JP2014196519A - Lubricant composition for internal-combustion engine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricant composition for internal-combustion engines which is excellent in heat and oxidation stability and low-temperature viscosity characteristics and is capable of achieving long draining and saving of fuel consumption.SOLUTION: A lubricant composition for internal-combustion engines comprises a lubricant base oil which has a content of the saturated portion to the total amount of the lubricant base oil is 90 mass% or higher and a urea adduct value of 4 mas% or lower and a viscosity index of 100 or higher, an ash-free antioxidant containing no sulfur as a constituent element and one or more selected from ash-free antioxidants containing sulfur as a constituent element and organic molybdenum compounds.

Description

  The present invention relates to a lubricating oil composition for an internal combustion engine, and more specifically, suitable as a lubricating oil for a motorcycle engine, a four-wheeled vehicle, a power generation engine, a marine gasoline engine, a diesel engine, an oxygen-containing compound-containing engine, a gas engine, or the like. The present invention relates to a lubricating oil composition for internal combustion engines.

  Lubricating oils used in internal combustion engines such as automobile engines are required to have thermal and oxidation stability to withstand long-term use under harsh conditions. Furthermore, in recent years, a base oil having a high viscosity index has been demanded from the viewpoint of fuel saving, and various studies on additives and base oils have been made. For example, it is common to mix sulfur-containing compounds with peroxide resolution such as zinc dithiophosphate and molybdenum dithiocarbamate as additives, or ashless antioxidants such as phenolic or amine antioxidants in the base oil (For example, refer to Patent Documents 1 to 4.)

  In addition, as a technique for improving viscosity-temperature characteristics / low-temperature viscosity characteristics and thermal oxidation stability, high viscosity index base oil is obtained by hydrocracking / hydroisomerizing raw oils containing natural or synthetic normal paraffins. Is known (see, for example, Patent Documents 5 to 6). Further, as a method for improving the low temperature viscosity characteristics of the lubricating oil, there is a method of blending an additive such as a pour point depressant with a highly refined mineral base oil.

JP-A-4-36391 JP 63-223094 A JP-A-8-302378 JP 9-003463 A JP-T-2006-502298 JP-T-2002-503754

  In recent years, in addition to the harsher use conditions of internal combustion engine lubricants, there has been a further demand for longer drains of lubricants from the viewpoint of effective use of resources, reduction of waste oil, and cost reduction of lubricant users. Along with the increase, there is an increasing demand for lowering the viscosity at low temperature when starting the engine and reducing the viscous resistance to increase the fuel saving effect. Even if a lubricating base oil used in conventional lubricating oil for internal combustion engines is called a high-performance base oil, its own thermal / oxidative stability is not necessarily sufficient. In addition, it is possible to improve the heat / oxidation stability to some extent by increasing the blending amount of the antioxidant, but the effect of improving the heat / oxidation stability by this method is naturally limited. Further, the viscosity-temperature characteristics / low-temperature viscosity characteristics can be improved to some extent by adding additives to the lubricating base oil, but this method has its limitations. In particular, the effect of the pour point depressant is not proportional to the concentration even if the blending amount is increased, and the shear stability is lowered as the blending amount is increased.

  Conventionally, as an evaluation index of the low temperature viscosity characteristics of the lubricating base oil and the lubricating oil, a pour point, a cloud point, a freezing point, and the like are generally used. Recently, a technique for evaluating low-temperature viscosity characteristics based on a lubricating base oil such as the content of normal paraffin or isoparaffin is also known. However, according to the inventor's study, in order to realize the lubricating base oil and lubricating oil that meet the above requirements, the low temperature viscosity characteristics of the lubricating base oil (e.g. ) Was not necessarily appropriate as an evaluation index.

  The present invention has been made in view of such circumstances, and is excellent in thermal / oxidation stability and viscosity-temperature characteristics / low-temperature viscosity characteristics, and can achieve sufficient long drain properties and fuel economy. It is an object to provide a lubricating oil composition.

In order to solve the above problems, the present invention has a saturated content of 90% by mass or more, a urea adduct value of 4% by mass or less, and a viscosity index of 100 based on the total amount of the lubricating base oil. Containing at least one selected from the above lubricating base oil, an ashless antioxidant not containing sulfur as a constituent element, and an ashless antioxidant containing an organic molybdenum compound and sulfur as constituent elements A lubricating oil composition for an internal combustion engine is provided.
The present invention also includes a lubricating base oil having a urea adduct value of 4% by mass or less and a viscosity index of 100 or more, an ashless antioxidant that does not contain sulfur as a constituent element, and sulfur as a constituent element. There is provided a lubricating oil composition for an internal combustion engine, comprising an ashless antioxidant and at least one selected from organic molybdenum compounds.

  The lubricating base oil contained in the lubricating oil composition for an internal combustion engine of the present invention satisfies the above conditions in terms of urea adduct value and viscosity index, and thus has excellent thermal and oxidation stability. Furthermore, the lubricating base oil, when an additive is blended, can exhibit its function at a higher level while stably dissolving and holding the additive. The lubricating base oil having such excellent characteristics includes an ashless antioxidant that does not contain sulfur as a constituent element (hereinafter sometimes referred to as “component (A)”), and a sulfur base ingredient that does not contain sulfur. By including both of the ash antioxidant and at least one selected from organic molybdenum compounds (hereinafter sometimes referred to as “component (B)”), the heat and heat generated by the synergistic action of components (A) and (B) The effect of improving the oxidation stability can be maximized. Therefore, it is possible to achieve a sufficiently long drain by the lubricating oil composition for an internal combustion engine of the present invention.

  Further, the lubricating base oil contained in the composition for internal combustion engines of the present invention is excellent in viscosity-temperature characteristics and friction characteristics because the urea adduct value and the viscosity index satisfy the above-mentioned conditions. . According to the lubricating base oil, viscosity resistance and stirring resistance in the practical temperature range can be reduced due to excellent viscosity-temperature characteristics. Especially, viscosity resistance and stirring resistance can be reduced under low temperature conditions of 0 ° C. or lower. Since the effect can be exhibited by drastically reducing, energy loss in the apparatus can be reduced and energy saving can be achieved. Furthermore, the lubricating base oil is excellent in terms of solubility and effectiveness of the additive as described above, and when a friction modifier is blended, the friction reducing effect can be obtained at a high level. is there. Therefore, according to the lubricating oil composition for an internal combustion engine of the present invention including such an excellent lubricating base oil, energy loss due to frictional resistance, stirring resistance, etc. in the sliding portion is reduced, and sufficient energy saving is achieved. Can be achieved.

  Furthermore, in the case of the conventional lubricating base oil, it has been difficult to achieve both the improvement of the low-temperature viscosity characteristics and the prevention of volatilization. However, according to the lubricating base oil of the present invention, the low-temperature viscosity characteristics and volatilization prevention Both can be achieved at a high level and in a well-balanced manner. Therefore, the lubricating oil composition for an internal combustion engine of the present invention is useful in terms of improving startability at low temperatures in addition to the long drain and energy saving of the internal combustion engine.

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

  Moreover, the viscosity index as used in the present invention and the kinematic viscosity at 40 ° C. or 100 ° C. described later mean a viscosity index measured according to JIS K 2283-1993 and a kinematic viscosity at 40 ° C. or 100 ° C., respectively. .

  In addition, as described above, improvement of the isomerization rate from normal paraffin to isoparaffin has been studied in the conventional refining method of lubricating base oil by hydrocracking / hydroisomerization. According to the above study, it is difficult to sufficiently improve the low-temperature viscosity characteristics simply by reducing the residual amount of normal paraffin. That is, the isoparaffin produced by hydrocracking / hydroisomerization contains components that adversely affect the low-temperature viscosity characteristics, but this point is not fully recognized in conventional evaluation methods. Analytical techniques such as gas chromatography (GC) and NMR are applied to the analysis of normal paraffin and isoparaffin. In these analytical techniques, components that adversely affect the low-temperature viscosity characteristics are separated or specified from isoparaffin. This cannot be said to be practically effective because it requires complicated work and a lot of time.

  On the other hand, in the measurement of the urea adduct value in the present invention, as urea adduct, a component that adversely affects low-temperature viscosity characteristics among isoparaffins, and further when normal paraffin remains in the lubricating base oil Since the normal paraffin can be collected accurately and reliably, it is excellent as an evaluation index for the low temperature viscosity characteristics of the lubricating base oil. The inventors of the present invention have analyzed by using GC and NMR that the main component of the urea adduct is a normal paraffin and an isoparaffin urea adduct having 6 or more carbon atoms from the end of the main chain to the branch position. Confirm that there is.

In the present invention, the above-mentioned lubricant base oil is about 90% by mass or more based on the total amount of the lubricant base oil, with respect to the raw material oil containing normal paraffin, the saturated content of the object to be processed obtained. It is preferably obtained by a process of hydrocracking / hydroisomerization so that the urea adduct value is 4% by mass or less and the viscosity index is 100 or more.
In addition, the above-mentioned lubricating base oil is hydrocracking / hydroisomerization so that the raw material oil containing normal paraffin has a urea adduct value of 4% by mass or less and a viscosity index of 100 or more. It is preferable that it is obtained by the process of performing chemical conversion. As a result, it is possible to more reliably obtain a lubricating oil composition in which thermal / oxidation stability, viscosity-temperature characteristics, and low-temperature viscosity characteristics are compatible at a high level.

  In addition, the above-mentioned lubricating base oil is hydrocracking / hydroisomerization so that the raw material oil containing normal paraffin has a urea adduct value of 4% by mass or less and a viscosity index of 100 or more. In the case where the raw material oil is obtained by the step of converting the oil, the raw material oil preferably contains 50% by mass or more of slack wax obtained by solvent dewaxing of the lubricating base oil.

  As described above, according to the present invention, it is possible to realize a lubricating oil composition for an internal combustion engine that is excellent in thermal / oxidative stability or further in viscosity-temperature characteristics / low temperature viscosity characteristics, friction characteristics, and volatilization prevention properties. And, by applying the lubricating oil composition for an internal combustion engine of the present invention to the internal combustion engine, it becomes possible to achieve a long drain and energy saving, and further to improve the low temperature startability. Become.

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

  The lubricating oil composition for internal combustion engines of the present invention comprises a lubricating base oil having a urea adduct value of 4% by mass or less and a viscosity index of 100 or more, and (A) ashless oxidation prevention containing no sulfur as a constituent element. And (B) an ashless antioxidant containing sulfur as a constituent element and at least one selected from organic molybdenum compounds.

  The urea adduct value of the lubricating base oil according to the present invention is required to be 4% by mass or less as described above from the viewpoint of improving the low temperature viscosity characteristics without impairing the viscosity-temperature characteristics, and preferably 3. 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2.5 mass% or less. Further, the urea adduct value of the lubricating base oil may be 0% by mass. However, it is possible to obtain a lubricating base oil having sufficient low-temperature viscosity characteristics and a higher viscosity index, and more preferably 0.1% by mass or more in terms of excellent economic efficiency by relaxing dewaxing conditions. Preferably it is 0.5 mass% or more, Most preferably, it is 0.8 mass% or more.

  The viscosity index of the lubricating base oil according to the present invention needs to be 100 or more as described above from the viewpoint of viscosity-temperature characteristics, preferably 110 or more, more preferably 120 or more, still more preferably 130 or more. Especially preferably, it is 140 or more.

  In producing the lubricating base oil according to the present invention, a normal oil containing normal paraffin or a wax containing normal paraffin can be used. The raw material oil may be either mineral oil or synthetic oil, or may be a mixture of two or more of these.

  The raw material oil used in the present invention is preferably a wax-containing raw material that boils in the lubricating oil range defined in ASTM D86 or ASTM D2887. The wax content of the raw material oil is preferably 50% by mass or more and 100% by mass or less based on the total amount of the raw material oil. The wax content of the raw material can be measured by an analytical technique such as nuclear magnetic resonance spectroscopy (ASTM D5292), correlated ring analysis (ndM) method (ASTMD3238), solvent method (ASTMD3235), or the like.

  Examples of the wax-containing raw material include oils derived from solvent refining methods such as raffinate, partial solvent dewaxed oil, dewaxed oil, distillate, reduced pressure gas oil, coker gas oil, slack wax, foots oil, and fisher Examples include Tropsch wax, and among these, slack wax and Fischer-Tropsch wax are preferable.

  Slack waxes are typically derived from hydrocarbon feedstocks by solvent or propane dewaxing. Slack wax may contain residual oil, which can be removed by deoiling. Foots oil corresponds to deoiled slack wax.

  Fischer-Tropsch wax is produced by a so-called Fischer-Tropsch synthesis method.

  Furthermore, you may use a commercial item as raw material oil containing normal paraffin. Specific examples include Paraflint 80 (hydrogenated Fischer-Tropsch wax) and Shell MDS waxy raffinate (hydrogenated and partially isomerized middle distillate synthetic waxy raffinate).

