kinematic viscosity is below this lower limit the lubricity will tend to be insufficient, while if it is greater than the upper limit the cold flow property will tend to be insufficient.
The kinematic viscosity at 40° C. of the lubricating base oil in the (III) lubricating oil composition for a final reduction gearbox is preferably 15-200 mm2/s, more preferably 20-150 mm2/s and even more preferably 23-80 mm2/s. If the kinematic viscosity is below this lower limit the lubricity will tend to be insufficient, while if it is greater than the upper limit the fuel savings will tend to be insufficient due to increased stirring resistance.
The viscosity index of the lubricating base oil of the invention in the (III) lubricating oil composition for a final reduction gearbox is preferably 130-170, more preferably 135-165 and even more preferably 140-160. A viscosity index within this range will allow the viscosity-temperature characteristic to be further improved.
As phosphorus-containing compounds to be added to the (III) lubricating oil composition for a final reduction gear there are preferred one or more selected from among phosphoric acid esters, phosphorous acid esters, thiophosphoric acid esters, thiophosphorous acid esters and salts of the foregoing, there are more preferred one or more selected from among phosphoric acid esters, phosphorous acid esters and their amine salts, and there are even more preferred one or more selected from among phosphorous acid esters, amine salts thereof and phosphoric acid esters.
The phosphorus-containing compound content of the (III) lubricating oil composition for a final reduction gear box is preferably 0.01-0.2% by mass, more preferably 0.05-0.15% by mass and even more preferably 0.1-0.14% by mass, as phosphorus element based on the total amount of the composition. If the phosphorus-containing compound content is below the aforementioned lower limit the lubricity will tend to be insufficient, while if it is greater than the aforementioned upper limit the fatigue life will tend to be insufficient.
The —BF viscosity at −40° C. of the (III) lubricating oil composition for a final reduction gear box is preferably not greater than 100,000 mPa·s, more preferably not greater than 50,000 mPa·s, even more preferably not greater than 20,000 mPa·s and yet more preferably not greater than 10,000 mPa·s. If the BF viscosity exceeds the aforementioned upper limit, the cold startability will tend to be insufficient.
The viscosity index of the (III) lubricating composition for automatic transmission or continuously variable transmission is preferably 100-250, more preferably 120-250 and even more preferably 125-250. If the viscosity index is below the aforementioned lower limit, the fuel savings will tend to be insufficient. A composition wherein the aforementioned upper limit is exceeded will have an excessive poly(meth)acrylate-based viscosity index improver content, and the shear stability will tend to be insufficient.
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.
The fraction separated by vacuum distillation in a process for refining of a solvent refined base oil was subjected to solvent extraction with furfural and then hydrotreatment, which was followed by solvent dewaxing with a methyl ethyl ketone-toluene mixed solvent. The wax portion obtained by further deoiling of slack wax removed during the solvent dewaxing (hereunder, “WAX1”) was used as feedstock oil for the lubricating base oil. The properties of WAX1 are shown in Table 1.
WAX1 was hydrocracked in the presence of a hydrocracking catalyst, under conditions with a hydrogen partial pressure of 5 MPa, a mean reaction temperature of 350° C. and a LHSV of 1 hr−1. The hydrocracking catalyst was used as the sulfidized form of a catalyst comprising 3% by mass nickel and 15% by mass molybdenum supported on an amorphous silica-alumina support (silica:alumina=20:80 (mass ratio)).
The decomposition product obtained by the hydrocracking was subjected to vacuum distillation to obtain a lube-oil distillate at 26% by volume with respect to the feedstock oil. The lube-oil distillate was subjected to solvent dewaxing using a methyl ethyl ketone-toluene mixed solvent under conditions with a solvent/oil ratio of 4 and a filtration temperature of −25° C., to obtain lubricating base oils (D1-D3, D4-D6, D7-D9) for Examples 1-3, 4-6 and 7-9 having different viscosity grades.
The results of evaluation testing of the properties and performance of the lubricating base oils of Examples 1-9 are shown in Tables 2-4. The results of evaluation testing of the properties and performance of the high viscosity index base oils R1-R9 as Comparative Examples 1-9 are shown in Tables 5-7.
The results shown in Tables 2-7 indicate that the lubricating base oils of Examples 1-9 had higher viscosity indexes and superior viscosity-temperature characteristics compared to the lubricating base oils of Comparative Examples 1-9. Also, based on the RBOT life comparison between Examples 1-3 and Comparative Examples 1-3 and between Examples 4-6 and Comparative Examples 4-6 shown in Tables 2-7, the lubricating base oils of Examples 1-3 had longer usable lives at each viscosity grade, and exhibited superiority in terms of heat and oxidation stability and antioxidant-addition effect.
For Examples 10 and 11 there were prepared lubricating oil compositions for an internal combustion engine having the compositions shown in Table 8, using base oil D4 of Example 4 and the base oils and additives listed below. For Comparative Examples 10-13 there were prepared lubricating oil compositions for an internal combustion engine having the compositions shown in Table 9, using the base oils and additives listed below. For Comparative Examples 14-16 there were prepared lubricating oil compositions for an internal combustion engine having the compositions shown in Table 10, using base oil 1 and the base oils and additives listed below. The sulfur contents, phosphorus contents, kinematic viscosities at 100° C., base numbers and acid values of the obtained lubricating oil compositions are shown in Tables 3-5. (Base oils)
[Heat and Oxidation Stability Evaluation Test]
The lubricating oil compositions for an internal combustion engine obtained in Examples 10 and 11 and Comparative Examples 10-16 were subjected to a heat and oxidation stability test according to the method described in JIS K 2514, Section 4. (ISOT) (test temperature: 165.5° C.), and the base number retention rates after 24 hours and 72 hours were measured. The results are shown in Tables 8-10.
