WO2013125106A1 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- WO2013125106A1 WO2013125106A1 PCT/JP2012/079079 JP2012079079W WO2013125106A1 WO 2013125106 A1 WO2013125106 A1 WO 2013125106A1 JP 2012079079 W JP2012079079 W JP 2012079079W WO 2013125106 A1 WO2013125106 A1 WO 2013125106A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/02—Specified values of viscosity or viscosity index
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
Definitions
- the present invention relates to a lubricating oil composition.
- lubricating oil is used in internal combustion engines, transmissions, and other mechanical devices in order to make their operations smooth.
- lubricating oil (engine oil) for internal combustion engines is required to have high performance as the performance of the internal combustion engine increases, the output increases, and the operating conditions become severe. Therefore, various additives such as antiwear agents, metal detergents, ashless dispersants, and antioxidants are blended in conventional engine oils in order to satisfy these required performances (for example, Patent Documents 1 to 5 listed below). 3).
- Patent Documents 1 to 5 listed below listed below. 3
- HTHS viscosity is also called “high temperature high shear viscosity”
- it is effective to lower the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C., but it has been very difficult to satisfy all these requirements with conventional lubricating oils.
- recent advances in engine technology have made it possible to reduce the HTHS viscosity at 150 ° C. while maintaining engine durability.
- engine oil that is less than 2.6 mPa ⁇ s, which is the lower limit of the HTHS viscosity at 150 ° C. of SAE 0W-20 engine oil, has been developed and applied.
- engine oil with an HTHS viscosity of less than 2.6 mPa ⁇ s at 150 ° C increases the coefficient of friction in the boundary lubrication region where metals contact each other in some engines and parts, and conversely deteriorates fuel economy.
- a technique for reducing the friction coefficient in the boundary lubrication region more than before is required. .
- the present invention has been made in view of such circumstances, and in an engine oil having an HTHS viscosity at 150 ° C. of less than 2.6 mPa ⁇ s, the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS at 100 ° C.
- Providing a lubricating oil composition that has a sufficiently low viscosity and that can sufficiently suppress an increase in the coefficient of friction in the boundary lubrication region, and that is excellent in fuel efficiency even in engines with more severe boundary lubrication regions The purpose is to do.
- the present invention provides a lubricating base oil having a kinematic viscosity at 100 ° C. of 1 to 5 mm 2 / s, (A) a weight average molecular weight (Mw) of 400,000 or less, and PSSI of 20 or less.
- a viscosity index improver (B) an overbased metal detergent with a metal ratio of 3.4 or less, and (C) a friction modifier, and an HTHS viscosity at 150 ° C. of less than 2.6 mPa ⁇ s.
- a lubricating oil composition is provided.
- the (A) viscosity index improver is preferably a viscosity index improver having a weight average molecular weight to PSSI ratio (Mw / PSSI) of 1 ⁇ 10 4 or more.
- the (B) overbased metal detergent is preferably an overbased alkaline earth metal salicylate obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal borate.
- the (C) friction modifier is preferably an organic molybdenum friction modifier.
- PSSI Permanent Shear Stability Index
- ASTM D 6022-01 Standard Practice for Performance Calculation of Permanent Shear Stability Index
- ASTM D 6278-02 Test Metohd Sfor Shear Quality of Containment Fluids Containing Fluids It means the permanent shear stability index (Permanent ⁇ ⁇ ⁇ Shear Stability Index) calculated based on data measured by European Diesel Injector Apparatus.
- the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C. can be sufficiently reduced.
- An increase in the friction coefficient in the lubricating region can be sufficiently suppressed, and a lubricating oil composition having excellent fuel economy can be provided.
- the lubricating oil composition of the present invention can also be suitably used for gasoline engines, diesel engines, gas engines, etc. for motorcycles, automobiles, power generation, cogeneration, etc. Not only can it be suitably used for these various engines using fuel of mass ppm or less, but it is also useful for various engines for ships and outboard motors.
- the lubricating oil composition according to the present invention comprises a lubricating base oil having a kinematic viscosity of 1 to 5 mm 2 / s at 100 ° C., and (A) a viscosity having a weight average molecular weight (Mw) of 400,000 or less and a PSSI of 20 or less. It contains an index improver, (B) an overbased metal detergent with a metal ratio of 3.4 or less, and (C) a friction modifier.
- a lubricating base oil having a kinematic viscosity at 100 ° C. of 1 to 5 mm 2 / s (hereinafter referred to as “the lubricating base oil according to the present invention”) is used.
- a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, contact.
- solvent removal, solvent extraction, hydrocracking, solvent dewaxing, contact Such as paraffinic mineral oil, normal paraffinic base oil, isoparaffinic base oil, etc. purified by combining one or more kinds of refining treatments such as dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc.
- refining treatments such as dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc.
- those having a kinematic viscosity at 100 ° C. of 1 to 5 mm 2 / s can be mentioned.
- Preferred examples of the lubricating base oil according to the present invention include the following base oils (1) to (8) as raw materials, and the raw oil and / or the lubricating oil fraction recovered from the raw oil
- recovering lubricating oil fractions can be mentioned.
- Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO) (3) Wax (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-liquid (GTL) process, etc.
- the above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred.
- one of these purification methods may be performed alone, or two or more may be combined.
- the order in particular is not restrict
- the lubricating base oil according to the present invention is obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment.
- the following base oil (9) or (10) is particularly preferred.
- the base oil selected from the above base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like.
- Hydrocracking base oil (10) obtained by subjecting the lubricating oil fraction to dewaxing treatment such as solvent dewaxing or catalytic dewaxing, or distillation after the dewaxing treatment, and the above base oils (1) to (The base oil selected from 8) or the lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic desorption. Hydroisomerized base oil obtained by performing dewaxing treatment such as wax or by distillation after the dewaxing treatment.
- a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.
- the catalyst used for the hydrocracking / hydroisomerization is not particularly limited, but a composite oxide having cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one kind of the composite oxide.