  Moreover, the raw material oil derived from solvent extraction is obtained by sending a high-boiling petroleum fraction from atmospheric distillation to a vacuum distillation apparatus and solvent-extracting the distillation fraction from this apparatus. The residue from the vacuum distillation may be denitrified. In the solvent extraction method, aromatic components are dissolved in the extraction phase while leaving more paraffinic components in the raffinate phase. Naphthene is partitioned into the extraction phase and the raffinate phase. As the solvent for solvent extraction, phenol, furfural, N-methylpyrrolidone and the like are preferably used. By controlling the solvent / oil ratio, the extraction temperature, the method of contacting the distillate to be extracted with the solvent, etc., the degree of separation between the extraction phase and the raffinate phase can be controlled. Furthermore, a bottom fraction obtained from a fuel oil hydrocracking apparatus may be used as a raw material by using a fuel oil hydrocracking apparatus having higher hydrogenation resolution.

The raw material oil is subjected to hydrocracking / hydroisomerization so that the urea adduct value of the material to be treated is 4% by mass or less and the viscosity index is 100 or more. Such a lubricating base oil can be obtained. The hydrocracking / hydroisomerization step is not particularly limited as long as the urea adduct value and the viscosity index of the obtained workpiece satisfy the above conditions. The preferred hydrocracking / hydroisomerization step in the present invention is:
A first step of hydrotreating a raw oil containing normal paraffin using a hydrotreating catalyst;
A second step of hydrodewaxing the object to be treated obtained in the first step using a hydrodewaxing catalyst;
The to-be-processed object obtained by a 2nd process is equipped with the 3rd process of hydrotreating using a hydrotreating catalyst.

  In the conventional hydrocracking / hydroisomerization, a hydrotreating step is provided before the hydrodewaxing step for the purpose of desulfurization / denitrogenation for the prevention of poisoning of the hydrodewaxing catalyst. There is a thing. On the other hand, in the first step (hydrotreating step) in the present invention, a part of the normal paraffin in the feedstock (for example, about 10% by mass, preferably in the previous stage of the second step (hydrodewaxing step), preferably 1 to 10% by mass), and desulfurization / denitrogenation is possible in the first step, but the purpose is different from that of the conventional hydrotreatment. Providing such a first step is preferable for ensuring that the urea adduct value of the article to be processed (lubricant base oil) obtained after the third step is 4% by mass or less.

  Examples of the hydrogenation catalyst used in the first step include a catalyst containing a Group 6 metal, a Group 8-10 metal, and a mixture thereof. Preferred metals include nickel, tungsten, molybdenum, cobalt, and mixtures thereof. The hydrogenation catalyst can be used in a form in which these metals are supported on a refractory metal oxide support, and the metal is usually present as an oxide or sulfide on the support. When a metal mixture is used, the metal may be present as a bulk metal catalyst in which the amount of metal is 30% by mass or more based on the total amount of the catalyst. Examples of the metal oxide support include oxides such as silica, alumina, silica-alumina, and titania, and among these, alumina is preferable. Preferred alumina is γ-type or β-type porous alumina. The amount of metal supported is preferably in the range of 0.5 to 35% by mass based on the total amount of the catalyst. Also, when using a mixture of Group 9-10 metal and Group 6 metal, either Group 9 or Group 10 metal is present in an amount of 0.1-5% by weight, based on the total amount of catalyst, The Group 6 metal is preferably present in an amount of 5 to 30% by mass. Metal loading may be measured by atomic absorption spectroscopy, inductively coupled plasma emission spectroscopy, or other methods specified by ASTM for individual metals.

  The acidity of the metal oxide support can be controlled by adding additives, controlling the nature of the metal oxide support (eg, controlling the amount of silica incorporated into the silica-alumina support), and the like. Examples of additives include halogens, especially fluorine, phosphorus, boron, yttria, alkali metals, alkaline earth metals, rare earth oxides, and magnesia. Cocatalysts such as halogen generally increase the acidity of the metal oxide support, but weakly basic additives such as yttria or magnesia tend to weaken the acidity of such support.

Regarding the hydrotreatment conditions, the treatment temperature is preferably 150 to 450 ° C., more preferably 200 to 400 ° C., the hydrogen partial pressure is preferably 1400 to 20000 kPa, more preferably 2800 to 14000 kPa, and the liquid space velocity (LHSV) is preferably 0.1 to 10 ^-1, more preferably 0.1～5Hr ^-1, a hydrogen / oil ratio is preferably 50~1780m ³ / ^{m 3,} more preferably 89～890M ³ / M ³ . In addition, said conditions are an example and the hydrotreating conditions in the 1st process for the urea adduct value and viscosity index of the to-be-processed object obtained after a 3rd process satisfy | fill the said conditions respectively are a raw material, a catalyst, an apparatus, etc. It is preferable to select appropriately according to the difference.

  The object to be processed after the hydrogenation treatment in the first step may be used as it is in the second step, but the object to be processed is stripped or distilled to generate gas from the object to be processed (liquid product). It is preferable to provide a step of separating and removing the object between the first step and the second step. Thereby, the nitrogen content and sulfur content contained in the object to be treated can be reduced to a level without affecting the long-term use of the hydrodewaxing catalyst in the second step. The object of separation and removal by stripping or the like is mainly gaseous foreign matters such as hydrogen sulfide and ammonia, and stripping can be performed by ordinary means such as a flash drum and a fractionator.

  Moreover, when the conditions of the hydrogenation treatment in the first step are mild, there is a possibility that the remaining polycyclic aromatics may pass through depending on the raw materials used. It may be removed by purification.

  Further, the hydrodewaxing catalyst used in the second step may contain either crystalline or amorphous material. Examples of the crystalline material include molecular sieves having a 10- or 12-membered ring passage mainly composed of aluminosilicate (zeolite) or silicoaluminophosphate (SAPO). Specific examples of zeolite include ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ferrierite, ITQ-13, MCM-68, MCM-71 and the like. Moreover, ECR-42 is mentioned as an example of an aluminophosphate. Examples of molecular sieves include zeolite beta and MCM-68. Among these, it is preferable to use 1 type, or 2 or more types selected from ZSM-48, ZSM-22, and ZSM-23, and ZSM-48 is particularly preferable. The molecular sieve is preferably in the hydrogen form. Although the reduction of the hydrodewaxing catalyst can occur in situ at the time of hydrodewaxing, a hydrodewaxing catalyst that has been subjected to a reduction treatment in advance may be subjected to hydrodewaxing.

  Examples of the amorphous material of the hydrodewaxing catalyst include alumina doped with a group 3 metal, fluorided alumina, silica-alumina, fluorided silica-alumina, silica-alumina, and the like.

  Preferred embodiments of the dewaxing catalyst include those equipped with bifunctional, ie, metal hydrogenation components that are at least one Group 6 metal, at least one Group 8-10 metal, or mixtures thereof. Preferred metals are group 9-10 noble metals such as Pt, Pd or mixtures thereof. The mounting amount of these metals is preferably 0.1 to 30% by mass based on the total amount of the catalyst. Examples of the catalyst preparation and the metal mounting method include an ion exchange method and an impregnation method using a decomposable metal salt.

  When molecular sieves are used, they may be combined with a binder material having heat resistance under hydrodewaxing conditions, or may be without a binder (self-bonding). As binder materials, silica, alumina, silica-alumina, combinations of two components of silica and other metal oxides such as titania, magnesia, tria, zirconia, silica-alumina-tria, silica-alumina-magnesia, etc. Inorganic oxides such as a combination of three components of oxides such as The amount of the molecular sieve in the hydrodewaxing catalyst is preferably 10 to 100% by mass, more preferably 35 to 100% by mass, based on the total amount of the catalyst. The hydrodewaxing catalyst is formed by a method such as spray drying or extrusion. The hydrodewaxing catalyst can be used in a sulfided or non-sulfided form, and a sulfided form is preferred.

Regarding hydrodewaxing conditions, the temperature is preferably 250-400 ° C., more preferably 275-350 ° C., and the hydrogen partial pressure is preferably 791-20786 kPa (100-3000 psig), more preferably 1480-17339 kPa (200- a 2500 psig), liquid hourly space velocity is preferably 0.1 to 10 ^-1, more preferably 0.1~5hr ^-1, a hydrogen / oil ratio is preferably 45~1780m ³ / ^{m 3} (250~10000scf / B), more preferably ^{89~890m 3 / m 3 (500~5000scf /} B). In addition, said conditions are an example and the hydrodewaxing conditions in the 2nd process for the urea adduct value and viscosity index of the to-be-processed object obtained after a 3rd process satisfy | fill the said conditions are a raw material, a catalyst, and an apparatus, respectively. It is preferable to select appropriately according to the difference.

  The object to be treated that has been hydrodewaxed in the second step is subjected to hydrorefining in the third step. Hydrorefining is a form of mild hydrotreating that aims to saturate olefins and residual aromatic compounds by hydrogenation in addition to removal of residual heteroatoms and hues. The hydrorefining in the third step can be carried out in cascade with the dewaxing step.

  The hydrorefining catalyst used in the third step is preferably a metal oxide carrier on which a Group 6 metal, a Group 8-10 metal or a mixture thereof is supported. Preferred metals include noble metals, especially platinum, palladium and mixtures thereof. If a mixture of metals is used, it may be present as a bulk metal catalyst where the amount of metal is 30% by weight or more based on the catalyst. The metal content of the catalyst is preferably 20% by mass or less for non-noble metals and 1% by mass or less for noble metals. The metal oxide support may be either amorphous or crystalline oxide. Specific examples include low acid oxides such as silica, alumina, silica-alumina or titania, and alumina is preferred. From the viewpoint of saturation of the aromatic compound, it is preferable to use a hydrorefining catalyst in which a metal having a relatively strong hydrogenation function is supported on a porous support.

  Preferred hydrorefining catalysts include mesoporous materials belonging to the M41S class or family of catalysts. M41S series catalysts are mesoporous materials with high silica content, and specifically include MCM-41, MCM-48 and MCM-50. Such a hydrorefining catalyst has a pore diameter of 15 to 100 mm, and MCM-41 is particularly preferable. MCM-41 is an inorganic porous non-layered phase having a hexagonal arrangement of uniformly sized pores. The physical structure of MCM-41 is like a bundle of straws where the opening of the straw (cell diameter of the pores) is in the range of 15-100 angstroms. MCM-48 has cubic symmetry, and MCM-50 has a layered structure. MCM-41 can be manufactured with pore openings of different sizes in the mesoporous range. The mesoporous material may have a metal hydrogenation component that is at least one of Group 8, Group 9 or Group 10 metal, and the metal hydrogenation component is preferably a noble metal, particularly a Group 10 noble metal, Pt , Pd or mixtures thereof are most preferred.

Regarding the hydrorefining conditions, the temperature is preferably 150-350 ° C, more preferably 180-250 ° C, the total pressure is preferably 2859-20786 kPa (about 400-3000 psig), and the liquid space velocity is preferably 0. 0.1 to 5 hr ⁻¹ , more preferably 0.5 to ³ hr ⁻¹ , and the hydrogen / oil ratio is preferably 44.5 to 1780 m ³ / m ³ (250 to 10,000 scf / B). In addition, said conditions are an example and the hydrogenation production | generation conditions in the 3rd process for the urea adduct value and viscosity index of the to-be-processed object obtained after a 3rd process satisfy | fill the said conditions respectively are the difference of a raw material or a processing apparatus. It is preferable to select appropriately according to.

  Moreover, about the to-be-processed object obtained after a 3rd process, you may separate and remove a predetermined component by distillation etc. as needed.

  In the lubricating base oil according to the present invention obtained by the above production method, the other properties are not particularly limited as long as the urea adduct value and the viscosity index satisfy the above-mentioned conditions. It is preferable that the following conditions are further satisfied.

  The content of the saturated component in the lubricating base oil according to the present invention is preferably 90% by mass or more, more preferably 93% by mass or more, and still more preferably 95% by mass or more, based on the total amount of the lubricating oil base oil. Moreover, the ratio of the cyclic | annular saturated part to the said saturated part becomes like this. Preferably it is 0.1-50 mass%, More preferably, it is 0.5-40 mass%, More preferably, it is 1-30 mass%, Most preferably, it is 5-20. % By mass. Viscosity-temperature characteristics and thermal / oxidative stability can be achieved by satisfying the above conditions for the content of the saturated component and the ratio of the cyclic saturated component in the saturated component, respectively. When the additive is blended, the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricating base oil. Furthermore, when the content of the saturated component and the ratio of the cyclic saturated component in the saturated component satisfy the above conditions, the friction characteristics of the lubricating base oil itself can be improved, and as a result, the friction reducing effect is improved. As a result, energy saving can be improved.