[Frictional Property Evaluation Test: SRV (Small Reciprocating Wear) Test]
The lubricating oil compositions for an internal combustion engine according to Examples 10 and 11 and Comparative Examples 10-16 were subjected to an SRV test in the following manner, and the frictional properties were evaluated. First, a test piece (steel ball (diameter: 18 mm)/disk, SUJ-2) was prepared for an SRV tester by Optimol Co., and it was finished to a surface roughness of Ra 0.2 μm. The test piece was mounted in the SRV tester by Optimol Co., and the lubricating oil composition for an internal combustion engine was dropped onto the sliding surface of the test piece and tested under conditions with a temperature of 80° C., a load of 30N, an amplitude of 3 mm and a frequency of 50 Hz, measuring the mean frictional coefficient from the period between 15 minutes and 30 minutes after start of the test. The results are shown in Tables 8-10.
The lubricating oil compositions for an internal combustion engine of Examples 10 and 11 and Comparative Examples 10-16 after 24 hours of the heat and oxidation stability evaluation test (hereinafter referred to as “used oils”) were used for an SRV test in the same manner as above. The results are shown in Tables 8-10.
As shown in Table 8, the lubricating oil compositions for an internal combustion engine of Examples 10 and 11 had low base number reduction rates after 24 hours in the oxidation stability test, while the residual base numbers were sufficient even after 72 hours, and therefore excellent oxidation stability was exhibited. The lubricating oil compositions for an internal combustion engine of Examples 10 and 11 also had low initial frictional coefficients, and even after 24 hours of the oxidation stability test had frictional coefficients of below 0.1, thus exhibiting excellent low friction maintenance.
On the other hand, the lubricating oil compositions for an internal combustion engine of Comparative Examples 10-16 exhibited inferior base number retention rate, and after 24 hours of the oxidation stability test had frictional coefficients above 0.1, thus exhibiting poor low friction maintenance.
Also, comparing Example 10 with Comparative Examples 14 and 16 and comparing Comparative Example 10 with Comparative 5 Examples 12 and 13 shows that the lubricating oil composition for an internal combustion engine of Example 10 exhibited notable improvement in the base number retention rate, oxidation stability and low friction maintenance due to addition of components (A) and (B).
For Examples 12 and 13 there were prepared lubricating oil compositions for an automatic transmission having the compositions shown in Table 11, using base oil D1 of Example 1, base oil D4 of Example 4, and the base oil R12 and additives C1, C2, D1 and P1 listed below. For Comparative Examples 17-19, base oil R12 mentioned below, R1 of Comparative Example 1, R4 of Comparative Example 4 and additives C1, C2, D1 and P1 were used to prepare lubricating oil compositions for an automatic transmission having the composition shown in Table 12. Kinematic viscosities at 40° C., viscosity indexes and phosphorus contents of the obtained lubricating oil compositions for an automatic transmission are shown in Tables 11 and 12.
The following evaluation test was then conducted using the lubricating oil compositions for an automatic transmission of Examples 12 and 13 and Comparative Examples 17-19.
[Cold Flow Property Test]
The —BF viscosity at −40° C. of each of the lubricating oil compositions was then measured according to ASTM D 2983. The obtained results are shown in Tables 11 and 12. For this test, a lower BF viscosity value represents a superior cold flow property.
[Shear Stability Test]
An ultrasonic shearing test was conducted under the following conditions according to JASO M347-95, and the kinematic viscosity at 100° C. of each lubricating oil composition was measured after the test. The obtained results are shown in Tables 11 and 12. For this test, a lower viscosity and a higher kinematic viscosity at 100° C. after ultrasonic shearing indicates superior shear stability.
[Antiwear Property Test]
A four ball test was conducted under the following conditions according to JPI-5S-32-90, and the wear scar diameter after the test was measured. The obtained results are shown in Tables 11 and 12. In this test, a smaller wear scar diameter indicates more excellent antiwear property.
[Heat and Oxidation Stability Test]
First, the acid value of each lubricating oil composition was measured. Next, each lubricating oil composition was subjected to forced aging under conditions of 165° C., 144 hours by ISOT according to JIS K 2514 and the acid value thereof was measured, and the increase amount in acid value from the measured acid values before and after the test. The obtained results are shown in Tables 11 and 12. For this test, a lower change in acid value indicates superior heat and oxidation stability.
For Example 14 there was prepared a lubricating oil composition for a manual transmission having the composition shown in Table 13, using base oil D4 of Example 4, base oil D7 of Example 7 and additive C1, as well as the following additives C3, D2 and P2. For Comparative Examples 20 and 21, base oil R4 of Comparative Example 4 and additive C1, or base oil R7 of Comparative Example 7 and additives C3, D2 and P2, was used to prepare lubricating oil compositions for a manual transmission having the composition shown in Table 13. The kinematic viscosities at 40° C., viscosity indexes and phosphorus contents of the obtained lubricating oil compositions for a manual transmission are shown in Table 13.
Next, the lubricating oil compositions for a manual transmission of Example 14 and Comparative Examples 20 and 21 were subjected to the same test as for the lubricating oil compositions for an automatic transmission of Examples 12 and 13 and Comparative Examples 17-19, and the cold flow property, shear stability and antiwear property of each was evaluated. The results are shown in Table 13.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-071152 | Mar 2006 | JP | national |
| 2006-071195 | Mar 2006 | JP | national |
| 2006-071200 | Mar 2006 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2007/055126 | 3/14/2007 | WO | 00 | 6/3/2009 |