- a hydrocracking catalyst in which a metal having hydrogenation ability (for example, one or more metals such as Group VIa metal and Group VIII metal in the periodic table) supported by a binder combined with the above is supported.
- the hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.
- the reaction conditions in the hydrocracking and hydroisomerization are not particularly limited, but the hydrogen partial pressure is 0.1 to 20 MPa, the average reaction temperature is 150 to 450 ° C., the LHSV is 0.1 to 3.0 hr ⁇ 1 , the hydrogen / oil ratio. 50 to 20000 scf / b is preferable.
- the kinematic viscosity at 100 ° C. of the lubricating base oil according to the present invention needs to be 5 mm 2 / s or less, preferably 4.5 mm 2 / s or less, more preferably 4 mm 2 / s or less, and still more preferably. Is 3.8 mm 2 / s or less, particularly preferably 3.7 mm 2 / s or less, and most preferably 3.6 mm 2 / s or less.
- the kinematic viscosity at 100 ° C. needs to be 1 mm 2 / s or more, preferably 1.5 mm 2 / s or more, more preferably 2 mm 2 / s or more, and still more preferably 2.
- the kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
- the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 5 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 1 mm 2 / s Since the formation of an oil film at the lubrication site is insufficient, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.
- the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present invention is preferably 40 mm 2 / s or less, more preferably 30 mm 2 / s or less, still more preferably 25 mm 2 / s or less, and particularly preferably 20 mm 2 / s. s or less, most preferably 17 mm 2 / s or less.
- kinematic viscosity at 40 ° C. of the lubricating base oil exceeds 40 mm 2 / s, the low-temperature viscosity characteristics may be deteriorated, and sufficient fuel economy may not be obtained, which is less than 6.0 mm 2 / s. In such a case, the oil film formation at the lubrication site is insufficient, so that the lubricity is poor, and the evaporation loss of the lubricating oil composition may be increased.
- the viscosity index of the lubricating base oil according to the present invention is preferably 100 or more. More preferably, it is 105 or more, More preferably, it is 110 or more, Especially preferably, it is 115 or more, Most preferably, it is 120 or more. Further, it is preferably 180 or less, more preferably 170 or less, and still more preferably 160 or less.
- the viscosity index is less than 100, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. . If the viscosity index exceeds 180, the fluidity at low temperatures may be deteriorated, which is not preferable.
- the viscosity index as used in the present invention means a viscosity index measured according to JIS K 2283-1993.
- the lubricating base oil used in the lubricating oil composition of the present invention has a first lubricating base oil component having a kinematic viscosity at 100 ° C. of 3.5 mm 2 / s or more, and a kinematic viscosity at 100 ° C. of 3.5 mm.
- a mixture of second lubricating base oil components that is less than 2 / s is preferred.
- the density ( ⁇ 15 ) at 15 ° C. of the first lubricating base oil component used in the lubricating oil composition of the present invention is preferably 0.860 g / cm 3 or less, more preferably 0.850 g / cm 3 or less, Preferably it is 0.840 g / cm 3 or less, particularly preferably 0.822 g / cm 3 or less.
- the density at 15 ° C. means a density measured at 15 ° C. in accordance with JIS K 2249-1995.
- the pour point of the first lubricating base oil component used in the lubricating oil composition of the present invention is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 12.5 ° C. or lower, still more preferably ⁇ 15 ° C. or lower, particularly preferably. It is ⁇ 20 ° C. or lower.
- the pour point as used in the present invention means a pour point measured according to JIS K 2269-1987.
- the kinematic viscosity at 100 ° C. of the first lubricating base oil component used in the lubricating oil composition of the present invention is preferably 5 mm 2 / s or less, more preferably 4.5 mm 2 / s or less, and still more preferably. It is 4.0 mm 2 / s or less, particularly preferably 3.9 mm 2 / s or less.
- the kinematic viscosity at 100 ° C. is preferably 3.5 mm 2 / s or more, more preferably 3.6 mm 2 / s or more, still more preferably 3.7 mm 2 / s or more, and particularly preferably 3. 8 mm 2 / s or more.
- the kinematic viscosity at 100 ° C. is more than 5 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 3.5 mm 2 / s at lubricating sites Insufficient oil film formation may result in poor lubricity and increase in evaporation loss of the lubricating oil composition.
- the kinematic viscosity at 40 ° C. of the first lubricating base oil component used in the lubricating oil composition of the present invention is preferably 40 mm 2 / s or less, more preferably 30 mm 2 / s or less, and even more preferably 25 mm 2 / s or less. Particularly preferably, it is 20 mm 2 / s or less, and most preferably 17 mm 2 / s or less.
- kinematic viscosity at 40 ° C. is more than 40 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 6.0 mm 2 / s at lubricating sites Insufficient oil film formation may result in poor lubricity and increase in evaporation loss of the lubricating oil composition.
- the viscosity index of the first lubricating base oil component used in the lubricating oil composition of the present invention is preferably 100 or more. More preferably, it is 110 or more, More preferably, it is 120 or more, Especially preferably, it is 130 or more, Most preferably, it is 140 or more.
- the viscosity index is less than 100, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. .
- the density ( ⁇ 15 ) at 15 ° C. of the second lubricating base oil component used in the lubricating oil composition of the present invention is preferably 0.860 g / cm 3 or less, more preferably 0.850 g / cm 3 or less, Preferably it is 0.840 g / cm 3 or less, particularly preferably 0.835 g / cm 3 or less.
- the pour point of the second lubricating base oil component used in the lubricating oil composition of the present invention is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 12.5 ° C. or lower, still more preferably ⁇ 15 ° C. or lower, particularly preferably. It is ⁇ 20 ° C. or lower.
- the pour point as used in the present invention means a pour point measured according to JIS K 2269-1987.
- the kinematic viscosity at 100 ° C. of the second lubricating base oil component used in the lubricating oil composition of the present invention is preferably less than 3.5 mm 2 / s, more preferably 3.4 mm 2 / s or less, Preferably it is 3.3 mm ⁇ 2 > / s or less.