  In addition, when content of a saturated part is less than 90 mass%, it exists in the tendency for a viscosity-temperature characteristic, thermal / oxidation stability, and a friction characteristic to become inadequate. Further, when the ratio of the cyclic saturated component to the saturated component is less than 0.1% by mass, when the additive is blended with the lubricating base oil, the solubility of the additive becomes insufficient, and the lubricating base Since the effective amount of the additive dissolved and retained in the oil is reduced, the function of the additive tends to be unable to be obtained effectively. Furthermore, when the ratio of the cyclic saturated component in the saturated component exceeds 50% by mass, the effectiveness of the additive tends to decrease when the additive is blended with the lubricating base oil.

  In the present invention, the ratio of the cyclic saturated component in the saturated component being 0.1 to 50% by mass is equivalent to the non-cyclic saturated component in the saturated component being 99.9 to 50% by mass. Here, the non-cyclic saturated component includes both normal paraffin and isoparaffin. The ratio of normal paraffin and isoparaffin in the lubricating base oil according to the present invention is not particularly limited as long as the urea adduct value satisfies the above conditions, but the ratio of isoparaffin is preferably 50 to 99 based on the total amount of the lubricating base oil. 9.9% by mass, more preferably 60 to 99.9% by mass, still more preferably 70 to 99.9% by mass, and particularly preferably 80 to 99.9% by mass. When the ratio of isoparaffin in the lubricating base oil satisfies the above conditions, the viscosity-temperature characteristics and thermal / oxidative stability can be further improved, and when the additive is added to the lubricating base oil Therefore, the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held.

  In addition, content of the saturated part said by this invention means the value (unit: mass%) measured based on ASTM D 2007-93.

  Moreover, the ratio of the cyclic saturated component and the non-cyclic saturated component in the saturated component referred to in the present invention is a naphthene component measured according to ASTM D 2786-91, respectively (measuring object: 1-ring to 6-ring naphthene, unit : Mass%) and alkane content (unit: mass%).

In addition, the ratio of normal paraffin in the lubricating base oil referred to in the present invention is a gas chromatographic analysis of the saturated component separated and fractionated by the method described in ASTM D 2007-93 under the following conditions. This means a value obtained by converting the measured value when the ratio of normal paraffin in the saturated content is identified and quantified, based on the total amount of the lubricating base oil. In the identification and quantification, a normal paraffin mixed sample having 5 to 50 carbon atoms is used as a standard sample, and the normal paraffin occupying the saturated component is the total peak area value of the chromatogram (the peak derived from the diluent). Is obtained as a ratio of the sum of peak area values corresponding to each normal paraffin.
(Gas chromatography conditions)
Column: non-polar liquid phase column (length 25 mm, inner diameter 0.3 mmφ, liquid phase film thickness 0.1 μm)
Temperature rising condition: 50 ° C. to 400 ° C. (temperature rising rate: 10 ° C./min)
Carrier gas: helium (linear velocity: 40 cm / min)
Split ratio: 90/1
Sample injection amount: 0.5 μL (injection amount of sample diluted 20 times with carbon disulfide)
Further, the ratio of isoparaffin in the lubricating base oil means a value obtained by converting the difference between the non-cyclic saturated component in the saturated component and the normal paraffin component in the saturated component, based on the total amount of the lubricant base oil. .

  In the method of separating saturated components, or in analyzing the composition of cyclic saturated components, non-cyclic saturated components, etc., a similar method can be used in which similar results can be obtained. For example, in addition to the above, a method described in ASTM D 2425-93, a method described in ASTM D 2549-91, a method using high performance liquid chromatography (HPLC), a method obtained by improving these methods, and the like can be given.

  In the lubricating base oil according to the present invention, when the bottom fraction obtained from the fuel oil hydrocracking apparatus is used as a raw material, the content of the saturated component is 90% by mass or more and occupies the saturated component. The proportion of cyclic saturated component is 30 to 50% by mass, the proportion of non-cyclic saturated component in the saturated component is 50 to 70% by mass, the proportion of isoparaffin in the lubricating base oil is 40 to 70% by mass, and the viscosity index is A base oil of 100 to 135, preferably 120 to 130 can be obtained. When the urea adduct value satisfies the above conditions, the effect of the present invention, in particular, the MRV viscosity at −40 ° C. is 20000 mPa · s or less, particularly 10000 mPa · s. A lubricating oil composition having the following excellent low-temperature viscosity characteristics can be obtained. In the lubricating base oil according to the present invention, when slack wax or Fischer-Tropsch wax, which is a raw material having a high wax content (for example, a normal paraffin content of 50% by mass or more) is used as a raw material, Of 90% by mass or more, the proportion of cyclic saturated component in the saturated component is 0.1 to 40% by mass, the proportion of non-cyclic saturated component in the saturated component is 60 to 99.9% by mass, lubrication A base oil having a ratio of isoparaffin in the oil base oil of 60 to 99.9% by mass and a viscosity index of 100 to 170, preferably 135 to 160 is obtained. Effect, particularly excellent in high viscosity index and low temperature viscosity characteristics of MRV viscosity at −40 ° C. of 12000 mPa · s or less, particularly 7000 mPa · s or less It can be obtained Namerayu composition.

  Moreover, the aromatic content in the lubricating base oil according to the present invention is preferably 5% by mass or less, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 3% by mass, based on the total amount of the lubricating base oil. 1% by mass, particularly preferably 0.1 to 0.5% by mass. If the aromatic content exceeds the above upper limit, the viscosity-temperature characteristics, thermal / oxidative stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to decrease. When an additive is blended with the additive, the effectiveness of the additive tends to decrease. Further, the lubricating base oil according to the present invention may not contain an aromatic component, but the solubility of the additive is further improved by setting the aromatic content to 0.05% by mass or more. Can be increased.

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

The% C _p of the lubricating base oil according to the present invention is preferably 80 or more, more preferably 82 to 99, still more preferably 85 to 98, and particularly preferably 90 to 97. If the% C _p of the lubricating base oil is less than 80, the viscosity-temperature characteristics, thermal / oxidative stability, and friction characteristics tend to be reduced, and when the additive is added to the lubricating base oil The effectiveness of the additive tends to decrease. Further, when the% C _p value of the lubricating base oil exceeds 99, the additive solubility will tend to be lower.

Moreover,% _{C N} of the lubricating base oil of the present invention is preferably 20 or less, more preferably 15 or less, more preferably 1 to 12, more preferably 3 to 10. If the% C _N value of the lubricating base oil exceeds 20, the viscosity - temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced. Moreover, when% _CN is less than 1, the solubility of the additive tends to decrease.

Moreover,% _{C A} of the lubricating base oil of the present invention is preferably 0.7 or less, more preferably 0.6 or less, more preferably 0.1 to 0.5. When% C _A of the lubricating base oil exceeds 0.7, the viscosity - temperature characteristic, heat and oxidation stability and frictional properties will tend to be reduced. Moreover,% C _A of the lubricating base oil of the invention may be 0% by 0.1 or more C _A, it is possible to further increase the solubility of additives.

Furthermore, the ratio of the lubricating base% in oil _{C P} and% _{C N} of the present _invention,% C is preferably P /% _{C N} is 7 or more, more preferably 7.5 or more, More preferably, it is 8 or more. When% C _P /% _CN is less than 7, viscosity-temperature characteristics, thermal / oxidative stability and friction characteristics tend to be reduced, and further when an additive is blended in the lubricating base oil. The effectiveness of the additive tends to decrease. _{Moreover,% C} P /% C _N is preferably 200 or less, more preferably 100 or less, more preferably 50 or less, particularly preferably 25 or less. By setting% C _P /% _CN to 200 or less, the solubility of the additive can be further increased.

Incidentally, _say% C P in the present invention,% _C A _N and% _{C A,} obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number The percentage of the total number of naphthene carbons to the total number of carbons, and the percentage of the total number of aromatic carbons to the total number of carbons. That is, the preferred ranges of% C _P ,% C _N and% C _A described above are based on the values obtained by the above method. For example, even a lubricating base oil containing no naphthene is obtained by the above method. is% C _N may indicate a value greater than zero.

  The iodine value of the lubricating base oil according to the present invention is preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.15 or less, and less than 0.01. However, it is preferably 0.001 or more, and more preferably 0.05 or more, from the viewpoint of a small effect that is commensurate with it and economic efficiency. By setting the iodine value of the lubricating base oil to 0.5 or less, the thermal and oxidation stability can be dramatically improved. In addition, the iodine value as used in the field of this invention means the iodine value measured by the indicator titration method of JIS K0070 "the acid value of a chemical product, the saponification value, the iodine value, the hydroxyl value, and the unsaponification value."

  Further, the sulfur content in the lubricating base oil according to the present invention depends on the sulfur content of the raw material. For example, when a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like is used, a lubricating base oil that does not substantially contain sulfur can be obtained. In addition, when using raw materials containing sulfur such as slack wax obtained in the refining process of the lubricating base oil and microwax obtained in the refining process, the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it. In the lubricating base oil according to the present invention, the content of sulfur is preferably 10 ppm by mass or less, from the viewpoint of further improving thermal and oxidation stability and reducing sulfur, and 5 ppm by mass or less. More preferred is 3 ppm by mass or less.

  Further, from the viewpoint of cost reduction, it is preferable to use slack wax or the like as a raw material. In that case, the sulfur content in the obtained lubricating base oil is preferably 50 ppm by mass or less, and preferably 10 ppm by mass or less. More preferred. In addition, the sulfur content as used in the field of this invention means the sulfur content measured based on JISK2541-1996.

  The nitrogen content in the lubricating base oil according to the present invention is not particularly limited, but is preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, and further preferably 1 ppm by mass or less. If the nitrogen content exceeds 5 ppm by mass, the thermal and oxidation stability tends to decrease. In addition, the nitrogen content as used in the field of this invention means the nitrogen content measured based on JISK2609-1990.

The kinematic viscosity of the lubricating base oil according to the present invention is preferably 1.5 to ²⁰ mm ² / s, more preferably 2.0 to 11 mm ² / s at 100 ° C. When the kinematic viscosity at 100 ° C. of the lubricating base oil is less than 1.5 mm ² / s, it is not preferable in terms of evaporation loss. In addition, when trying to obtain a lubricating base oil having a kinematic viscosity at 100 ° C. exceeding 20 mm ² / s, the yield decreases, and the decomposition rate can be increased even when heavy wax is used as a raw material. Since it becomes difficult, it is not preferable.

In the present invention, it is preferable to use a lubricating base oil having a kinematic viscosity at 100 ° C. in the following range by distillation or the like.
(I) less than the kinematic viscosity at 100 ° C. is 1.5 mm ² / s or more 3.5 mm ² / s, more preferably kinematic viscosity at 2.0 to 3.0 mm ² / s lubricating base oils (II) 100 ° C. There 3.0 mm ² / s or more 4.5mm less than ² / s, more preferably a kinematic viscosity at 3.5~4.1mm ² / s lubricating base oil (III) 100 ℃ 4.5~20mm ² / s, more preferably 4.8 to 11 mm ² / s, particularly preferably 5.5 to 8.0 mm ² / s.

Moreover, the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present invention is preferably 6.0 to 80 mm ² / s, more preferably 8.0 to 50 mm ² / s. In the present invention, it is preferable to use a lubricating oil fraction having a kinematic viscosity at 40 ° C. in the following range by fractionation by distillation or the like.
(IV) less than the kinematic viscosity at 40 ° C. is 6.0 mm ² / s or more 12 mm ² / s, more preferably 8.0~12mm ² / s lubricating base oil (V) kinematic viscosity at 40 ° C. is 12 mm ² / More than s and less than 28 mm < ² > / s, more preferably 13-19 mm < ² > / s lubricating base oil (VI) The kinematic viscosity at 40 [deg.] C. is 28-50 mm < ² > / s, more preferably 29-45 mm < ² > / s, particularly preferred. Is a lubricating base oil of 30 to 40 mm ² / s.

  The above-mentioned lubricating base oils (I) and (IV) have a viscosity-temperature characteristic and low temperature compared with conventional lubricating base oils having the same viscosity grade by satisfying the above conditions for the urea adduct value and the viscosity index, respectively. Viscosity characteristics can be achieved at a high level, in particular, low temperature viscosity characteristics are excellent, and viscosity resistance and stirring resistance can be significantly reduced. Moreover, the BF viscosity in -40 degreeC can be 2000 mPa * s or less by mix | blending a pour point depressant. The BF viscosity at −40 ° C. means the viscosity measured according to JPI-5S-26-99.

