EP2457985B1 - Composition d'huile lubrifiante pour lubrifier des moteurs d'automobile - Google Patents

Composition d'huile lubrifiante pour lubrifier des moteurs d'automobile Download PDF

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Publication number
EP2457985B1
EP2457985B1 EP11190695.4A EP11190695A EP2457985B1 EP 2457985 B1 EP2457985 B1 EP 2457985B1 EP 11190695 A EP11190695 A EP 11190695A EP 2457985 B1 EP2457985 B1 EP 2457985B1
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EP
European Patent Office
Prior art keywords
oil composition
lubricating oil
lubricating
viscosity
amount
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EP11190695.4A
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German (de)
English (en)
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EP2457985A1 (fr
Inventor
Hiroki Andoh
Morikuni Nakazato
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Chevron Japan Ltd
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Chevron Japan Ltd
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Priority claimed from US13/294,910 external-priority patent/US8784642B2/en
Application filed by Chevron Japan Ltd filed Critical Chevron Japan Ltd
Publication of EP2457985A1 publication Critical patent/EP2457985A1/fr
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • 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
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • 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
    • C10M2223/042—Metal salts thereof
    • 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
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/74—Noack Volatility
    • 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
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/253—Small diesel engines
    • 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 of low viscosity type for lubricating automotive engines, which shows good fuel economy.
  • the invention is directed to a lubricating oil composition of a low viscosity type for lubricating automotive engines which shows high wear inhibition performance, though which gives good fuel economy.
  • the lubricating oil composition of the invention is favorably employable for lubricating a four cycle gasoline engine of motorcycles and a diesel engine mounted on motor cars equipped with an exhaust gas post-processing apparatus.
  • lubricating oil compositions to be used for lubricating engines mounted in gasoline engine-mounted automobiles and diesel engine-mounted automobiles engine oils of a low viscosity type giving good fuel economy have been required.
  • SAE viscosity grade of 0W20 showing a high temperature-high shear viscosity (HTHS viscosity determined at 150°C under the condition of a shear rate of 10 6 /s) of approx. 2.6 mPa ⁇ s is employed in practice.
  • ACEA C1-08 & C2-08 that is, European Specifications for the engine oils, indicate that the lower limit of the high temperature high shear viscosity (at 10 6 /s) is 2.9 mPa ⁇ s s and that the upper limit of Noack evaporation loss is 13%.
  • Patent Publication JP 6-306384A describes a fuel economy type-lubricating oil for internal combustion engines comprising a mineral base oil showing a kinematic viscosity of 3-5 cST (at 100°C), a viscosity index of 135 or higher, and a paraffin/total hydrocarbon ratio (namely, % Cp) of 90% or more and a specific amount of an organic molybdenum compound.
  • Patent Publication JP 2003-505533A describes a low-volatile fuel economy type lubricating oil composition showing NOACK volatility of 15 wt.% or less, which comprises at least 50 wt.% of a mineral oil, at least 95 wt.% of a saturated product and not more than 25 wt.% of naphthenes, which shows a kinematic viscosity of 4.0-5.5 mm 2 /s, a viscosity index of at least 120 and NOACK volatility of 15.5 wt.% or less, a specific amount of a calcium-containing detergent and a specific amount of an oil-soluble organic friction modifier.
  • Patent Publication JP 2000-87070A describes an engine oil composition for four cycle engine motorcycles showing low oil consumption and good fuel economy, which comprises a hydrocarbon base oil showing a kinematic viscosity of 3-10 mm 2 /s (at 100°C) and a viscosity index of 120 or higher or a mixed base oil containing 15 wt.% of more of the hydrocarbon base oil, a zinc dialkyldithiophosphate, a metal-containing detergent, an ashless dispersant, a friction modifier and a viscosity index improver (which imparts a kinematic viscosity of 9.3-16.5 mm 2 /s at 100°C to the oil composition).
  • a hydrocarbon base oil showing a kinematic viscosity of 3-10 mm 2 /s (at 100°C) and a viscosity index of 120 or higher or a mixed base oil containing 15 wt.% of more of the hydrocarbon base oil
  • Patent Publication JP 2000-87070A further describes engine oil compositions of SAE viscosity grade of 10W30 and 10W40 for four cycle engine motorcycles.