- the kinematic viscosity at 100 ° C. is preferably 1 mm 2 / s or more, more preferably 2 mm 2 / s or more, further preferably 2.5 mm 2 / s or more, and particularly preferably 3.0 mm. 2 / s or more.
- the kinematic viscosity at 40 ° C. of the second lubricating base oil component used in the lubricating oil composition of the present invention is preferably 20 mm 2 / s or less, more preferably 18 mm 2 / s or less, and even more preferably 16 mm 2 / s or less. Particularly preferably, it is 14 mm 2 / s or less.
- kinematic viscosity at 40 ° C. is more than 20 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 6.0 mm 2 / s at lubricating sites Insufficient oil film formation may result in poor lubricity and increase in evaporation loss of the lubricating oil composition.
- the viscosity index of the second lubricating base oil component used in the lubricating oil composition of the present invention is preferably 100 or more. More preferably, it is 105 or more, More preferably, it is 110 or more. When the viscosity index is less than 100, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. .
- the sulfur content in the lubricating base oil used in the present invention depends on the sulfur content of the raw material.
- a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
- a lubricating base oil that does not substantially contain sulfur can be obtained.
- the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it.
- the sulfur content is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, from the viewpoint of further improvement in thermal and oxidation stability and low sulfur content. More preferably, it is more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.
- the nitrogen content in the lubricating base oil used in the present invention is preferably 7 ppm by mass or less, more preferably 5 ppm by mass or less, and even more preferably 3 ppm by mass or less. If the nitrogen content exceeds 7 ppm by mass, the thermal and oxidation stability tends to decrease.
- the nitrogen content in the present invention means a nitrogen content measured according to JIS K 2609-1990.
- The% C p of the lubricating base oil used in the present invention is preferably 70 or more, preferably 80 to 99, more preferably 85 to 95, still more preferably 87 to 94, particularly preferably 90 to 90. 94. If the% C p of the lubricating base oil is less than 70, 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.
- % C A of the lubricating base oil used in the present invention is preferably 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less. If the% C A value of the lubricating base oil exceeds 2, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.
- % C N of the lubricating base oil used in the present invention is preferably 30 or less, more preferably 4 to 25, more preferably 5-13, particularly preferably from 5 to 8. If the% C N value of the lubricating base oil exceeds 30, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties will tend to be reduced. Moreover, when% CN is less than 4, the solubility of the additive tends to decrease.
- % 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 preferred ranges of% C P ,% C N and% C A described above are based on the values obtained by the above method. For example, even for a lubricating base oil containing no naphthene, it can be obtained by the above method.
- is% C N may indicate a value greater than zero.
- the content of the saturated component in the lubricating base oil used in the present invention is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass, based on the total amount of the lubricating oil base oil.
- the ratio of the cyclic saturated component in the saturated component is preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass. % Or less, and more preferably 21% by mass or less.
- annular saturated part to the said saturated part becomes like this. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more.
- the viscosity-temperature characteristics and the heat / oxidation stability can be improved.
- the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricating base oil. Furthermore, according to the present invention, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in the friction reduction effect and an improvement in energy saving.
- the saturated content in the present invention is measured by the method described in ASTM D 2007-93.
- a similar method that can obtain the same result can be used in the separation method of the saturated component or the composition analysis of the cyclic saturated component and the non-cyclic saturated component.
- the method described in ASTM D 2425-93, the method described in ASTM D 2549-91, the method using high performance liquid chromatography (HPLC), or a method obtained by improving these methods can be used.
- the aromatic content in the lubricating base oil used in the present invention is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, based on the total amount of the lubricating oil base oil.
- it is 2 mass% or less, Preferably it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Most preferably, it is 1.5 mass% or more. If the aromatic content exceeds 5% by mass, the viscosity-temperature characteristics, thermal / oxidative stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to decrease.
- 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 0.1% by mass or more. Can be increased.
- the aromatic content in the present invention means a value measured according to ASTM D 2007-93.
- 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.
- a synthetic base oil may be used as the lubricating base oil according to the present invention.
- Synthetic base oils include poly ⁇ -olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate) having a kinematic viscosity at 100 ° C. of 1 to 5 mm 2 / s.
- di-2-ethylhexyl adipate diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.
- polyol ester trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, Pentaerythritol pelargonate
- polyoxyalkylene glycols dialkyldiphenyl ethers, polyphenyl ethers, etc., among which poly ⁇ -olefins are preferred.
- the production method of poly- ⁇ -olefin is not particularly limited.
- Friedel Crafts containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester examples thereof include a method of polymerizing ⁇ -olefin in the presence of a polymerization catalyst such as a catalyst.
- the lubricating base oil according to the present invention may be used alone, and the lubricating base oil according to the present invention may be one or more of other base oils. You may use together.
- 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.
- a kinematic viscosity at 100 ° C. is 5 mm 2 / s, greater 100 mm 2 / s or less in , Solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil, solvent dewaxed base oil, and the like.
- Other synthetic base oils used in combination with the lubricating base oil according to the present invention include the above-described synthetic base oils having a kinematic viscosity at 100 ° C. outside the range of 1 to 5 mm 2 / s. .
- the lubricating oil composition according to the present invention contains (A) a viscosity index improver having a weight average molecular weight (Mw) of 400,000 or less and a PSSI of 20 or less.
- Mw weight average molecular weight
- PSSI weight average molecular weight
- Specific compounds include non-dispersed or dispersed ester group-containing viscosity index improvers, non-dispersed or dispersed poly (meth) acrylate viscosity index improvers, styrene-diene hydrogenated copolymers, non-dispersed Type or dispersion type ethylene- ⁇ -olefin copolymer or hydride thereof, polyisobutylene or hydride thereof, styrene-maleic anhydride ester copolymer, polyalkylstyrene and (meth) acrylate-olefin copolymer or these A mixture etc. can be mentioned.
- Poly (meth) acrylate-based viscosity index improver that can be used as the viscosity index improver of the present invention
- the poly (meth) acrylate-based herein is a general term for polyacrylate-based compounds and polymethacrylate-based compounds.