  The lubricating base oils (II) and (V) have a viscosity-temperature characteristic compared to a conventional lubricating base oil having the same viscosity grade by satisfying the above conditions for the urea adduct value and the viscosity index, respectively. And low-temperature viscosity characteristics can be achieved at a high level. In particular, the low-temperature viscosity characteristics are excellent, and further, volatilization prevention and lubricity are excellent. For example, in the lubricating base oils (II) and (V), the CCS viscosity at −35 ° C. can be set to 3000 mPa · s or less.

  In addition, the lubricating base oils (III) and (VI) have viscosity-temperature characteristics compared to conventional lubricating base oils having the same viscosity grade by satisfying the above conditions for the urea adduct value and the viscosity index, respectively. And low-temperature viscosity characteristics can be achieved at a high level. In particular, the low-temperature viscosity characteristics are excellent, and further, volatilization prevention, thermal / oxidative stability, and lubricity are excellent.

  Further, the refractive index at 20 ° C. of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, but for example, the refractive index at 20 ° C. of the lubricating base oils (I) and (IV). Is preferably 1.455 or less, more preferably 1.453 or less, and still more preferably 1.451 or less. Moreover, the refractive index at 20 ° C. of the lubricating base oils (II) and (V) is preferably 1.460 or less, more preferably 1.457 or less, and still more preferably 1.455 or less. The refractive index of the lubricating base oils (III) and (VI) at 20 ° C. is preferably 1.465 or less, more preferably 1.463 or less, and still more preferably 1.460 or less. If the refractive index exceeds the above upper limit, the viscosity-temperature characteristics and thermal / oxidative stability of the lubricating base oil tend to be reduced, and further, the volatilization preventing properties and low-temperature viscosity characteristics tend to deteriorate. When an additive is blended with the additive, the effectiveness of the additive tends to decrease.

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

  In addition, the CCS viscosity of the lubricating base oil according to the present invention at −35 ° C. depends on the viscosity grade of the lubricating base oil, for example, the lubricating base oils (I) and (IV) at −35 ° C. The CCS viscosity is preferably 1000 mPa · s or less. Further, the CCS viscosity at −35 ° C. of the lubricating base oils (II) and (V) is preferably 3000 mPa · s or less, more preferably 2400 mPa · s or less, still more preferably 2000 mPa · s or less, and further preferably 1800 mPa · s. · S or less, particularly preferably 1600 mPa · s or less. The CCS viscosity of the lubricating base oils (III) and (VI) at −35 ° C. is preferably 15000 mPa · s or less, more preferably 10000 mPa · s or less. When the CCS viscosity at −35 ° C. exceeds the upper limit, the low-temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease. In addition, the CCS viscosity at −35 ° C. in the present invention means a viscosity measured according to JIS K 2010-1993.

  Further, the BF viscosity at −40 ° C. of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, but for example, at −40 ° C. of the lubricating base oils (I) and (IV). The BF viscosity is preferably 10,000 mPa · s or less, more preferably 8000 mPa · s, and still more preferably 6000 mPa · s or less. Moreover, the BF viscosity at −40 ° C. of the lubricating base oils (II) and (V) is preferably 1500,000 mPa · s or less, more preferably 1000000 mPa · s or less. When the BF viscosity at −40 ° C. exceeds the upper limit, the low-temperature fluidity of the entire lubricating oil using the lubricating base oil tends to decrease.

Further, the density (ρ ₁₅ ) at 15 ° C. of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, but is not more than the value of ρ represented by the following formula (1), that is, ρ It is preferable that ₁₅ ≦ ρ.
ρ = 0.0025 × kv100 + 0.816 (1)
[Wherein, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil at 100 ° C. ]
When ρ ₁₅ > ρ, the viscosity-temperature characteristics and thermal / oxidation stability, volatilization prevention properties and low-temperature viscosity characteristics tend to decrease, and additives are added to the lubricating base oil. In some cases, the effectiveness of the additive tends to decrease.

For example, ρ ₁₅ of the lubricating base oils (I) and (IV) is preferably 0.825 or less, more preferably 0.820 or less. Moreover, ρ ₁₅ of the lubricating base oils (II) and (V) is preferably 0.835 or less, more preferably 0.830 or less. The ρ ₁₅ of the lubricating base oils (III) and (VI) is preferably 0.840 or less, more preferably 0.835 or less.

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

In addition, the aniline point (AP (° C.)) of the lubricating base oil according to the present invention depends on the viscosity grade of the lubricating base oil, but is not less than the value of A represented by the following formula (2), that is, AP It is preferable that ≧ A.
A = 4.3 × kv100 + 100 (2)
[Wherein, kv100 represents the kinematic viscosity (mm ² / s) of the lubricating base oil at 100 ° C. ]
When AP <A, viscosity-temperature characteristics and thermal / oxidative stability, volatilization prevention properties and low-temperature viscosity characteristics tend to decrease, and when additives are added to the lubricating base oil In addition, the effectiveness of the additive tends to decrease.

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

  Further, the NOACK evaporation amount of the lubricating base oil according to the present invention is not particularly limited. For example, the NOACK evaporation amount of the lubricating base oils (I) and (IV) is preferably 20% by mass or more, and more preferably Is 25% by mass or more, more preferably 30 or more, preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. The NOACK evaporation amount of the lubricating base oils (II) and (V) is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, and preferably 20%. It is at most mass%, more preferably at most 16 mass%, still more preferably at most 15 mass%. The NOACK evaporation amount of the lubricating base oils (III) and (VI) is preferably 0% by mass or more, more preferably 1% by mass or more, and preferably 6% by mass or less, more preferably 5%. It is at most 4% by mass, more preferably at most 4% by mass. When the NOACK evaporation amount is the lower limit value, it tends to be difficult to improve the low temperature viscosity characteristics. Further, when the NOACK evaporation amount exceeds the upper limit value, when the lubricating base oil is used as the lubricating oil for an internal combustion engine, the evaporation loss amount of the lubricating oil increases, and accordingly, catalyst poisoning is promoted. Therefore, it is not preferable. In addition, the NOACK evaporation amount as used in the field of this invention means the evaporation loss amount measured based on ASTM D 5800-95.

  Further, the distillation properties of the lubricating base oil according to the present invention are preferably gas chromatography distillation, wherein the initial boiling point (IBP) is 290 to 440 ° C. and the end point (FBP) is 430 to 580 ° C. Lubricating base oils (I) to (III) and (IV) to (VI) having the preferred viscosity ranges described above are obtained by rectifying one or more fractions selected from the fractions in the range. Can be obtained.

  For example, regarding the distillation properties of the lubricating base oils (I) and (IV), the initial boiling point (IBP) is preferably 260 to 340 ° C, more preferably 270 to 330 ° C, and still more preferably 280 to 320 ° C. It is. Moreover, 10% distillation temperature (T10) becomes like this. Preferably it is 310-390 degreeC, More preferably, it is 320-380 degreeC, More preferably, it is 330-370 degreeC. Moreover, 50% distillation point (T50) becomes like this. Preferably it is 340-440 degreeC, More preferably, it is 360-430 degreeC, More preferably, it is 370-420 degreeC. Moreover, 90% distillation point (T90) becomes like this. Preferably it is 405-465 degreeC, More preferably, it is 415-455 degreeC, More preferably, it is 425-445 degreeC. Moreover, an end point (FBP) becomes like this. Preferably it is 430-490 degreeC, More preferably, it is 440-480 degreeC, More preferably, it is 450-490 degreeC. Moreover, T90-T10 becomes like this. Preferably it is 60-140 degreeC, More preferably, it is 70-130 degreeC, More preferably, it is 80-120 degreeC. Moreover, FBP-IBP becomes like this. Preferably it is 140-200 degreeC, More preferably, it is 150-190 degreeC, More preferably, it is 160-180 degreeC. Further, T10-IBP is preferably 40 to 100 ° C, more preferably 50 to 90 ° C, and further preferably 60 to 80 ° C. Moreover, FBP-T90 becomes like this. Preferably it is 5-60 degreeC, More preferably, it is 10-55 degreeC, More preferably, it is 15-50 degreeC.

  Further, regarding the distillation properties of the lubricating base oils (II) and (V), the initial boiling point (IBP) is preferably 310 to 400 ° C, more preferably 320 to 390 ° C, still more preferably 330 to 380 ° C. It is. Moreover, 10% distillation temperature (T10) becomes like this. Preferably it is 350-430 degreeC, More preferably, it is 360-420 degreeC, More preferably, it is 370-410 degreeC. The 50% distillation point (T50) is preferably 390 to 470 ° C, more preferably 400 to 460 ° C, still more preferably 410 to 450 ° C. Moreover, 90% distillation point (T90) becomes like this. Preferably it is 420-490 degreeC, More preferably, it is 430-480 degreeC, More preferably, it is 440-470 degreeC. Moreover, an end point (FBP) becomes like this. Preferably it is 450-530 degreeC, More preferably, it is 460-520 degreeC, More preferably, it is 470-510 degreeC. Moreover, T90-T10 becomes like this. Preferably it is 40-100 degreeC, More preferably, it is 45-90 degreeC, More preferably, it is 50-80 degreeC. Moreover, FBP-IBP becomes like this. Preferably it is 110-170 degreeC, More preferably, it is 120-160 degreeC, More preferably, it is 130-150 degreeC. T10-IBP is preferably 5 to 60 ° C, more preferably 10 to 55 ° C, and still more preferably 15 to 50 ° C. Moreover, FBP-T90 becomes like this. Preferably it is 5-60 degreeC, More preferably, it is 10-55 degreeC, More preferably, it is 15-50 degreeC.

  The initial boiling point (IBP) of the lubricating base oils (III) and (VI) is preferably 440 to 480 ° C, more preferably 430 to 470 ° C, and still more preferably 420 to 460 ° C. It is. Moreover, 10% distillation temperature (T10) becomes like this. Preferably it is 450-510 degreeC, More preferably, it is 460-500 degreeC, More preferably, it is 460-480 degreeC. The 50% distillation point (T50) is preferably 470 to 540 ° C, more preferably 480 to 530 ° C, still more preferably 490 to 520 ° C. Moreover, 90% distillation point (T90) becomes like this. Preferably it is 470-560 degreeC, More preferably, it is 480-550 degreeC, More preferably, it is 490-540 degreeC. Moreover, an end point (FBP) becomes like this. Preferably it is 505-565 degreeC, More preferably, it is 515-555 degreeC, More preferably, it is 525-565 degreeC. Moreover, T90-T10 becomes like this. Preferably it is 35-80 degreeC, More preferably, it is 45-70 degreeC, More preferably, it is 55-80 degreeC. Moreover, FBP-IBP becomes like this. Preferably it is 50-130 degreeC, More preferably, it is 60-120 degreeC, More preferably, it is 70-110 degreeC. Further, T10-IBP is preferably 5 to 65 ° C, more preferably 10 to 55 ° C, and still more preferably 10 to 45 ° C. Moreover, FBP-T90 becomes like this. Preferably it is 5-60 degreeC, More preferably, it is 5-50 degreeC, More preferably, it is 5-40 degreeC.

  In each of the lubricating base oils (I) to (VI), IBP, T10, T50, T90, FBP, T90-T10, FBP-IBP, T10-IBP, and FBP-T90 are set to the above preferable ranges. Further, it is possible to further improve the low temperature viscosity and further reduce the evaporation loss. In addition, about each of T90-T10, FBP-IBP, T10-IBP, and FBP-T90, when the distillation range is made too narrow, the yield of lubricating base oil is deteriorated, which is not preferable in terms of economy. .

  In the present invention, IBP, T10, T50, T90 and FBP mean distillate points measured in accordance with ASTM D 2887-97, respectively.

  Further, although the residual metal content in the lubricating base oil according to the present invention is derived from the metal content included in the catalyst and raw materials that are inevitably mixed in the manufacturing process, it is preferable that the residual metal content be sufficiently removed. . For example, the contents of Al, Mo, and Ni are each preferably 1 mass ppm or less. If the content of these metals exceeds the above upper limit, the function of the additive blended with the lubricating base oil tends to be inhibited.

  In addition, the residual metal content as used in the field of this invention means the metal content measured based on JPI-5S-38-2003.

  Moreover, it is preferable that the lubricating base oil according to the present invention exhibits the RBOT life shown below according to its kinematic viscosity. For example, the RBOT life of the lubricating base oils (I) and (IV) is preferably 290 min or more, more preferably 300 min or more, and further preferably 310 min or more. The RBOT life of the lubricating base oils (II) and (V) is preferably 375 min or more, more preferably 400 min or more, and further preferably 425 min or more. The RBOT life of the lubricating base oils (III) and (VI) is preferably 400 min or longer, more preferably 425 min or longer, and further preferably 440 min or longer. When the RBOT life is less than the lower limit, the viscosity-temperature characteristics and thermal / oxidative stability of the lubricating base oil tend to decrease. Further, when an additive is blended in the lubricating base oil, The effectiveness of the additive tends to decrease.