  • EP 2009084 describes a lubricating base oil comprising saturated components of 90 % by mass or greater, wherein the proportion of cyclic saturated components among the saturated components is not greater than 40 % by mass, and by having a viscosity index of 110 or higher and an iodine value of 2.5.
  • WO 98/23711 describes lubricant compositions for automotive engines having a kinematic viscosity at 100 °C of less than 12.5 mm 2 /s and a high temperature, high shear dynamic viscosity (i.e.
  • a temperature of 150 °C and a shear rate of 10 6 /s) of at least 2.9 mPa.s and comprising: 70 to 99.5 wt.% of a base oil having a kinematic viscosity at 100 °C of 2 to 8 mm 2 /s and a viscosity index of at least 120; and 0.5 to 3 wt.% of an alkenylarene-conjugated diene copolymer as a viscosity index improver.
  • the present invention provides a lubrication oil composition as set out in claim 1, uses as set out in claims 5 and 6, a method of lubrication a four cycle gasoline engine as set out in claim 7, and a method of lubrication a diesel engine as set out in claim 8.
  • a lubricating oil composition having a low viscosity is effective to increase fuel economy of automotive engines. Therefore, as described herein before, a lubricating oil composition of SAE viscosity grade of 0W20 showing a HTHS viscosity (at 10 6 /s) of approximately 2.6 mPa ⁇ s s is employed in practice.
  • a lubricating oil composition of SAE viscosity grade of 0W20 which shows a viscosity index in the range of 200 to 240, a high HTHS viscosity (at 150°C and 10 6 /s) such as 2.9 mPa ⁇ s s or higher, a Noack evaporation loss of 13% or less, and a satisfactorily high wear inhibition can be produced by the use of a base oil showing an extremely high viscosity index such as in the range of approximately 133 to 160 which is prepared by subjecting slack wax or synthetic wax obtained by Fischer-Tropsh process to a hydrogenation-isomerization process, distillation and dewaxing and has recently become available on market, as well as optimization of an additive composition and additive contents.
  • a lubricating oil composition of SAE viscosity grade of 0W20 gives good fuel economy for the reason of a relatively low kinematic viscosity at either a high temperature or a low temperature.
  • a lubricating oil composition of SAE viscosity grade 0W20 for lubricating automotive engines which comprises a base oil and the below-described additive components and which shows a viscosity index in the range of 200 to 240, a high temperature-high shear viscosity (i.e., HTHS viscosity) of not less than 2.9 mPa ⁇ s s at 150°C under a shear rate of 10 6 /s, and a Noack evaporation loss of not more than 13%:
  • the amounts of the additive components are in terms of wt.% based on a total amount of the oil composition, wherein the base oil shows a viscosity index in the range of 133 to 160 and is produced by subjecting slack wax or synthetic wax obtained by Fischer-Tropsch process to a hydrogenation-isomerization process, distillation and dewaxing.
  • the lubricating oil composition of SAE viscosity grade 0W20 means a lubricating oil composition satisfying the viscosity property for "0W20" described in "SAE Viscosity Grades for Engine Oils” issued (updated in 2007) by API.
  • the high shear viscosity means a shear viscosity determined at the shear rate of 10 6 /s.
  • the lubricating oil composition of the invention of SAE viscosity grade 0W20 shows such a high HTHS viscosity as 2.9 m Pa ⁇ s or higher and hence shows good fuel economy and good wear inhibition. Accordingly, the lubricating oil composition of the invention is favorably employable for lubricating a four cycle gasoline engine of motorcycles as well as a diesel engine of automotives equipped with an exhaust gas post-processing apparatus.
  • the base oil of the lubricating oil composition according to the invention preferably is a mineral oil.
  • the base oil can be a mixture of a relatively large amount (not less than 50 wt.%) of a mineral oil and a relatively small amount (less than 50 wt.%) of a synthetic oil.
  • the base oil for the lubricating oil composition of the invention preferably is a base oil (specifically a mineral oil) that has a saturated hydrocarbon content of 95 wt.% or more, particularly 98 wt.% or more, and shows a kinematic viscosity in the range of 2 to 9 mm 2 /s and a viscosity index of 133 or higher (particularly 135 or higher, further particularly 145 or higher).
  • the preferred base oil may be a single base oil or a mixture of two or more base oils.
  • the preferred base oil can be mixed with a small amount of a base oil having a different composition and showing different characteristics. However, it is preferred that the mixture of base oils has the above-mentioned preferred composition and shows the above-mentioned preferred characteristics.