- R 1 represents hydrogen or a methyl group
- R 2 represents a linear or branched hydrocarbon group having 1 to 5000 carbon atoms.
- the poly (meth) acrylate compound obtained by one type of homopolymer of the monomer represented by the general formula (1) or two or more types of copolymerization is a so-called non-dispersed poly (meth) acrylate.
- the poly (meth) acrylate-based compound includes a monomer represented by the general formula (1) and one or more monomers selected from the following general formulas (2) and (3) (hereinafter referred to as “monomer M- 2 ”and“ monomer M-3 ”) may be copolymerized so-called dispersed poly (meth) acrylates.
- R 3 represents a hydrogen atom or a methyl group
- R 4 represents an alkylene group having 1 to 18 carbon atoms
- E 1 represents 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
- Each represents an amine residue or a heterocyclic residue
- a represents 0 or 1.
- R 5 represents a hydrogen atom or a methyl group
- E 2 represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
- Specific examples of the group represented by E 1 and E 2 include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, and a benzoylamino group.
- 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-2 and the monomer M-3 are specifically dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate. Morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures thereof.
- the styrene-diene hydrogenated copolymer that can be used as the viscosity index improver of the present invention is a compound obtained by hydrogenating a copolymer of styrene and diene.
- the diene include butadiene and isoprene.
- a hydrogenated copolymer of styrene and isoprene is preferable.
- the ethylene- ⁇ -olefin copolymer or hydride thereof that can be used as the viscosity index improver of the present invention is a compound obtained by hydrogenating a copolymer of ethylene and ⁇ -olefin or the copolymer thereof.
- the ⁇ -olefin include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like.
- the ethylene- ⁇ -olefin copolymer is not only a so-called non-dispersed type composed of only hydrocarbons, but also a so-called dispersed type ethylene- ⁇ -olefin copolymer obtained by reacting a polar compound such as a nitrogen-containing compound with the copolymer. Can be used.
- the weight average molecular weight (M w ) of the viscosity index improver according to the present invention needs to be 400,000 or less, preferably 380,000 or less, and more preferably 360,000 or less. Moreover, it is preferable that it is 10,000 or more, More preferably, it is 50,000 or more, More preferably, it is 100,000 or more, Especially preferably, it is 200,000 or more. If the weight average molecular weight is less than 10,000, the effect of improving the viscosity index when dissolved in a lubricating base oil is small, resulting in poor fuel economy and low temperature viscosity characteristics, and may increase costs.
- the PSSI (Permanent Cystability Index) of the viscosity index improver according to the present invention needs to be 20 or less, more preferably 17 or less, still more preferably 16 or less, and particularly preferably 15 or less.
- PSSI Permanent Cystability Index
- the shear stability is deteriorated, so that it is necessary to increase the initial kinematic viscosity, which may deteriorate the fuel economy.
- PSSI is less than 1, the viscosity index improvement effect when dissolved in a lubricating base oil is small, and it is not only inferior in fuel efficiency and low-temperature viscosity characteristics, but also may increase costs. Is preferably 1 or more.
- the weight average molecular weight and PSSI ratio of viscosity index improver according to the present invention is preferably 1.0 ⁇ 10 4 or more, more preferably 1.5 ⁇ 10 4 or more, more preferably Is 2.0 ⁇ 10 4 or more. If M W / PSSI is below 1.0 ⁇ 10 4, there is a possibility that fuel saving properties and low-temperature startability i.e. viscosity temperature characteristics and low temperature viscosity characteristics are deteriorated.
- the ratio (M W / M N ) of the weight average molecular weight (M W ) and the number average molecular weight (M N ) of the viscosity index improver according to the present invention is preferably 5.0 or less, more preferably 4.0. Hereinafter, it is further preferably 3.5 or less, particularly preferably 3.0 or less. Further, it is preferred that the M W / M N is 1.0 or more, more preferably 2.0 or more, more preferably 2.5 or more, and particularly preferably 2.6 or more. If MW / MN exceeds 5.0 or less than 1.0, the effect of improving the solubility and viscosity temperature characteristics may deteriorate, and sufficient storage stability and fuel economy may not be maintained. There is.
- the content of the viscosity index improver in the lubricating oil composition of the present invention is preferably 0.1 to 50% by mass, preferably 0.5 to 20% by mass, more preferably based on the total amount of the composition. It is 1.0 to 15% by mass, more preferably 1.5 to 12% by mass. If the content is less than 0.1% by mass, the low temperature characteristics may be insufficient, and if the content exceeds 50% by mass, the shear stability of the composition may be deteriorated.
- the lubricating oil composition according to the present invention contains (B) an overbased metal detergent having a metal ratio of 3.4 or less. Thereby, compared with the case where this structure is not provided, a fuel-saving performance can be improved.
- an overbased compound of an oil-soluble metal salt of a compound containing an OH group and / or a carbonyl group can be used.
- alkaline earth metal sulfonates, alkaline earth metal carboxylates, alkaline earth metal salicylates, alkaline earth metal phenates, alkaline earth metal phosphonates and other overbased metal salts, alkaline earth metal hydroxides or oxides As well as overbased metal salts obtainable by reacting boric acid or boric anhydride.
- the alkaline earth metal include magnesium, calcium, barium and the like, and calcium is preferable.
- overbased metal salt it is preferable to use an overbased compound of an oil-soluble metal salt of an OH group and / or carbonyl group-containing hydrocarbon compound, which is overbased with an alkaline earth metal borate. It is more preferable to use an oil-soluble metal salt of an OH group and / or carbonyl group-containing hydrocarbon compound. Moreover, it is preferable to use an alkaline earth metal salicylate, and it is more preferable to use an alkaline earth metal salicylate overbased with an alkaline earth metal borate.