  The RBOT life as used herein refers to a composition in which 0.2% by mass of a phenolic antioxidant (2,6-di-tert-butyl-p-cresol; DBPC) is added to a lubricating base oil. It means the RBOT value measured according to JIS K 2514-1996.

  The lubricating base oil according to the present invention having the above structure is excellent in viscosity-temperature characteristics and low-temperature viscosity characteristics, has low viscosity resistance and stirring resistance, and further has improved thermal / oxidation stability and friction characteristics. Yes, it is possible to improve the friction reducing effect, and thus improve the energy saving property. In addition, when an additive is blended in the lubricating base oil according to the present invention, the function of the additive (the effect of improving the low temperature viscosity characteristics by the pour point depressant, the effect of improving the heat and oxidation stability by the antioxidant, the friction The friction reducing effect by the adjusting agent and the wear resistance improving effect by the antiwear agent can be expressed at a higher level. Therefore, the present invention is a lubricating oil for internal combustion engines used for internal combustion engines such as gasoline engines for passenger cars, gasoline engines for motorcycles, diesel engines, gas engines, gas heat pump engines, marine engines, power generation engines, etc. The lubricating base oil according to the present invention includes other lubricating oils (drive transmission oils), shock absorbers, construction machinery used in drive transmission devices such as automatic transmissions, manual transmissions, continuously variable transmissions, and final reduction gears. Hydraulic fluids used in hydraulic equipment such as compressor oil, turbine oil, industrial gear oil, refrigeration oil, rust prevention oil, heat medium oil, gas holder seal oil, bearing oil, paper machine oil, machine tool oil, It can also be suitably used for sliding guide surface oil, electrical insulating oil, cutting oil, press oil, rolling oil, heat treatment oil, etc., and the lubricating base oil according to the present invention can be used for these applications. To improve the viscosity-temperature characteristics, thermal / oxidation stability, energy savings, fuel efficiency, etc. of each lubricating oil, and to extend the life of each lubricating oil and reduce environmentally hazardous substances at a high level. Will be able to.

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

Although it does not restrict | limit especially as another base oil used together with the lubricating base oil which concerns on this invention, As a mineral oil type | system | group base oil, solvent refined mineral oil whose dynamic viscosity in 100 degreeC is 1-100 mm < ² > / s, for example, hydrogen Examples include hydrocracked mineral oil, hydrorefined mineral oil, and solvent dewaxing base oil.

  Synthetic base oils include poly α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridec Decyl adipate, di-2-ethylhexyl sebacate, etc.), polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyl Examples thereof include diphenyl ether and polyphenyl ether, and among them, poly α-olefin is preferable. As the poly α-olefin, typically, an oligomer or co-oligomer (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and those. Of the hydrides.

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

  Moreover, the lubricating oil composition for internal combustion engines of this invention contains the ashless antioxidant which does not contain sulfur as a structural element as (A) component. As the component (A), a phenol-based or amine-based ashless antioxidant that does not contain sulfur as a constituent element is suitable.

  Specific examples of the phenol-based ashless antioxidant that does not contain sulfur as a constituent element include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2 , 6-di-tert-butylphenol), 4,4'-bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-isopropylidenebis (2,6-di-tert-butylphenol) ), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-isobutylidenebis (4,6-dimethylphenol) 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethyl) Phenol), 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 thereof. Among these, hydroxyphenyl group-substituted ester-based antioxidant (octyl-3- (3,5-di-tert-butyl-4-hydroxy), which is an ester of a hydroxyphenyl group-substituted fatty acid and an alcohol having 4 to 12 carbon atoms. Phenyl) propionate, octyl-3- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, etc.) and bisphenol antioxidants are preferred, and hydroxyphenyl group-substituted ester antioxidants are more preferred. A phenol compound having a molecular weight of 240 or more is preferable because it has a high decomposition temperature and exhibits its effect even under higher temperature conditions.

  Specific examples of amine-based ashless antioxidants that do not contain sulfur as a constituent element include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, alkyldiphenylamine, dialkyldiphenylamine, N, N′-diphenyl- p-Phenylenediamine and mixtures thereof are mentioned. As the alkyl group possessed by these amine-based ashless antioxidants, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 4 to 12 carbon atoms is more preferable. .

  The content of the component (A) in the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more based on the total amount of the composition. Especially preferably, it is 1.0 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it is 2 mass% or less. When the content is less than 0.01% by mass, the heat / oxidation stability of the lubricating oil composition becomes insufficient, and in particular, it tends to be impossible to maintain excellent cleanliness over a long period of time. On the other hand, when content of (A) component exceeds 5 mass%, it exists in the tendency for the storage stability of a lubricating oil composition to fall.

  In the present invention, as component (A), 0.4 to 2% by mass of a phenol-based ashless antioxidant and 0.4 to 2% by mass of an amine-based ashless antioxidant are used in combination based on the total amount of the composition. Alternatively, it is particularly preferable to use 0.5 to 2% by mass, more preferably 0.6 to 1.5% by mass of an amine-based antioxidant alone, thereby maintaining excellent cleanliness over a long period of time. be able to.

  The lubricating oil composition for an internal combustion engine of the present invention has at least one selected from (B-1) an ashless antioxidant containing sulfur as a constituent element and (B-2) an organic molybdenum compound as the component (B). Contains seeds.

  (B-1) Ashless antioxidants containing sulfur as a constituent element include sulfurized fats and oils, dihydrocarbyl polysulfides, dithiocarbamates, thiadiazoles, and phenol-based ashless antioxidants containing sulfur as a constituent element. Is preferred.

  Examples of sulfurized fats and oils include sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil, and sulfurized rice bran oil; disulfide fatty acids such as sulfurized oleic acid; and sulfurized esters such as methyl sulfide oleate. .

Examples of the sulfurized olefin include compounds represented by the following general formula (4).
R ¹¹ -S _x -R ¹² (4)
[In General Formula (4), R ¹¹ represents an alkenyl group having 2 to 15 carbon atoms, R ¹² represents an alkyl group or alkenyl group having 2 to 15 carbon atoms, and x represents an integer of 1 to 8. ]
The compound represented by the general formula (4) can be obtained by reacting an olefin having 2 to 15 carbon atoms or a dimer or tetramer thereof with a sulfurizing agent such as sulfur or sulfur chloride. As the olefin, for example, propylene, isobutene, diisobutene and the like are preferably used.

Dihydrocarbyl polysulfide is a compound represented by the following general formula (5).
R ¹³ -S _y -R ¹⁴ (5)
[In General Formula (5), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms (including a cycloalkyl group), an aryl group having 6 to 20 carbon atoms, or a 7 to 20 carbon atom. Represents an arylalkyl group, which may be the same or different from each other, and y represents an integer of 2 to 8; ]
Specific examples of R ¹³ and R ¹⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and various pentyl groups. Groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, cyclohexyl groups, phenyl groups, naphthyl groups, tolyl groups, xylyl groups, benzyl groups, and phenethyl groups. be able to.

  Specific examples of preferred dihydrocarbyl polysulfides include dibenzyl polysulfide, di-tert-nonyl polysulfide, didodecyl polysulfide, di-tert-butyl polysulfide, dioctyl polysulfide, diphenyl polysulfide, and dicyclohexyl polysulfide. It is done.

  Specific examples of dithiocarbamates include compounds represented by the following general formula (6) or (7).

In the general formulas (6) and (7), R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, e represents an integer of 0 to 4, and f represents an integer of 0 to 6. .

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

  Examples of the thiadiazoles include a 1,3,4-thiadiazole compound represented by the following general formula (8), a 1,2,4-thiadiazole compound represented by the general formula (9), and a general formula (10). Mention may be made of 1,4,5-thiadiazole compounds.

In the general formulas (8) to (10), R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ may be the same or different, and each independently represents a hydrogen atom or 1 to 30 carbon atoms. And g, h, i, j, k, and l each independently represent an integer of 0 to 8.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

  Examples of the phenol-based ashless antioxidant containing sulfur as a constituent element include 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.

  Among the above components (B-1), dihydrocarbyl polysulfide, dithiocarbamates and thiadiazoles are preferably used from the viewpoint that more excellent thermal / oxidative stability can be obtained.

  When the ashless antioxidant containing (B-1) sulfur as a constituent element is used as the component (B) in the present invention, the content is not particularly limited, but preferably in terms of elemental sulfur based on the total amount of the composition. Is 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and preferably 0.2% by mass or less, more preferably 0.1% by mass or less. Especially preferably, it is 0.04 mass% or less. When the content is less than the lower limit, the thermal and oxidation stability of the lubricating oil composition becomes insufficient, and in particular, it tends to be impossible to maintain excellent cleanliness over a long period of time. On the other hand, when the above upper limit is exceeded, the adverse effect on the exhaust gas purification device due to the high sulfur content of the lubricating oil composition tends to increase.

  The (B-2) organic molybdenum compound as the component (B) includes (B-2-1) an organic molybdenum compound containing sulfur as a constituent element, and (B-2-2) sulfur as a constituent element. Both organomolybdenum compounds are included.

  (B-2-1) Examples of the organic molybdenum compound containing sulfur as a constituent element include organic molybdenum complexes such as molybdenum dithiophosphate and molybdenum dithiocarbamate.

  Specific examples of molybdenum dithiophosphate include compounds represented by the following general formula (11).

In the general formula ^{(11), R 28, R} 29, R 30 and ^{R 31} may be different from each other in the same, having 2 to 30 carbon atoms, preferably 5 to 18 carbon atoms, more preferably 5 carbon atoms A hydrocarbon group such as an alkyl group having ˜12 or a (alkyl) aryl group having 6 to 18 carbon atoms, preferably 10 to 15 carbon atoms. Y ¹ , Y ² , Y ³ and Y ⁴ each represents a sulfur atom or an oxygen atom.

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

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

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

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

In the general formula ^{(12), R 32, R} 33, R 34 and ^{R 35} may be the same as or different from each other, from 2 to 24 carbon atoms, preferably an alkyl group having 4 to 13 carbon atoms, or carbon atoms A hydrocarbon group such as an (alkyl) aryl group having 6 to 24, preferably 10 to 15 carbon atoms is shown. Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ each represent a sulfur atom or an oxygen atom.

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

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

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

  Other organic molybdenum complexes containing sulfur include molybdenum compounds (for example, molybdenum dioxide, molybdenum oxide such as molybdenum trioxide, orthomolybdic acid, paramolybdic acid, molybdic acid such as (poly) sulfurized molybdenum acid, These metal salts of molybdate, molybdenum salts such as ammonium salts, molybdenum sulfides such as molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, and polysulfide molybdenum, molybdenum sulfides, metal salts or amine salts of molybdenum sulfides, chlorides Molybdenum halides such as molybdenum) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbylthiuram disulfide, bis (di (thio) hydrocarb) (Ludithiophosphonate) disulfide, organic (poly) sulfide, sulfurized ester, etc.) or other organic compounds, etc., or complexes of sulfur-containing molybdenum compounds such as molybdenum sulfide and sulfurized molybdic acid with alkenyl succinimides, etc. Can be mentioned.

  When an organic molybdenum compound containing (B-2-1) sulfur as a constituent element is used as the component (B) in the present invention, it is preferable because a friction reducing effect can be obtained in addition to the effect of improving thermal and oxidation stability. Of these, molybdenum dithiocarbamate is particularly preferred.

  (B-2-2) Specific examples of the organic molybdenum compound not containing sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, molybdenum salts of alcohols, and the like. Among them, a molybdenum-amine complex, a molybdenum salt of an organic acid, and a molybdenum salt of an alcohol are preferable.

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

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

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

  The molybdenum-succinimide complex is a complex of a sulfur-free molybdenum compound as exemplified in the description of the molybdenum-amine complex and a succinimide having an alkyl group or alkenyl group having 4 or more carbon atoms. Is mentioned. As the succinimide, succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof, or an alkyl group having 4 to 39 carbon atoms, preferably 8 to 18 carbon atoms. Or the succinimide etc. which have an alkenyl group are mentioned. If the alkyl group or alkenyl group in the succinimide has less than 4 carbon atoms, the solubility tends to deteriorate. A succinimide having an alkyl group or an alkenyl group having more than 30 carbon atoms and not more than 400 carbon atoms can also be used. By setting the alkyl group or alkenyl group to 30 or less carbon atoms, molybdenum-succinimide is obtained. The molybdenum content in the complex can be relatively increased, and the effects of the present invention can be further enhanced with a small amount of compounding.

  Examples of the molybdenum salt of an organic acid include salts of molybdenum bases such as molybdenum oxide or molybdenum hydroxide, molybdenum carbonate or molybdenum chloride exemplified in the description of the molybdenum-amine complex with an organic acid. It is done. As an organic acid, the phosphorus compound and carboxylic acid which are represented with the following general formula (P-1) or (P-2) are preferable.