  • the above-mentioned preferred base oil preferably shows an evaporation loss (according to ASTM D5800) of 16% or less, more preferably 15% or less, further preferably 13% or less. If the engine oil (i.e., lubricating oil composition) employs a base oil showing a high evaporation loss, the engine oil shows high oil consumption and high viscosity increase when the engine oil is kept at elevated temperatures. Thus, the fuel economy decreases.
  • the base oil preferably is a base oil having a high viscosity index in the range of 133-160, which is produced by subjecting slack wax or synthetic wax obtained from natural gas by Fischer-Tropsch process to a hydrogenation-isomerization process, distillation and dewaxing, in the case that the base oil is a mineral base oil.
  • the above-mentioned high viscosity index base oil is preferably employed for the preparation of the lubricating oil composition of the invention, because the base oil shows a high kinematic viscosity at 100°C and a good low temperature viscosity characteristic and lowers the evaporation loss of the oil composition.
  • the above-mentioned mineral base oil having a high viscosity index can be used in a mixture with a synthetic oil.
  • the synthetic oil preferably shows the above-mentioned preferred characteristics.
  • the preferred synthetic oil can be selected from a variety of known synthetic oils. Examples of the known synthetic oils include esters, alkylbenzenes, and poly- ⁇ -olefins (PAOs). Most preferred is poly- ⁇ -olefins (PAOs).
  • the lubricating oil composition of the invention contains a nitrogen-containing ashless dispersant (component (a)) in an amount of 0.01 to 0.3 wt.% in terms of nitrogen content.
  • the nitrogen-containing ashless dispersant preferably has a weight average molecular weight in the range of 4,500 to 20,000.
  • the "weight average molecular weight” used herein means a molecular weight determined by GPC analysis (reference material: polystyrene).
  • nitrogen-containing ashless dispersants examples include an alkenyl- or alkyl-succinimide (wherein the alkenyl or alkyl group is derived from polyolefin) or its derivatives.
  • the nitrogen-containing ashless dispersant is preferably contained in the lubricating oil composition in an amount of 0.01 to 0.3 wt.%, based on the total amount of the lubricating oil composition.
  • a representative succinimide dispersant can be prepared from a succinic anhydride having a high molecular weight alkyl or alkenyl substituent and a polyalkyleneamine containing average 4-10 nitrogen atoms, preferably 5-7 nitrogen atoms, per one molecule.
  • the high molecular weight alkyl or alkenyl substituent is preferably derived from polyalkene, particularly polybutene, having a number average molecular weight of approx. 900 to 5,000.
  • the process for obtaining the polybutenyl-succinic acid anhydride by the reaction of polybutene and maleic anhydride is generally performed by the chlorination process using a chloride compound.
  • the chlorination process is advantageous in its reaction yield.
  • the reaction product obtained by the chlorination process contains a large amount (for instance, approx. 2,000 ppm) of chlorine. If the thermal reaction process using no chloride compound is employed, the reaction product contains only an extremely small chlorine (for instance, 30 ppm or less).
  • a highly reactive polybutene containing a methylvinylidene structure at least approx.
  • the thermal reaction process can give a high reaction yield. If the reaction yield is high, the reaction product necessarily contains a reduced amount of the unreacted polybutene. This means that a dispersant containing a large amount of the effective component (succinimide) is obtained. Accordingly, it is preferred that the polybutenyl succinic acid anhydride is produced from the highly reactive polybutene by the thermal reaction and that the produced polybutenyl succinic acid anhydride is reacted with polyalkylenepolyamine having an average nitrogen atom number in the range of 4 to 10 (in one molecule) to give the succinimide.
  • the succinimide further can be reacted with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, organic acid or the like, to give a modified succinimide.
  • a borated alkenyl(or alkyl)-succinimide which is obtained by the reaction with boric acid or a boron compound is advantageous from the viewpoints of thermal and oxidation stability.
  • the succinimide can be one of mono-type, bis-type and poly-type which are named according to the imide structure(s) contained in the succinimide molecule.
  • the succinimide of bis-type or poly-type can be preferably employed as the ashless dispersant in the lubricating oil composition of the invention.
  • nitrogen-containing ashless dispersants include polymeric succinimide dispersants derived from ethylene- ⁇ -olefin copolymer (for instance, the molecular weight is 1,000 to 15,000), and alkenylbenzyl amine ashless dispersants.