- the base number of the overbased metal detergent having a metal ratio of 3.4 or less used in the present invention is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, and 120 mgKOH / g. More preferably, it is more preferably 140 mgKOH / g or more, and most preferably 150 mgKOH / g or more. Moreover, it is preferable that it is 300 mgKOH / g or less, It is more preferable that it is 200 mgKOH / g or less, It is further more preferable that it is 180 mgKOH / g or less, It is especially preferable that it is 170 mgKOH / g or less.
- the base number in the present invention is a value measured according to JIS K 2501 5.2.3.
- the particle size of the (B) overbased metal detergent having a metal ratio of 3.4 or less used in the present invention is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
- the method for producing the (B) overbased metal detergent having a metal ratio of 3.4 or less used in the present invention is arbitrary, but for example, the oil-soluble metal salt, alkaline earth metal hydroxide or oxide, and Boric acid or anhydrous boric acid is reacted at 20 to 200 ° C. for 2 to 8 hours in the presence of water, an alcohol such as methanol, ethanol, propanol, or butanol and a diluting solvent such as benzene, toluene, xylene, and then 100 to 200. It is obtained by heating to 0 ° C. to remove water and optionally alcohol and diluting solvent.
- These detailed reaction conditions are appropriately selected according to the raw materials, the amount of reactants, and the like.
- the oil-soluble metal salt overbased with the alkaline earth metal borate produced by the above method has a particle size of usually 0.1 ⁇ m or less and a total base number of usually 100 mgKOH / g or more. It can be preferably used in an oil composition.
- the overbased metal detergent used in the present invention must have a metal ratio of 3.4 or less.
- the metal ratio is preferably 3.2 or less, more preferably 3.0 or less, further preferably 2.8 or less, particularly preferably 2.6 or less, and most preferably 2.5 or less. System cleaner. If the metal ratio exceeds 3.4, the friction torque is reduced, that is, the fuel efficiency becomes insufficient.
- the metal ratio is preferably 1.0 or more, more preferably 1.1 or more, further preferably 1.5 or more, particularly preferably 1.9 or more, and most preferably 2.2 or more. This is a metallic detergent.
- the metal ratio in the present invention is represented by the valence of the metal element in the metal-based detergent ⁇ metal element content (mol%) / soap group content (mol%), and the metal element is calcium,
- a soap group such as magnesium means a sulfonic acid group, a phenol group, a salicylic acid group, or the like.
- the alkyl group or alkenyl group of the overbased metal detergent (B) having a metal ratio of 3.4 or less used in the present invention has 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 19 or less. Or an alkenyl group. A carbon number of less than 8 is not preferable because the oil solubility is not sufficient.
- Such an alkyl group or alkenyl group may be linear or branched, but is preferably linear. These may be a primary alkyl group, an alkenyl group, a secondary alkyl group, an alkenyl group, a tertiary alkyl group or an alkenyl group, but in the case of a secondary alkyl group, an alkenyl group, a tertiary alkyl group or an alkenyl group, a branch is formed.
- the position of is preferably only carbon bonded to an aromatic group.
- the content of the (B) overbased metal detergent having a metal ratio of 3.4 or less is preferably 0.01 to 30% by mass, based on the total amount of the lubricating oil composition.
- the content is 0.05 to 5% by mass. If the content is less than 0.01% by mass, the fuel saving effect may last only for a short period of time, and if it exceeds 30% by mass, the effect corresponding to the content may not be obtained. There is not preferable.
- the content of the (B) overbased metal detergent having a metal ratio of 3.4 or less in the lubricating oil composition according to the present invention is preferably 0.01 in terms of metal elements, based on the total amount of the lubricating oil composition.
- % By mass or more, more preferably 0.05% by mass or more, further preferably 0.10% by mass or more, particularly preferably 0.15% by mass or more, and preferably 0.5% by mass or less, more preferably 0.4% by mass or less, more preferably 0.3% by mass or less, particularly preferably 0.25% by mass or less, and most preferably 0.22% by mass or less.
- the content of the (B) overbased metal detergent having a metal ratio of 3.4 or less in the lubricating oil composition according to the present invention is preferably 0.01 in terms of boron element based on the total amount of the lubricating oil composition.
- % By mass or more more preferably 0.03% by mass or more, further preferably 0.04% by mass or more, particularly preferably 0.05% by mass or more, and preferably 0.20% by mass or less, more preferably It is 0.10% by mass or less, more preferably 0.08% by mass or less, particularly preferably 0.07% by mass or less, and most preferably 0.06% by mass or less.
- the ratio (MB1) / (MB2) of the metal content (MB1) derived from the component (B) and the boron content (MB2) derived from the component (B) in the lubricating oil composition according to the present invention is preferably It is 1 or more, more preferably 2 or more, still more preferably 2.5 or more, particularly preferably 3.0 or more, and most preferably 3.5 or more. If (MB1) / (MB2) is less than 1, it is not preferable because fuel economy may be deteriorated. (MB1) / (MB2) is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 5 or less. If (MB1) / (MB2) exceeds 20, the fuel economy may be deteriorated, which is not preferable.
- the lubricating oil composition according to the present invention contains (C) a friction modifier. Thereby, compared with the case where it does not have this structure, a fuel-saving performance can be improved.
- C) As a friction modifier 1 or more types of friction modifiers chosen from an organic molybdenum compound and an ashless friction modifier are mentioned.
- organic molybdenum compound used in the present invention examples include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, orthomolybdic acid, Molybdic acid such as paramolybdic acid, (poly) sulfurized molybdic acid, metal salts of these molybdic acids, molybdate such as ammonium salt, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polysulfide molybdenum, Sulfurized molybdic acid, metal salts or amine salts of sulfurized molybdic acid, molybdenum halides such as molybdenum chloride, etc.) and sulfur-containing organic mo
- organic molybdenum compound an organic molybdenum compound that does not contain sulfur as a constituent element can be used.
- organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.
- the content thereof is not particularly limited, but is preferably 0.001% by mass or more in terms of molybdenum element based on the total amount of the lubricating oil composition.
- it is 0.005 mass% or more, More preferably, it is 0.01 mass% or more, Most preferably, it is 0.03 mass% or more, Preferably it is 0.2 mass% or less, More preferably, it is 0.1 mass%
- it is more preferably 0.08% by mass or less, particularly preferably 0.06% by mass or less.