[In Formula (P-1), R ⁵⁷ represents a hydrocarbon group having 1 to 30 carbon atoms, and R ⁵⁸ and R ⁵⁹ may be the same or different, and each represents a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. Represents a group, and n represents 0 or 1. ]

[In Formula (P-2), R ⁶⁰ , R ⁶¹ and R ⁶² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and n represents 0 or 1. ]
Moreover, as carboxylic acid which comprises the molybdenum salt of carboxylic acid, either a monobasic acid or a polybasic acid may be sufficient.

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

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

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

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

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

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

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

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

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

  When an organic molybdenum compound not containing (B-2-2) sulfur as a constituent element is used as the component (B) in the present invention, the high-temperature cleanliness and base number retention of the lubricating oil composition can be improved, It is preferable in that the initial friction reducing effect can be maintained for a long time, and a molybdenum-amine complex is particularly preferable.

  In the present invention, (B-2-1) an organic molybdenum compound containing sulfur as a constituent element and (B-2-2) an organic molybdenum compound not containing sulfur as a constituent element may be used in combination.

  When the (B) organomolybdenum compound is used as the (B) component in the present invention, its content is not particularly limited, but is preferably 0.001% by mass or more, more preferably in terms of molybdenum element, based on the total amount of the composition. Is 0.005 mass% or more, more preferably 0.01 mass% or more, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, particularly preferably 0.04 mass% or less. It is. When the content is less than 0.001% by mass, the thermal and oxidation stability of the lubricating oil composition becomes insufficient, and in particular, it tends to be impossible to maintain excellent cleanliness over a long period of time. On the other hand, when content of (B-1) component exceeds 0.2 mass%, the effect corresponding to content is not acquired, and it exists in the tendency for the storage stability of a lubricating oil composition to fall.

  The lubricating oil composition for an internal combustion engine of the present invention may be composed only of the above-described lubricating base oil and the components (A) and (B), but if necessary, in order to further improve its performance. In addition, various additives shown below may be further contained.

  The lubricating oil composition for an internal combustion engine of the present invention preferably further contains an antiwear agent from the viewpoint of further improving the wear resistance. As such extreme pressure agents, phosphorus extreme pressure agents, phosphorus-sulfur extreme pressure agents and the like are preferably used.

  Phosphorus extreme pressure agents include phosphoric acid, phosphorous acid, phosphoric acid esters (including phosphoric acid monoesters, phosphoric acid diesters and phosphoric acid triesters), phosphorous acid esters (phosphorous acid monoesters) Esters, phosphite diesters and phosphite triesters), and salts thereof (amine salts or metal salts). As phosphoric acid esters and phosphorous acid esters, those having a hydrocarbon group usually having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms are used.

  Phosphorus-sulfur extreme pressure agents include thiophosphoric acid, thiophosphorous acid, thiophosphoric acid esters (including thiophosphoric acid monoesters, thiophosphoric acid diesters, thiophosphoric acid triesters), and thiophosphorous acid esters. (Including thiophosphite monoesters, thiophosphite diesters, thiophosphite triesters), salts thereof, and zinc dithiophosphate. As the thiophosphates and thiophosphites, those having a hydrocarbon group usually having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms are used.

  Although content in particular of said extreme pressure agent is not restrict | limited, Preferably it is 0.01-5 mass%, More preferably, it is 0.1-3 mass% on the composition whole quantity basis.

  In the present invention, zinc dithiophosphate is particularly preferable among the above extreme pressure agents. As zinc dithiophosphate, the compound represented, for example by following General formula (13) can be illustrated.

R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ in the general formula (13) each independently represent a hydrocarbon group having 1 to 24 carbon atoms. Examples of these hydrocarbon groups include linear or branched alkyl groups having 1 to 24 carbon atoms, linear or branched alkenyl groups having 3 to 24 carbon atoms, and cycloalkyl groups having 5 to 13 carbon atoms. Or a linear or branched alkylcycloalkyl group, an aryl group having 6 to 18 carbon atoms, or a linear or branched alkylaryl group, an arylalkyl group having 7 to 19 carbon atoms, or the like. It is desirable to be. The alkyl group or alkenyl group may be any of primary, secondary, and tertiary.

Specific examples of R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, etc. Propenyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and oleyl Etc. Alkenyl groups such as decenyl group, nonadecenyl group, icocenyl group, heicosenyl group, dococenyl group, tricocenyl group and tetracocenyl group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group, methylcyclopentyl group, dimethylcyclopentyl group, Ethylcyclopentyl group, propylcyclopentyl group, ethylmethylcyclopentyl group, trimethylcyclopentyl group, diethylcyclopentyl group, ethyldimethylcyclopentyl group, propylmethylcyclopentyl group, propylethylcyclopentyl group, di-propylcyclopentyl group, propylethylmethylcyclopentyl group, methylcyclohexyl Xyl group, dimethyl cyclohexyl group, ethyl cyclohexyl group, propyl cyclohexyl group, ethyl methyl group Rohexyl group, trimethylcyclohexyl group, diethylcyclohexyl group, ethyldimethylcyclohexyl group, propylmethylcyclohexyl group, propylethylcyclohexyl group, di-propylcyclohexyl group, propylethylmethylcyclohexyl group, methylcycloheptyl group, dimethyl Cycloheptyl group, ethylcycloheptyl group, propylcycloheptyl group, ethylmethylcycloheptyl group, trimethylcycloheptyl group, diethylcycloheptyl group, ethyldimethylcycloheptyl group, propylmethylcycloheptyl group, propylethylcycloheptyl group, di- Alkylcycloalkyl groups such as propylcycloheptyl group and propylethylmethylcycloheptyl group; aryl groups such as phenyl group and naphthyl group; tolyl group; Group, ethylphenyl group, propylphenyl group, ethylmethylphenyl group, trimethylphenyl group, butylphenyl group, propylmethylphenyl group, diethylphenyl group, ethyldimethylphenyl group, tetramethylphenyl group, pentylphenyl group, hexylphenyl group Alkylaryl groups such as heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group and dodecylphenyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, phenethyl group, methylphenethyl group and dimethyl group Examples thereof include arylalkyl groups such as phenethyl group. And so on. The hydrocarbon group includes all possible straight chain structures and branched structures, and also includes the position of the double bond of the alkenyl group, the position of bond of the alkyl group to the cycloalkyl group, and the alkyl group. The position of bonding of the aryl group to the aryl group and the position of bonding of the aryl group to the alkyl group are arbitrary.

  Preferred examples of the zinc dithiophosphate include, for example, 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 mixtures of these arbitrary combinations.

The manufacturing method of the said zinc dithiophosphate is not specifically limited, It can manufacture by employ | adopting arbitrary conventional methods. Specifically, for example, alcohol or phenol having a hydrocarbon group corresponding to R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ in the above formula (13) is reacted with niline pentasulfide to obtain dithiophosphoric acid, It can be synthesized by neutralizing with zinc oxide. In addition, the structure of the said zinc dithiophosphate changes with raw material alcohol etc. to be used.

  Further, the content of the zinc dithiophosphate is not particularly limited, but from the viewpoint of suppressing catalyst poisoning of the exhaust gas purification apparatus, it is preferably 0.2% by mass or less in terms of phosphorus element based on the total amount of the composition. More preferably, it is 0.1 mass% or less, More preferably, it is 0.08 mass% or less, Most preferably, it is 0.06 mass% or less. It is preferable that it is 0.06% or less. Further, the content of zinc dithiophosphate is preferably 0.01% by mass in terms of phosphorus element, based on the total amount of the composition, from the viewpoint of the formation of a metal phosphate that exerts the effect of the antiwear additive. As mentioned above, More preferably, it is 0.02 mass% or more, More preferably, it is 0.04 mass% or more. When the content of zinc dithiophosphate is less than the lower limit, the effect of improving the wear resistance due to the addition tends to be insufficient.

  The lubricating oil composition for internal combustion engines of the present invention preferably further contains an ashless dispersant from the viewpoint of cleanliness and sludge dispersibility. Such ashless dispersants include alkenyl succinimides, alkyl succinimides and their derivatives derived from polyolefins. A typical succinimide is a polyalkylene polyamine containing an average of 4 to 10 (preferably 5 to 7) nitrogen atoms per molecule, and a succinic anhydride substituted with a high molecular weight alkenyl or alkyl group. It can obtain by reaction with. The high molecular weight alkenyl group or alkyl group is preferably polybutene (polyisobutene) having a number average molecular weight of 700 to 5,000, and more preferably polybutene (polyisobutene) having a number average molecular weight of 900 to 3,000.

  Examples of the polybutenyl succinimide preferably used in the lubricating oil composition for an internal combustion engine of the present invention include compounds represented by the following general formula (14) or (15).

  PIB in the general formula (14) or (15) represents a polybutenyl group, and is obtained from polybutene obtained by polymerizing a high purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride catalyst or an aluminum chloride catalyst. In the polybutene mixture, those having a vinylidene structure at the terminal are usually contained in an amount of 5 to 100 mol%. Further, n is an integer of 2 to 5, preferably 3 to 4 from the viewpoint of excellent sludge suppression effect.

  Although there is no restriction | limiting in particular as a manufacturing method of the succinimide represented by General formula (14) or (15), For example, what chlorinated the said polybutene, Preferably the said high purity isobutene is a boron fluoride type catalyst. Polybutenyl succinic acid obtained by reacting polymerized highly reactive polybutene (polyisobutene), more preferably polybutene from which chlorine and fluorine have been sufficiently removed, with maleic anhydride at 100 to 200 ° C. is converted into diethylenetriamine, triethylenetetramine. It can be obtained by reacting with a polyamine such as tetraethylenepentamine or pentaethylenehexamine. In the case of producing bissuccinimide, the polybutenyl succinic acid may be reacted twice as much as the polyamine (molar ratio). In the case of producing monosuccinimide, the polybutenyl succinic acid and the polyamine are used. May be reacted in an equal amount (molar ratio). Among these, polybutenyl bissuccinimide is preferable from the viewpoint of excellent sludge dispersibility.

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

  In the step of obtaining polybutenyl succinic anhydride by reaction of polybutene and maleic anhydride, a chlorination method using chlorine is often applied conventionally. However, this method results in a large amount of chlorine (eg, about 2000 to 3000 ppm) remaining in the succinimide final product. On the other hand, in a method that does not use chlorine, for example, when the above highly reactive polybutene is used and / or in a thermal reaction method, chlorine remaining in the final product can be suppressed to an extremely low level (for example, 0 to 30 ppm). Therefore, in order to suppress the chlorine content in the lubricating oil composition to an amount in the range of 0 to 30 ppm by weight, the method using the highly reactive polybutene and / or the thermal reaction method is used without using the chlorination method. It is preferable to use the obtained polybutenyl succinic anhydride.

  Moreover, as a derivative | guide_body of polybutenyl succinimide, in addition to the compound represented by the said General formula (14) or (15), boron compounds, such as a boric acid, alcohol, an aldehyde, a ketone, alkylphenol, cyclic carbonate, organic It can be used as a so-called modified succinimide in which an oxygen-containing organic compound such as an acid is allowed to act to neutralize or amidate part or all of the remaining amino group and / or imino group. In particular, a boron-containing alkenyl (or alkyl) succinimide obtained by a reaction with a boron compound such as boric acid is advantageous in terms of thermal and oxidation stability.

  Examples of the boron compound that acts on the compound represented by the general formula (14) or (15) include boric acid, borates, and borate esters. Specific examples of boric acid include orthoboric acid, metaboric acid, and tetraboric acid. Examples of borates include alkali metal salts, alkaline earth metal salts or ammonium salts of boric acid, and more specifically, for example, lithium metaborate, lithium tetraborate, lithium pentaborate, perborate. Lithium borate such as lithium; sodium borate such as sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate; potassium metaborate, potassium tetraborate, Potassium borates such as potassium pentaborate, potassium hexaborate and potassium octaborate; calcium borates such as calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate and calcium hexaborate ; Magnesium metaborate, magnesium diborate, trimagnesium tetraborate, pentaborate Neshiumu, magnesium borate and magnesium hexaborate acid; and ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium borate such as ammonium eight borate. Examples of the boric acid ester include esters of boric acid and preferably an alkyl alcohol having 1 to 6 carbon atoms. More specifically, examples thereof include monomethyl borate, dimethyl borate, trimethyl borate, and boric acid. Examples include monoethyl, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, tributyl borate and the like. The succinimide derivative in which the boron compound is allowed to act is preferably used since it is excellent in heat resistance and oxidation stability.