  • the nitrogen-containing ashless dispersant can be replaced with a nitrogen-containing dispersant-type viscosity index improver.
  • a nitrogen-containing dispersant-type viscosity index improver a nitrogen-containing olefin copolymer or a nitrogen-containing polymethacrylate each having a weight mean molecular weight of 90,000 or more (in terms of polystyrene converted-molecular weight determined by GPC analysis).
  • the former nitrogen-containing olefin copolymer is advantageous.
  • the lubricating oil composition of the invention necessarily contains the nitrogen-containing ashless dispersant and/or the nitrogen-containing dispersant-type viscosity index improver. If desired, the other ashless dispersants such as an alkenylsuccinic acid ester dispersant can be employed in combination.
  • the lubricating oil composition of the invention contains an alkaline earth metal-containing detergent (component (b)) in an amount of 0.08 to 0.3 wt.% in terms of alkaline earth metal content.
  • alkaline earth metals include calcium, barium and magnesium. Preferred is calcium.
  • the alkaline earth metal-containing detergent preferably is an alkaline earth metal sulfonate or an alkaline earth metal phenate.
  • the alkaline earth metal sulfonate and alkaline earth metal phenate can be employed in combination.
  • these metal-containing detergents can be used in combination with other metal-containing detergent such as an alkaline earth metal (particularly calcium) salt of an alkyl-salicylate and/or an alkylcarboxylate.
  • overbased calcium sulfonates having a TBN in the range of 150 to 500 mgKOH/g and low base number calcium sulfonates having a TBN in the range of 5 to 60 mgKOH/g.
  • the overbased calcium sulfonate preferably is an overbased calcium salt of an alkylated benzenesulfonate having an alkyl group of 10 or more carbon atoms and an overbased calcium salt of an alkylated toluenesulfonate having an alkyl group of 10 or more carbon atoms.
  • the degree of the overbasing preferably is in the range of 5 to 25.
  • the low base number calcium sulfonate preferably is a calcium salt of an alkylated benzenesulfonate or a calcium salt of an alkylated benzenesulfonate.
  • the alkyl group preferably contains 10 or more carbon atoms.
  • the low base number calcium sulfonate preferably is a neutral salt or the like (preferably having an overbasing degree in the range of 0.1 to 1.5) having been subjected to no overbasing process. Preferred is a combination of an overbased calcium sulfonate and a low base number calcium sulfonate.
  • the sulfonate can be a synthetic sulfonate or a petroleum-origin sulfonate which is prepared by the steps of sulfonating a lubricating oil fraction of a mineral oil and reacting it with a calcium compound. Therefore, the low base number calcium sulfonate and/or the overbased calcium sulfonate derived from petroleum products can also be favorably employed.
  • overbased sulfurized calcium phenates having a TBN of 120-350 mgKOH/g.
  • Preferred is an overbased sulfurized calcium phenate having an alkyl group of 10 carbon atoms or more.
  • the lubricating oil composition of the invention contains a phosphorus-containing wear inhibitor (component (c)) in an amount of 0.05 to 0.12 wt.% in terms of phosphorus content.
  • the phosphorus-containing wear inhibitor preferably is zinc dihydrocarbyldithiophosphate or a zinc dihydrocarbylphosphate, both of which are known as multifunctional lubricating oil additives showing oxidation inhibition performance and wear inhibition performance.
  • the zinc dihydrocarbyldithiophosphate generally is a zinc dialkyldithiophosphate having a primary alkyl or a secondary alkyl. From the viewpoint of anti-wear performance, preferred is a zinc dialkyldithiophosphate having a secondary alkyl group which is derived from a secondary alcohol having 3 to 18 carbon atoms. In contrast, a zinc dialkyldithiophosphate having a primary alkyl group which is derived from a primary alcohol having 3 to 18 carbon atoms is advantageous in its excellent heat resistance and friction reducing function.
  • the zinc dialkyldithiophosphate having a secondary alkyl group and the zinc dialkyldithiophosphate having a primary alkyl group can be used in combination.
  • a zinc dialkyldithiophosphate having a primary alkyl group and a secondary alkyl group which can be obtained from a mixture of a primary alcohol and a secondary alcohol can also be favorably employed.