- the content When the content is less than 0.001% by mass, the friction reduction effect due to the addition tends to be insufficient, and the fuel economy and thermal / oxidation stability of the lubricating oil composition tend to be insufficient. . On the other hand, when the content exceeds 0.2% by mass, an effect commensurate with the content cannot be obtained, and the storage stability of the lubricating oil composition tends to decrease.
- any compound usually used as a friction modifier for lubricating oil can be used.
- one or two selected from oxygen atom, nitrogen atom, sulfur atom in the molecule examples thereof include compounds having 6 to 50 carbon atoms and containing at least a hetero element. More specifically, it has at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a straight chain alkyl group, straight chain alkenyl group, branched alkyl group or branched alkenyl group having 6 to 30 carbon atoms in the molecule.
- Ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, fatty alcohols, aliphatic ethers, urea compounds, hydrazide compounds, and the like.
- the content of the ashless friction modifier in the lubricating oil composition according to the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably, based on the total amount of the lubricating oil composition. It is 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
- the content of the ashless friction modifier is less than 0.01% by mass, the effect of reducing friction due to the addition tends to be insufficient, and when the content exceeds 3% by mass, the effect of an antiwear additive or the like. Tends to be inhibited, or the solubility of the additive tends to deteriorate.
- the (C) friction modifier is preferably an organic molybdenum friction modifier, more preferably an organic molybdenum compound containing sulfur, and even more preferably molybdenum dithiocarbamate.
- any additive commonly used in lubricating oils can be contained depending on the purpose.
- additives include metal detergents other than the component (B), ashless dispersants, antiwear agents (or extreme pressure agents), antioxidants, corrosion inhibitors, rust inhibitors, and demulsifiers.
- additives such as metal deactivators and antifoaming agents.
- metal detergents other than the component (B) include normal salts or basic salts such as alkali metal / alkaline earth metal sulfonate, alkali metal / alkaline earth metal phenate, and alkali metal / alkaline earth metal salicylate. Can be mentioned.
- alkali metal include sodium and potassium
- examples of the alkaline earth metal include magnesium, calcium, and barium. Magnesium or calcium is preferable, and calcium is more preferable.
- any ashless dispersant used in lubricating oils can be used.
- antioxidants examples include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum.
- phenol-based ashless antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-
- amine-based ashless antioxidants include phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine, and dialkyldiphenylamine.
- any antiwear agent / extreme pressure agent used for lubricating oil can be used.
- sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used.
- addition of a sulfur-based extreme pressure agent is preferable, and sulfurized fats and oils are particularly preferable.
- corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
- rust preventive examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
- demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylene alkyl naphthyl ether.
- metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
- metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
- Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and ⁇ - (o-carboxybenzylthio) propiononitrile.
- antifoaming agent examples include silicone oil having a kinematic viscosity at 25 ° C. of 1,000 to 100,000 mm 2 / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Examples thereof include hydroxybenzyl alcohol.
- the content thereof is preferably 0.01 to 10% by mass based on the total amount of the lubricating oil composition.
- the kinematic viscosity at 100 ° C. of the lubricating oil composition according to the present invention is preferably 4 to 12 mm 2 / s, preferably 9.0 mm 2 / s or less, more preferably 8.0 mm 2 / s or less, Preferably it is 7.0 mm ⁇ 2 > / s or less, Most preferably, it is 6.8 mm ⁇ 2 > / s or less. Further, the kinematic viscosity at 100 ° C.
- the kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the kinematic viscosity at 100 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and if it exceeds 12 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
- the kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present invention is preferably 4 to 50 mm 2 / s, preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less, particularly preferably 30 mm 2. / S or less, most preferably 27 mm 2 / s or less.
- the kinematic viscosity at 40 ° C. of the lubricating oil composition of the present invention is preferably 15 mm 2 / s or more, more preferably 18 mm 2 / s or more, further preferably 20 mm 2 / s or more, and particularly preferably 22 mm 2 / s. That's it.
- the kinematic viscosity at 40 ° C. here refers to the kinematic viscosity at 40 ° C. as defined in ASTM D-445.
- the kinematic viscosity at 40 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and when it exceeds 50 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
- the viscosity index of the lubricating oil composition according to the present invention is preferably in the range of 140 to 400, preferably 190 or more, more preferably 200 or more, still more preferably 210 or more, particularly preferably 220 or more, most preferably. 230 or more.
- the viscosity index of the lubricating oil composition of the present invention is less than 140, it may be difficult to improve fuel economy while maintaining the HTHS viscosity at 150 ° C. Further, the low temperature viscosity at ⁇ 35 ° C. There is a risk that it will be difficult to reduce.
- the viscosity index of the lubricating oil composition according to the present invention exceeds 400, there is a possibility that the evaporability may be deteriorated, and there is a problem due to insufficient solubility of the additive and compatibility with the sealing material. May occur.
- the HTHS viscosity at 100 ° C. of the lubricating oil composition according to the present invention is preferably 5.2 mPa ⁇ s or less, more preferably 5.0 mPa ⁇ s or less, still more preferably 4.7 mPa ⁇ s or less, particularly preferably. Is 4.5 mPa ⁇ s or less. Further, it is preferably 3.0 mPa ⁇ s or more, more preferably 3.5 mPa ⁇ s or more, particularly preferably 4.0 mPa ⁇ s or more, and most preferably 4.1 mPa ⁇ s or more.
- referred to in the present invention indicates a high temperature and high shear viscosity at 100 ° C. as defined in ASTM D-4683.
- the HTHS viscosity at 100 ° C. is less than 3.0 mPa ⁇ s, there is a risk of insufficient lubricity, and when it exceeds 5.2 mPa ⁇ s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.