  Specific examples of the oxygen-containing organic compound that acts on the compound represented by the general formula (14) or (15) include formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, Carbon such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid, eicosanoic acid C1-C30 monocarboxylic acid, oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc., C2-C30 polycarboxylic acid or their anhydrides, ester compounds, C2-C6 Examples include alkylene oxide and hydroxy (poly) oxyalkylene carbonate. By allowing such an oxygen-containing organic compound to act, for example, part or all of the amino group or imino group in the compound represented by the general formula (14) or (15) is represented by the following general formula (16). Presumed to be a structure.

R ⁴⁰ in the general formula (16) is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, or —O— (R ⁴¹ O) _m. A hydroxy (poly) oxyalkylene group represented by H, wherein R ⁴¹ represents an alkylene group having 1 to 4 carbon atoms, and m represents an integer of 1 to 5; Among these, polybutenyl bissuccinimides mainly composed of those in which these oxygen-containing organic compounds are allowed to act on all amino groups or imino groups are preferably used since they are excellent in sludge dispersibility. Such a compound can be obtained, for example, by allowing (n-1) mol of an oxygen-containing organic compound to act on 1 mol of the compound of the formula (11). A succinimide derivative having such an oxygen-containing organic compound acted thereon is excellent in sludge dispersibility, and in particular, one having hydroxy (poly) oxyalkylene carbonate acted thereon is preferable.

  The weight average molecular weight of polybutenyl succinimide and / or a derivative thereof as an ashless dispersant used in the present invention is preferably 5000 or more, more preferably 6500 or more, still more preferably 7000 or more, and particularly preferably 8000 or more. is there. When the weight average molecular weight is less than 5,000, the molecular weight of the non-polar polybutenyl group is small and the sludge dispersibility is poor, and the amine portion of the polar group which may become an active site for oxidative degradation is relatively increased and oxidized. Since it is inferior in stability, it is considered that the effect of extending the life as in the present invention cannot be obtained. On the other hand, the weight average molecular weight of polybutenyl succinimide and / or a derivative thereof is preferably 20000 or less and particularly preferably 15000 or less from the viewpoint of preventing deterioration of low temperature viscosity characteristics. Here, the weight average molecular weight means that two columns of Tosoh GMHHR-M (7.8 mm ID × 30 cm) are used in series on a Waters 150-CALC / GPC apparatus, and the solvent is tetrahydrofuran, temperature. 23 ° C., flow rate of 1 mL / min, sample concentration of 1% by mass, sample injection amount of 75 μL, and weight average molecular weight in terms of polystyrene measured with a detector differential refractometer (RI).

  In the present invention, as the ashless dispersant, in addition to the above succinimide and / or derivative thereof, alkyl or alkenyl polyamine, alkyl or alkenyl benzylamine, r- or alkenyl succinate, Mannich base and derivatives thereof Etc. can be used.

  The content of the ashless dispersant in the lubricating oil composition for an internal combustion engine of the present invention is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, in terms of nitrogen element, based on the total amount of the composition. More preferably, it is 0.05 mass% or more, Preferably it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less, More preferably, it is 0.015 mass% or less. When the content of the ashless dispersant is less than the above lower limit value, a sufficient cleansing effect cannot be exhibited, while when the content exceeds the above upper limit value, the low temperature viscosity characteristics are deteriorated and the demulsibility is decreased. Since it deteriorates, it is not preferable respectively. In addition, when using a succinimide-based ashless dispersant having a weight average molecular weight of 6500 or more, the content is based on the total amount of the composition in terms of exhibiting sufficient sludge dispersibility and excellent low-temperature viscosity characteristics. It is preferable to set it as 0.005-0.05 mass% in conversion of nitrogen element, and it is more preferable to set it as 0.01-0.04 mass%.

  Further, when using a high molecular weight ashless dispersant, the content is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, in terms of nitrogen element, based on the total amount of the composition, Moreover, Preferably it is 0.1 mass% or less, More preferably, it is 0.05 mass% or less. When the content of the high molecular weight ashless dispersant is less than the above lower limit value, a sufficient cleansing effect cannot be exerted. On the other hand, when the content exceeds the above upper limit value, the low temperature viscosity characteristics are deteriorated and the resistance Since the emulsifying properties deteriorate, each is not preferable.

  Further, when using an ashless dispersant modified with a boron compound, the content is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, in terms of boron element, based on the total amount of the composition. More preferably, it is 0.02 mass% or more, preferably 0.2 mass% or less, more preferably 0.1 mass% or less. When the content of the ashless dispersant modified with a boron compound is less than the above lower limit value, a sufficient cleansing effect cannot be exhibited, while when the content exceeds the above upper limit value, Since deterioration and demulsibility deteriorate, it is not preferable respectively.

  Moreover, it is preferable that the lubricating oil composition for internal combustion engines of this invention contains an ashless friction modifier from the point which can further improve the friction characteristic. As the ashless friction modifier, any compound usually used as a friction modifier for lubricating oils can be used. For example, an alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a straight chain having 6 to 30 carbon atoms. Amine compound, fatty acid ester, fatty acid amide, fatty acid, fatty alcohol, aliphatic ether, hydrazide (eg oleyl hydrazide), semicarbazide, urea, ureido, biuret having at least one chain alkyl group or straight chain alkenyl group in the molecule And ashless friction modifiers.

  The content of the friction modifier in the lubricating oil composition for an internal combustion engine of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.00% by mass based on the total amount of the composition. It is 3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. If the content of the friction modifier is less than the lower limit, the effect of reducing friction due to the addition tends to be insufficient, and if the content exceeds the upper limit, the effects of the wear resistance additive and the like are hindered. It tends to be easy or the solubility of the additive tends to deteriorate.

  Moreover, it is preferable that the lubricating oil composition for internal combustion engines of this invention further contains a metal type detergent from the point of detergency. It is preferable to use at least one alkaline earth metal detergent selected from alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates as the metal detergent.

  Alkaline earth metal sulfonates include alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by sulfonated alkyl aromatic compounds having a molecular weight of 300 to 1,500, preferably 400 to 700, particularly magnesium salts and / or Or it is a calcium salt and a calcium salt is used preferably. Specific examples of the alkyl aromatic sulfonic acid include so-called petroleum sulfonic acid and synthetic sulfonic acid. As the petroleum sulfonic acid here, generally used are those obtained by sulfonating an alkyl aromatic compound in a lubricating oil fraction of mineral oil, or so-called mahoganic acid that is by-produced when white oil is produced. As synthetic sulfonic acids, for example, sulfonated alkylbenzenes having linear or branched alkyl groups, which are obtained as a by-product from an alkylbenzene production plant, which is a raw material for detergents, or are obtained by alkylating polyolefins to benzene. Or sulfonated alkylnaphthalene such as dinonylnaphthalene is used. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or anhydrous sulfuric acid is used.

  Alkaline earth metal phenates include alkylphenols, alkylphenol sulfides, alkaline earth metal salts of Mannich reactants of alkylphenols, particularly magnesium salts and / or calcium salts. For example, in the following general formulas (17) to (19): Mention may be made of the compounds represented.

In the general formulas (17) to (19), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ may be the same or different and each have 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms. Wherein M ¹ , M ² and M ³ each represent an alkaline earth metal, preferably calcium and / or magnesium, and x represents 1 or 2. In the above formula, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are specifically butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group , Octacosyl group, nonacosyl group, triacontyl group and the like, which may be linear or branched. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.

  Examples of the alkaline earth metal salicylate include alkaline earth metal salts of allyl salicylic acid, particularly magnesium salts and / or calcium salts, and examples include those represented by the following general formula (20).

In the general formula (20), R ⁴⁷ represents a linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, and M ⁴ represents an alkaline earth metal, preferably calcium and / or magnesium. Show. Specific examples of R ⁴⁷ include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl Group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc. It may be a branch. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.

  Further, as the alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate, the above alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, allylic salicylic acid, etc. are directly used as magnesium and Reacting with alkaline earth metal bases such as calcium alkaline earth metal oxides and hydroxides, or once replacing alkali metal salts such as sodium salts and potassium salts with alkaline earth metal salts Neutral (normal salt) alkaline earth metal sulfonate, neutral (normal salt) alkaline earth metal phenate and neutral (normal salt) alkaline earth metal salicylate as well as neutral alkaline earth metal sulfonate obtained by , Neutral alkaline earth metal fer Basic alkaline earth metal sulfonate, basic alkaline earth metal obtained by heating a salt and neutral alkaline earth metal salicylate and excess alkaline earth metal salt or alkaline earth metal base in the presence of water Alkaline earth metal hydroxide and carbon dioxide in the presence of phenate and basic alkaline earth metal salicylate, neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate Or overbased (superbasic) alkaline earth metal sulfonates, overbased (superbasic) alkaline earth metal phenates and overbased (superbasic) alkaline earths obtained by reacting with boric acid Metal salicylates are also included.

  In the present invention, the above-mentioned neutral alkaline earth metal salts, basic alkaline earth metal salts, overbased (superbasic) alkaline earth metal salts, and mixtures thereof can be used. Among these, from the viewpoint of maintaining cleanliness over a long period of time, it is preferable to use a combination of overbased calcium sulfonate and overbased calcium phenate, or overbased calcium salicylate. It is particularly preferred to use calcium salicylate. Metal-based detergents are usually commercially available in a state diluted with a light lubricating base oil or the like, and are available, but generally the metal content is 1.0 to 20% by mass, preferably Is preferably 2.0 to 16% by mass. Although the total base number of the alkaline earth metal detergent used in the present invention is arbitrary, it is usually desirable to use a total base number of 500 mgKOH / g or less, preferably 150 to 450 mgKOH / g. The total base number referred to here is JISK2501 (1992) "Petroleum products and lubricants-Neutralization number test method". It means the total base number by the perchloric acid method measured according to the above.

  The content of the metallic detergent in the lubricating oil composition for an internal combustion engine of the present invention is arbitrary, but is 0.1 to 10% by mass, preferably 0.5 to 8% by mass, more preferably based on the total amount of the composition. It is desirable to contain 1-5 mass%. When this content exceeds 10 mass%, since the effect only corresponding to the content is not acquired, it is unpreferable.

  Moreover, it is preferable that the lubricating oil composition for internal combustion engines of this invention contains a viscosity index improver from the point which can further improve a viscosity-temperature characteristic. Such viscosity index improvers include non-dispersed or dispersed polymethacrylates, dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or hydrides thereof, styrene-diene hydrogenated copolymers, styrene. -Maleic anhydride ester copolymers and polyalkylstyrenes, among others, a non-dispersed viscosity index having a weight average molecular weight of 50,000 or less, preferably 40,000 or less, most preferably 10,000 to 35,000. An improver and / or a dispersion type viscosity index improver is preferably used.

  Specifically, as the non-dispersion type viscosity index improver, a monomer selected from compounds represented by the following general formulas (21), (22) and (23) (hereinafter referred to as “monomer (M-1)”) And a copolymer of two or more monomers (M-1) or a hydride thereof. On the other hand, as the dispersion type viscosity index improver, specifically, a monomer selected from the compounds represented by the general formulas (24) and (25) (hereinafter referred to as “monomer (M-2)”). One of the monomers (M-1) selected from the compounds represented by the general formulas (21) to (23) or those obtained by introducing an oxygen-containing group into two or more types of copolymers or hydrides thereof Examples thereof include copolymers of two or more types and one or more types of monomers (M-2) selected from the compounds represented by the general formulas (24) and (25), or hydrides thereof. .

In the general formula ^{(21), R 48} represents a hydrogen atom or a methyl ^{group, R 49} represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 18 carbon atoms represented by R ⁴⁹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Examples thereof include a group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group (these alkyl groups may be linear or branched).

In the general formula (22), R ⁵⁰ represents a hydrogen atom or a methyl group, and R ⁵¹ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ⁵¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as decyl group, undecyl group, dodecyl group (these alkyl groups may be linear or branched); cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl group, cyclohexyl group and cycloheptyl group; methyl Cyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group, diethylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, diethyl Cycloheptyl group, etc. An alkylcycloalkyl group having 6 to 11 carbon atoms (the substitution position of these alkyl groups with the cycloalkyl group is arbitrary);
Alkenyl groups such as butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc. (These alkenyl groups may be linear or branched, and position of double bond Is also optional);
Aryl group such as phenyl group, naphthyl group: alkylaryl group having 7 to 12 carbon atoms such as tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group (these alkyl groups) May be linear or branched, and the position of substitution on the aryl group is also arbitrary); carbon number of benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, etc. 7-12 arylalkyl groups (these alkyl groups may be linear or branched); and the like.

In the general formula (23), X ¹ and X ² are each independently a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms (—OR ⁵² : R ⁵² is an alkyl group having 1 to 18 carbon atoms) or a carbon number. 1-18 monoalkylamino group ^{(-NHR 53: R} 53 is an alkyl group having 1 to 18 carbon atoms).