  • a zinc dialkylaryldithiophosphate e.g., zinc dialkylaryldithiophosphate obtainable using dodecylphenyl
  • zinc dialkylaryldithiophosphate obtainable using dodecylphenyl
  • the phosphorus-containing wear inhibitor can be a phosphorus ester, a phosphite ester, or a thiophosphate ester.
  • the lubricating oil composition of the invention further contains at least one oxidation inhibitor (component (d)) selected from the group consisting of phenol compounds (phenolic oxidation inhibitors), amine compounds (amine oxidation inhibitors), and molybdenum compounds (molybdenum oxidation inhibitors) in an amount of 0.1 to 7 wt.%.
  • at least one oxidation inhibitor selected from the group consisting of phenol compounds (phenolic oxidation inhibitors), amine compounds (amine oxidation inhibitors), and molybdenum compounds (molybdenum oxidation inhibitors) in an amount of 0.1 to 7 wt.%.
  • a representative phenolic oxidation inhibitor is a hindered phenol compound, and a representative amine oxidation inhibitor is a diarylamine compound.
  • the hindered phenol compound and diarylamine compound are advantageous because both further provide high detergency at high temperatures.
  • the diarylamine oxidation inhibitor is particularly advantageous because it has a base number derived from the contained nitrogen which serves to increase detergency at high temperatures.
  • the hindered phenol oxidation inhibitor is effective to reduce oxidative deterioration caused by NO x .
  • hindered phenol oxidation inhibitors examples include 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isopropylidenebis(2, 6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis[3-(3,5 -di-t-butyl-4-hydoxyphenyl)propionate], octyl 3 -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)
  • diarylamine oxidation inhibitors examples include alkyldiphenylamine having a mixture of alkyl groups of 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylated N-naphthylamine, and alkylated phenyl-1-naphthylamine.
  • the molybdenum oxidation inhibitor can be an oxymolybdenum complex of a basic nitrogen compound.
  • Preferred examples of the oxymolybdenum complex of a basic nitrogen compound include an oxymolybdenum complex of succinimide and an oxymolybdenum complex of carboxylamide.
  • the oxymolybdenum complex of a basic-nitrogen compound can be prepared by the following process: an acidic molybdenum compound or its salt is caused to react with a basic nitrogen-containing compound such as succinimide, carboxylamide, hydrocarbyl monoamine, hydrocarbyl polyamine, Mannich base, phosphonamide, thiophosphonamide, phosphoramide and a dispersant-type viscosity index improver (or a mixture thereof) at a temperature of 120°C or lower.
  • a basic nitrogen-containing compound such as succinimide, carboxylamide, hydrocarbyl monoamine, hydrocarbyl polyamine, Mannich base, phosphonamide, thiophosphonamide, phosphoramide and a dispersant-type viscosity index improver (or a mixture thereof) at a temperature of 120°C or lower.
  • Molybdenum-containing compounds other than the above-mentioned oxymolybdenum complex of a basic nitrogen compound can be employed in place of the oxymolybdenum complex of a basic nitrogen compound or in combination with the oxymolybdenum complex of a basic nitrogen compound.
  • the above-mentioned "other molybdenum-containing compound” can be sulfurized oxymolybdenum dithiocarbamate or sulfurized oxymolybdenum dithiophosphate.
  • Each of the phenolic oxidation inhibitor (particularly, hindered phenol oxidation inhibitor), amine oxidation inhibitor (particularly, diarylamine oxidation inhibitor) and a molybdenum oxidation inhibitor (particularly, oxymolybdenum complex of a basic nitrogen compound) can be employed singly or in combination. If desired, other oil soluble oxidation inhibitors can be employed in combination with the above-mentioned oxidation inhibitor(s).
  • the lubricating oil composition of the invention further contains a viscosity index improver (component (e)) in an amount of 0.5 to 20 wt.%.
  • a viscosity index improver component (e)
  • examples of the viscosity index improvers include polymethacryl viscosity improvers such as polyalkyl methacrylate and olefin copolymer viscosity index improvers such as ethylene-propylene copolymer, styrenebutadiene copolymer, and polyisoprene.
  • the viscosity index improvers can be used singly or in combination.
  • the lubricating oil composition of the invention preferably contains an organic sulfur compound which is effective in wear inhibition and oxidation inhibition.
  • organic sulfur compounds include sulfurized olefin, sulfurized ester, sulfurized oil/fat, polysulfide, dimercaptothiazole, dithiophosphate ester, and dithiocarbamate.