- the HTHS viscosity at 150 ° C. of the lubricating oil composition according to the present invention is less than 2.6 mPa ⁇ s, more preferably 2.5 mPa ⁇ s or less, still more preferably 2.45 mPa ⁇ s or less, particularly preferably 2 .4 mPa ⁇ s or less. Further, it is preferably 2.0 mPa ⁇ s or more, more preferably 2.1 mPa ⁇ s or more, further preferably 2.2 mPa ⁇ s or more, and particularly preferably 2.3 mPa ⁇ s or more.
- the ratio of the HTHS viscosity at 150 ° C. to the HTHS viscosity at 100 ° C. (HTHS viscosity at 150 ° C./HTHS viscosity at 100 ° C.) of the lubricating oil composition according to the present invention is preferably 0.50 or more, More preferably 0.52 or more, still more preferably 0.54, particularly preferably 0.55 or more, and most preferably 0.56 or more. If the ratio is less than 0.50, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained.
- the lubricating oil composition according to the present invention has sufficiently low kinematic viscosity at 40 ° C, kinematic viscosity at 100 ° C, and HTHS viscosity at 100 ° C in an engine oil having an HTHS viscosity at 150 ° C of less than 2.6 mPa ⁇ s.
- the increase in the coefficient of friction in the boundary lubrication region can be sufficiently suppressed, and the fuel efficiency is excellent.
- the lubricating oil composition of the present invention having such excellent characteristics can be suitably used as fuel-saving engine oils such as fuel-saving gasoline engine oil and fuel-saving diesel engine oil.
- Example 1 Comparative Examples 1 to 4
- lubricating oil compositions having the compositions shown in Table 2 were prepared using the following base oils and additives, respectively.
- Table 1 shows the properties of the base oils O-1, O-2, and O-3.
- the lubricating oil compositions of Examples 1 to 5 containing all of the components (A) to (C) have the same HTHS viscosity at 150 ° C. as the component (B) or (C)
- the friction improvement rate in the valve-operated motoring friction test is high, and the fuel economy is excellent.
- a viscosity index improver having a PSSI of the component (A) exceeding 20 while the friction improvement ratio of the lubricating oil composition parts of Comparative Examples 1 to 3 in which the metal ratio of the component (B) exceeds 3.4 is significantly inferior.
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Abstract
Description
例えば、一般的な省燃費化の手法として、潤滑油の動粘度の低減および粘度指数の向上(低粘度基油と粘度指数向上剤の組合せによるマルチグレード化)や摩擦低減剤の配合が知られている。低粘度化の場合、潤滑油またはそれを構成する基油の粘度の低減に起因して、厳しい潤滑条件下(高温高せん断条件下)での潤滑性能が低下し、摩耗や焼付き、疲労破壊等の不具合の発生が懸念される。また、摩擦低減剤の配合については、無灰系やモリブデン系の摩擦調整剤が知られているが、一般的なこれら摩擦低減剤配合油をさらに上回る省燃費油が求められている。
しかしながら、近年のエンジン技術の進歩により、エンジンの耐久性を維持しながら150℃におけるHTHS粘度を低減することが可能となった。更なる省燃費性の向上のため、例えばSAE 0W-20エンジン油の150℃におけるHTHS粘度の下限である2.6mPa・sを下回るエンジン油が開発、適用されている。しかしながら、150℃におけるHTHS粘度が2.6mPa・sを下回るエンジン油は、一部のエンジンや部品において金属同士が接触する境界潤滑領域の摩擦係数を上昇させ、逆に省燃費性を悪化させることが確認されている。
150℃におけるHTHS粘度が2.6mPa・sを下回るエンジン油を適用した全てのエンジンの省燃費性を向上するためには、境界潤滑領域の摩擦係数をこれまで以上に低減する技術が必要である。
(1)パラフィン基系原油および/または混合基系原油の常圧蒸留による留出油
(2)パラフィン基系原油および/または混合基系原油の常圧蒸留残渣油の減圧蒸留による留出油(WVGO)
(3)潤滑油脱ろう工程により得られるワックス(スラックワックス等)および/またはガストゥリキッド(GTL)プロセス等により得られる合成ワックス(フィッシャートロプシュワックス、GTLワックス等)
(4)基油(1)~(3)から選ばれる1種または2種以上の混合油および/または当該混合油のマイルドハイドロクラッキング処理油
(5)基油(1)~(4)から選ばれる2種以上の混合油
(6)基油(1)、(2)、(3)、(4)または(5)の脱れき油(DAO)
(7)基油(6)のマイルドハイドロクラッキング処理油(MHC)
(8)基油(1)~(7)から選ばれる2種以上の混合油。
(9)上記基油(1)~(8)から選ばれる基油または当該基油から回収された潤滑油留分を水素化分解し、その生成物またはその生成物から蒸留等により回収される潤滑油留分について溶剤脱ろうや接触脱ろうなどの脱ろう処理を行い、または当該脱ろう処理をした後に蒸留することによって得られる水素化分解基油