In the general formula (23), R ⁵⁴ represents a hydrogen atom or a methyl group, R ⁵⁵ represents an alkylene group having 1 to 18 carbon atoms, Y ¹ represents ¹ to 2 nitrogen atoms, and 0 to 2 oxygen atoms. 1 represents an amine residue or heterocyclic residue, and m is 0 or 1. Specific examples of the alkylene group represented by R ⁵⁵ having 1 to 18 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, Examples include an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group (these alkylene groups may be linear or branched). Specific examples of the group represented by Y ¹ include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, anilino group, toluidino group, xylidino group, acetylamino group, benzoylamino group, Examples thereof include a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, and a pyrazino group.

In the above general formula (25), R ⁵⁶ represents a hydrogen atom or a methyl group, and Y ² represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms. Specific examples of the group represented by Y ² include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, and a morpholino group. Pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, pyrazino group and the like.

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

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

  Copolymerization of a copolymer of one or more monomers selected from the (M-1) compound and one or more monomers selected from the (M-2) compound. The molar ratio is generally about monomer (M-1): monomer (M-2) = 80: 20 to 95: 5. The production method is arbitrary, but usually a copolymer is easily obtained by radical solution polymerization of monomer (M-1) and monomer (M-2) in the presence of a polymerization initiator such as benzoyl peroxide. It is done.

  Among the above-described viscosity index improvers, polymethacrylate viscosity index improvers are preferable because they are superior in low-temperature fluidity.

  The blending amount of the viscosity index improver in the lubricating oil composition for internal combustion engines of the present invention is preferably 0.1 to 15% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the composition. When the content of the viscosity index improver is less than 0.1% by mass, the effect of improving the viscosity-temperature characteristics due to the addition tends to be insufficient, and when it exceeds 10% by mass, the initial extreme pressure property is reduced. It tends to be difficult to maintain for a long time.

  In the lubricating oil composition for an internal combustion engine of the present invention, for the purpose of further improving its performance, in addition to the above additives, a corrosion inhibitor, a rust inhibitor, a demulsifier, and a metal deactivation are added as necessary. You may mix | blend various additives, such as an agent, a pour point depressant, a rubber swelling agent, an antifoamer, and a coloring agent, individually or in combination.

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

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

  Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

  Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.

  As the pour point depressant, a known pour point depressant can be arbitrarily selected according to the properties of the lubricating base oil, but the weight average molecular weight is 1 to 300,000, preferably 5 to 200,000. Methacrylate is preferred.

  In particular, in the present invention, since the effect of adding the pour point depressant by the lubricating base oil is maximized, excellent low-temperature viscosity characteristics (MRV viscosity at −40 ° C. is preferably 20000 mPa · s or less, more preferably 15000 mPa · s or less, more preferably 10000 mPa · s or less). In addition, MRV viscosity at -40 degreeC here means MRV viscosity at -40 degreeC measured based on JPI-5S-42-93. For example, when a pour point depressant is blended with the base oils (II) and (V), the MRV viscosity at −40 ° C. can be 12000 mPa · s or less, more preferably 10000 mPa · s or less, and still more preferably. Can obtain a lubricating oil composition having extremely excellent low-temperature viscosity characteristics of 8000 mPa · s, particularly preferably 6500 mPa · s or less. In this case, the blending amount of the pour point depressant is 0.05 to 2% by mass, preferably 0.1 to 1.5% by mass, based on the total amount of the composition, but in particular the MRV viscosity can be lowered. The range of 0.15 to 0.8% by mass is the best.

  As the antifoaming agent, any compound usually used as an antifoaming agent for lubricating oil can be used, and examples thereof include silicones such as dimethyl silicone and fluorosilicone. One or two or more compounds arbitrarily selected from these can be blended in any amount.

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

  When these additives are contained in the lubricating oil composition of the present invention, the content is based on the total amount of the composition, 0.005 to 5% by mass for the corrosion inhibitor, the rust inhibitor, and the demulsifier, respectively, and the metal inertness. 0.005 to 1% by mass for the agent, 0.05 to 1% by mass for the pour point depressant, 0.0005 to 1% by mass for the antifoaming agent, and 0.001 to 1.0% by mass for the colorant. Usually selected by range.

  The lubricating oil composition for an internal combustion engine of the present invention can contain an additive containing sulfur as a constituent element as described above, but the total sulfur content of the lubricating oil composition (sulfur resulting from the lubricating base oil and additives) The total amount of min) is preferably 0.05 to 0.3% by mass from the viewpoint of suppressing the solubility of the additive and the consumption of the base number due to the generation of sulfur oxides under high-temperature oxidation conditions. More preferably, it is 0.1-0.2 mass%, Most preferably, it is 0.12-0.18 mass%.

Further, the kinematic viscosity at 100 ° C. of the lubricating oil composition for an internal combustion engine of the present invention is usually 4 to 24 mm ² / s, but the oil film thickness that suppresses seizure and wear is maintained, and stirring resistance From the point which suppresses the increase in this, Preferably it is 5-18 mm < ² > / s, More preferably, it is 6-15 mm < ² > / s, More preferably, it is 7-12 mm < ² > / s.

  The lubricating oil composition for an internal combustion engine of the present invention having the above-described configuration is excellent in thermal / oxidation stability or further in viscosity-temperature characteristics, friction characteristics and volatilization prevention, and is used for two-wheeled vehicles, four-wheeled vehicles, power generation, When used as a lubricating oil for an internal combustion engine such as a marine gasoline engine, a diesel engine, an oxygen-containing compound-containing engine, a gas engine, etc., long drain and energy saving can be sufficiently realized.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
[Raw material wax]
The fraction separated by vacuum distillation in the step of refining the solvent refined base oil was subjected to hydrogenation after solvent extraction with furfural and then dewaxed with a methyl ethyl ketone-toluene mixed solvent. Table 1 shows the properties of the wax (hereinafter referred to as “WAX1”) that was removed during solvent dewaxing and obtained as slack wax.

  Table 2 shows the properties of the wax obtained by further deoiling WAX1 (hereinafter referred to as “WAX2”).

  Table 3 shows the properties of WAX3 using an FT wax having a paraffin content of 95% by mass and a carbon number distribution of 20 to 80 (hereinafter referred to as “WAX3”).

[Manufacture of lubricating base oil]
WAX1, WAX2 and WAX3 were used as feedstocks, and hydrotreating was performed using a hydrotreating catalyst. At this time, the reaction temperature and the liquid space velocity were adjusted so that the decomposition rate of normal paraffin in the raw material oil was 10% by mass or less.

  Next, about the to-be-processed object obtained by said hydrogenation process, in the temperature range of 315 degreeC-325 degreeC using the zeolite-type hydrodewaxing catalyst adjusted to noble metal content 0.1 to 5 weight%. Hydrodewaxing was performed.

  Furthermore, the to-be-processed object (raffinate) obtained by the above hydrodewaxing was hydrorefined using a hydrogenation catalyst. Thereafter, a light component and a heavy component were separated by distillation to obtain a lubricating base oil having the composition and properties shown in Table 4. In Table 4, “the ratio of the components derived from normal paraffin in the urea adduct” is obtained by performing a gas chromatography analysis on the urea adduct obtained in the measurement of the urea adduct value. Yes (hereinafter the same).

  Next, a polymethacrylate pour point depressant (weight average molecular weight: about 60,000) generally used for lubricating oil for automobiles was added to the lubricating base oil in Table 4. The addition amount of the pour point depressant was three conditions of 0.3% by mass, 0.5% by mass and 1.0% by mass based on the total amount of the composition. Next, with respect to each of the obtained lubricating oil compositions, the MRV viscosity at −40 ° C. was measured, and the obtained results are shown in Table 4.

[Examples 1-7, Comparative Examples 1-8]
In Examples 1-7, the lubricating oil composition which has a composition shown in Table 5 using base oil 1-1, base oil 1-2 or base oil 1-3, and the base oil and additive shown below. Was prepared. In Comparative Examples 1 to 8, lubricating oil compositions having the compositions shown in Tables 6 and 7 were prepared using the base oils and additives shown below. Properties of the resulting lubricating oil composition are shown in Tables 5-7.
(Base oil)
Base oil 2: Paraffinic hydrocracked base oil (saturated component: 94.8% by mass, ratio of cyclic saturated component in saturated component: 46.8% by mass, sulfur component: less than 0.001% by mass, at 100 ° C. (Kinematic viscosity: 4.1 mm ² / s, viscosity index: 121, refractive index at ₂₀ ° C .: 1.4640, n ₂₀ −0.002 × kv100: 1.456)
Base oil 3: highly refined paraffin base oil (saturation: 99.7% by mass, sulfur content: 0.01% by mass, kinematic viscosity at 100 ° C .: 4.0 mm ² / s, viscosity index: 125)
Base oil 4: paraffinic solvent refined base oil (saturated content: 77% by mass, sulfur content: 0.12% by mass, kinematic viscosity at 100 ° C .: 4.0 mm ² / s, viscosity index: 102)
(Ashless antioxidant that does not contain sulfur as a constituent element)
A1: Alkyldiphenylamine A2: Octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (ashless antioxidant containing sulfur as a constituent element and organic molybdenum compound)
B1: Ashless dithiocarbamate (sulfur content: 29.4% by mass)
B2: Ditridecylamine complex of molybdenum (molybdenum content: 10.0% by mass)
(Antiwear agent)
C1: zinc dialkyldithiophosphate (phosphorus content: 7.4% by mass, alkyl group: primary octyl group)
C2: zinc dialkyldithiophosphate (phosphorus content: 7.2 mass%, alkyl group: secondary butyl group or secondary hexyl group mixture)
(Ashless dispersant)
D1: Polybutenyl succinimide (bis type, weight average molecular weight: 8,500, nitrogen content: 0.65 mass%)
(Ashless friction modifier)
E1: Glycerin fatty acid ester (trade name: MO50, manufactured by Kao Corporation)
(Other additives)
F1: A package containing a metallic detergent, a viscosity index improver, a pour point depressant and an antifoaming agent.
[Heat and oxidation stability evaluation test]
Regarding the lubricating oil compositions of Examples 1 to 7 and Comparative Examples 1 to 8, JIS K 2514, 4. The thermal / oxidation stability test (test temperature: 165.5 ° C.) was performed in accordance with the method (ISOT) in the item, and the base number retention rate after 24 hours and 72 hours was obtained. The obtained results are shown in Tables 5-7.

[Friction characteristic evaluation test: SRV (micro reciprocating friction) test]
About the lubricating oil composition of Examples 1-7 and Comparative Examples 1-8, the SRV test was implemented as follows and the friction characteristic was evaluated. First, test pieces (steel balls (diameter 18 mm) / disk, SUJ-2) for SRV testing machine manufactured by Optimol were prepared, and the surface roughness was finished to Ra 0.2 μm or less. This test piece is mounted on an SRV testing machine manufactured by Optimol Co., Ltd., and the shell lubricating oil composition is dropped on the sliding surface of the test piece, and the test is performed under the conditions of a temperature of 80 ° C., a load of 30 N, an amplitude of 3 mm, and a frequency of 50 Hz. The average coefficient of friction from the time when 15 minutes passed until the time when 30 minutes passed after the start of the test was measured. The obtained results are shown in Tables 5-7.

  From Tables 5-7, it turns out that the thermal-oxidation stability, friction characteristic, and low temperature viscosity characteristic of the lubricating oil composition for internal combustion engines of Examples 1-7 are superior to those of Comparative Examples 1-8.

Claims (5)

A lubricating base oil having a saturated content of 90% by mass or more, a urea adduct value of 4% by mass or less, and a viscosity index of 100 or more, based on the total amount of the lubricating base oil;
An ashless antioxidant that does not contain sulfur as a constituent element;
A lubricating oil composition for an internal combustion engine comprising an organic molybdenum compound and at least one selected from ashless antioxidants containing sulfur as constituent elements.   The raw material oil in which the lubricating base oil contains normal paraffin has a saturated content of the product to be processed of 90% by mass or more based on the total amount of the lubricating base oil, and a urea adduct value of 4 2. The internal combustion engine according to claim 1, which is a lubricating base oil obtained by a hydrocracking / hydroisomerization process so that the viscosity index is 100% or less and the viscosity index is 100 or more. Lubricating oil composition for engines.   The lubricating oil composition for internal combustion engines according to claim 2, wherein the raw material oil contains 50% by mass or more of slack wax obtained by solvent dewaxing of a lubricating base oil.   A polybutenyl succinimide having a weight average molecular weight of 5000 or more and / or a derivative thereof is contained in an amount of 0.005 to 0.3% by mass in terms of nitrogen, based on the total amount of the lubricating oil composition for an internal combustion engine. The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 3.   The lubricating oil composition for an internal combustion engine according to any one of claims 1 to 4, wherein the organic molybdenum compound does not contain sulfur as a constituent element.