  • the lubricating oil composition of the invention may further contain an alkali metal borate hydrate for increasing high temperature detergency and a basic number.
  • the alkali metal borate hydrate can be contained in an amount of 5 wt.% or less, particularly 0.01 to 5 wt.%.
  • Some alkali metal borate hydrates contain an ash component and a sulfur component. Therefore, the alkali metal borate hydrate can be used in an appropriate amount in consideration of the composition of the resulting lubricating oil composition.
  • the lubricating oil composition of the invention may further contain a small amount of various auxiliary additives. Examples of the auxiliary additives are described below.
  • organic amide compounds e.g., oleylamide
  • benzotriazol compounds and thiadiazol compounds functioning as metal deactivating agent
  • nonionic polyoxyalkylene surface active agents such as polyoxyethylene alky
  • the auxiliary additives can be preferably incorporated into the lubricating oil composition in an amount of 3 wt% or less (particularly, 0.001 to 3 wt.%).
  • a lubricating oil composition of the invention (SAE viscosity grade: 0W20, High temperature high shear viscosity: 2.9 mPa ⁇ s or higher) was prepared using the following additives and base oil in Examples 1 and 2.
  • a lubricating oil composition (SAE viscosity grade: 0W20, High temperature high shear viscosity: 2.6 mPa ⁇ s) was prepared.
  • a lubricating oil composition SAE viscosity grade: 10W30, High temperature high shear viscosity: 2.9 mPa ⁇ s or higher) was prepared.
  • Base oil-1 a mixture of base oil (a) and base oil (b) in a weight ratio of 60:40 (base oil (a):base oil (b), viscosity index: 142; kinematic viscosity at 100°C: 4.9 mm 2 /s; Noack evaporation loss: 10.1%) in which the base oil (a) was a mineral oil-origin base oil prepared by subjecting slack wax to hydrogenation-isomerization, distillation and dewaxing(viscosity index: 137; kinematic viscosity at 100°C: 4.1 mm 2 /s; Noack evaporation loss: 13.6%) and base oil (b) was a mineral oil-origin base oil prepared by subjecting slack wax to hydrogenation-isomerization, distillation and dewaxing; viscosity index: 148; kinematic viscosity at 100°C: 6.6 mm 2 /s, Noack evaporation loss: 5.0
  • Base oil-2 hydrocracked mineral oil (viscosity index: 128; kinematic viscosity at 100°C: 4.2 mm 2 /s, Noack evaporation loss: 14.2%).
  • Base oil-3 a mixture of hydrocracked mineral oil (a) and hydrocracked mineral oil (b) in a weight ratio of 73:27 (mineral oil (a):mineral oil (b); viscosity index: 115; kinematic viscosity at 100°C: 6.7 mm 2 /s, Noack evaporation loss: 10.8%) in which the hydrocracked mineral oil (a) had viscosity index: 122; kinematic viscosity at 100°C: 5.6 mm 2 /s, Noack evaporation loss: 12.4%, and the hydrocracked mineral oil (b) had viscosity index: 99; kinematic viscosity at 100°C: 10.7 mm 2 /s, Noack evaporation loss: 6.0%.
  • the base oil was used in an amount to give in combination with the additives a total 100 wt.% of the lubricating oil composition.
  • Zinc di(secondary alkyl)dithiophosphate P: 7.2 wt.%, Zn: 7.8 wt.%, S: 14 wt.%, prepared by using a secondary alcohol having 3 to 8 carbon atoms): 0.06 wt.% (in terms of P content)
  • Zinc di(primary alkyl)dithiophosphate P: 7.3 wt.%, Zn: 8.4 wt.%, S: 14 wt.%, prepared by using a primary alcohol having 8 carbon atoms): 0.03 wt.% (in terms of P content)
  • Dialkyldiphenylamine having a mixture of C 4 and C 8 alkyl groups (N: 4.6 wt.%): 0.45 wt.%
  • Each of the lubricating oil compositions was subjected to Shell Four Ball Test under the conditions of oil temperature of 75°C, load of 40 kgf, and rotation for 60 minutes at 1,200 rpm, to evaluate its wear inhibition property.
  • the wear inhibition property was evaluated by determining a wear mark formed on the surfaces of the tested balls.
  • Table 1 shows physical properties of the lubricating oil compositions of Examples 1, 2, Comparison Example, and Reference Example.