(10)上記基油(1)~(8)から選ばれる基油または当該基油から回収された潤滑油留分を水素化異性化し、その生成物またはその生成物から蒸留等により回収される潤滑油留分について溶剤脱ろうや接触脱ろうなどの脱ろう処理を行い、または、当該脱ろう処理をしたあとに蒸留することによって得られる水素化異性化基油。
なお、本発明でいう15℃における密度とは、JIS K 2249-1995に準拠して15℃において測定された密度を意味する。
また、飽和分の分離方法、あるいは環状飽和分、非環状飽和分等の組成分析の際には、同様の結果が得られる類似の方法を使用することができる。例えば、上記の他、ASTM D 2425-93に記載の方法、ASTM D 2549-91に記載の方法、高速液体クロマトグラフィ(HPLC)による方法、あるいはこれらの方法を改良した方法等を挙げることができる。
また、本発明に係る潤滑油基油と併用される他の合成系基油としては、100℃における動粘度が1~5mm2/sの範囲外である、前記した合成系基油が挙げられる。
α-オレフィンとしては具体的にプロピレン、イソブチレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、1-デセン、1-ドデセン等が使用される。エチレン-α-オレフィン共重合体は、炭化水素のみからなるいわゆる非分散型のほか、共重合体に窒素含有化合物等の極性化合物を反応させた、いわゆる分散型エチレン-α-オレフィン共重合体も使用することができる。
金属比は3.2以下であることが好ましく、より好ましくは3.0以下、さらに好ましくは2.8以下、特に好ましくは2.6以下、最も好ましくは2.5以下に調整されてなる金属系清浄剤である。金属比が3.4を超えると摩擦トルクの低減すなわち省燃費性が不十分となる。
また金属比は1.0以上であることが好ましく、より好ましくは1.1以上、さらに好ましくは1.5以上、特に好ましくは1.9以上に、最も好ましくは2.2以上に調整されてなる金属系清浄剤である。金属比が1.0未満では内熱機関用潤滑油組成物の動粘度や低温粘度が高くなるため潤滑性や始動性に不具合が生じる可能性があるためである。
より高い摩擦低減効果を得るためには、単独で合成されたものを用いることが好ましい。
実施例1~5および比較例1~4においては、それぞれ以下に示す基油および添加剤を用いて表2に示す組成を有する潤滑油組成物を調製した。基油O-1、O-2、O-3の性状を表1に示す。
(基油)
O-1(基油1):n-パラフィン含有油を水素化分解/水素化異性化した鉱油
O-2(基油2):水素化分解鉱油
O-3(基油3):水素化分解鉱油
(添加剤)
A-1:非分散型PMA系粘度指数向上剤(Mw=36万,PSSI=15,Mw/PSSI=2.4×104)
A-2:非分散型PMA系粘度指数向上剤(Mw=33万,PSSI=15,Mw/PSSI=2.2×104)
a-1:非分散型PMA系粘度指数向上剤(Mw=38万,PSSI=27,Mw/PSSI=1.4×104)
a-2:分散型PMA系粘度指数向上剤(Mw=40万,PSSI=45,Mw/PSSI=0.88×104)
B-1:過塩基性ホウ酸カルシウムサリシレートA(金属比2.0、塩基価139mgKOH/g,Ca含有量4.9mass%、B含有量1.3mass%、Ca/B比3.8、アルキル基鎖長14~18)
B-2:過塩基性ホウ酸カルシウムサリシレートB(金属比2.5、塩基価158mgKOH/g,Ca含有量5.6mass%、B含有量1.7mass%、Ca/B比3.3、アルキル基鎖長14~18)
b-1:過塩基性ホウ酸カルシウムサリシレートC(金属比3.5、塩基価192mgKOH/g,Ca含有量6.8mass%、B含有量2.7mass%、Ca/B比2.5、アルキル基鎖長14~18)
C-1:MoDTC(アルキル基鎖長C8/C13、Mo含有量10mass%、硫黄量11mass%)
d-1:コハク酸イミド系分散剤(Mw13000、アルキル基鎖長1900、窒素量0.6mass%)
e-1:ZnDTP(アルキル基鎖長C4/C6、二級、Zn量7.8mass%、P量7.2mass%、S量15.0mass%)
f-1:その他添加剤(酸化防止剤、摩耗防止剤、流動点降下剤、消泡剤等)
実施例1~5および比較例1~4の各潤滑油組成物について、40℃または100℃における動粘度、粘度指数、100℃または150℃におけるHTHS粘度を測定した。また、省燃費性の測定は動弁系モータリング摩擦トルクを測定した。各物性値、省燃費性の測定は以下の評価方法により行った。得られた結果を表2に示す。
(1)動粘度:ASTM D-445
(2)粘度指数:JIS K 2283-1993
(3)HTHS粘度:ASTM D-4683
(4)動弁系モータリング摩擦試験:直打型4気筒エンジンの動弁系のカムおよびタペット一対の摩擦トルクを測定可能とする装置を用い、油温100℃、回転数350rpmにおける摩擦トルクを測定した。比較例1を基準油としたときのモータリングフリクション改善率を算出した。
Claims (4)
- 100℃における動粘度が1~5mm2/sである潤滑油基油と、(A)重量平均分子量(Mw)が40万以下でPSSIが20以下の粘度指数向上剤と、(B)金属比3.4以下の過塩基性金属系清浄剤と、(C)摩擦調整剤とを含有し、150℃におけるHTHS粘度が2.6mPa・s未満であることを特徴とする潤滑油組成物。
- 前記粘度指数向上剤が、重量平均分子量とPSSIの比(Mw/PSSI)が1×104以上である粘度指数向上剤であることを特徴とする、請求項1に記載の潤滑油組成物。
- 前記過塩基性金属系清浄剤が、アルカリ土類金属サリシレートをアルカリ土類金属ホウ酸塩で過塩基化した過塩基性アルカリ土類金属サリシレートであることを特徴とする、請求項1または2に記載の潤滑油組成物。
- 前記摩擦調整剤が、有機モリブデン系摩擦調整剤であることを特徴とする、請求項1~3のいずれか1項に記載の潤滑油組成物。
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WO2017105747A1 (en) * | 2015-12-18 | 2017-06-22 | The Lubrizol Corporation | Nitrogen-functionalized olefin polymers for engine lubricants |
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WO2018125956A1 (en) * | 2016-12-30 | 2018-07-05 | Exxonmobil Research And Engineering Company | Low viscosity lubricating oil compositions for turbomachines |
US10443008B2 (en) | 2017-06-22 | 2019-10-15 | Exxonmobil Research And Engineering Company | Marine lubricating oils and method of making and use thereof |
CN110770331B (zh) * | 2017-06-30 | 2023-01-24 | 雪佛龙奥伦耐有限责任公司 | 含有异构化酚基清净剂的低粘度发动机油 |
US20190270946A1 (en) * | 2018-03-02 | 2019-09-05 | Chevron Oronite Technology B.V. | Lubricating oil composition providing wear protection at low viscosity |
JP2021515070A (ja) * | 2018-03-02 | 2021-06-17 | シェブロン・オロナイト・テクノロジー・ビー.ブイ. | 低粘度で摩耗防止を提供する潤滑油組成物 |
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