  • Table 1 Ex. 1 Ex. 2 Com.Ex. Ref.Ex. SAE 0W20 0W20 0W20 10W30 Base oil Base oil-1 Base oil-1 Base oil-2 Base oil-3 HTHS viscosity 2.97 3.00 2.62 3.15 Kinematic viscosity at 100°C 9.16 9.20 8.02 10.1 at 40°C 41.9 42.2 36.3 65.7
  • Viscosity index 209 209 203 139 Cranking viscosity at -25°C - - - 5815 at -35°C 5854 5859 5254 - Pumping viscosity Pass (-40°C) Pass (-40°C) Pass (-40°C) Pass (-30°C) Noack evaporation loss (%) 9.9 10.3 14.0 11.5 Shell wear test, Average wear diameter (mm) 0.49 0.48 0.55 0.49
  • HTHS viscosity viscosity (unit: mPa ⁇ s, determined at 150°C at a shear rate of 10 6 /s.
  • Kinematic viscosity unit mm 2 /s Cranking viscosity: unit mPa ⁇ s "Pass" for Pumping viscosity means that the lubricating oil composition satisfies the pumping viscosity at -40°C which is indicated for SAE 0W20 or the pumping viscosity at - 30°C which is indicated for SAE 10W30.

Claims (8)

  1. Une composition d'huile lubrifiante de grade de viscosité SAE 0W20 pour lubrifier des moteurs automobiles qui comprend une huile de base et les composants additifs décrits ci-dessous et qui présente un indice de viscosité dans la plage de 200 à 240, une viscosité de cisaillement élevée à haute température d'au moins 2,9 mPa×s s à 150°C sous un taux de cisaillement de 106/s et une perte d'évaporation Noack non supérieure à 13%:
    a) un dispersant sans cendres contenant de l'azote en une quantité de 0,01 à 0,3% en poids en termes de teneur en azote;
    b) un détergent contenant des métaux alcalino-terreux en une quantité de 0,08 à 0,3% en poids en termes de teneur en métaux alcalino-terreux;
    c) un inhibiteur d'usure contenant du phosphore en une quantité de 0,05 à 0,12% en poids en termes de teneur en phosphore;
    d) un inhibiteur d'oxydation choisi parmi le groupe constitué en les composés d'amine, les composés de phénol et les composés de molybdène, en une quantité de 0,1 à 7% en poids, et
    e) un améliorant d'indice de viscosité en une quantité de 0,5 à 20% en poids,
    dans laquelle les quantités des composants additifs sont exprimées en termes de % en poids sur la base d'une quantité totale de la composition d'huile lubrifiante,
    dans laquelle l'huile de base présente un indice de viscosité compris entre 133 et 160 et est produite en soumettant de la paraffine brute ou de la cire synthétique obtenue par le procédé Fischer-Tropsch à un procédé d'hydrogénation-isomérisation, de distillation et de déparaffinage.
  2. La composition d'huile lubrifiante selon la revendication 1, qui présente une viscosité cinématique non inférieure à 8,5 mm2/s à 100°C.
  3. La composition d'huile lubrifiante selon la revendication 1 ou 2, qui a une viscosité cinématique non supérieure à 9,3 mm2/s à 100°C.
  4. La composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, qui contient un composé organique contenant du soufre.
  5. L'utilisation de la composition d'huile lubrifiante selon l'une quelconque des revendications précédentes, pour lubrifier des motocycles équipés avec un moteur à essence à quatre temps.
  6. L'utilisation de la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 4, pour lubrifier un moteur diesel monté sur des véhicules à moteur équipés avec un appareil de post-traitement de gaz d'échappement.
  7. Un procédé de lubrification d'un moteur à essence à quatre temps de motocycles avec la composition d'huile lubrifiante selon l'une quelconque des revendications 1 à 4.
  8. Un procédé de lubrification d'un moteur diesel monté sur des véhicules à moteur équipés avec un appareil de post-traitement de gaz d'échappement utilisant la composition d'huile de lubrification selon l'une quelconque des revendications 1 à 4.
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JP6339593B2 (ja) * 2013-03-04 2018-06-06 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ 潤滑組成物

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WO1998023711A1 (fr) * 1996-11-25 1998-06-04 Exxon Research And Engineering Company Composition lubrifiante pour moteurs ayant un grand pouvoir lubrifiant et de reduction de la consommation carburant

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JP2693698B2 (ja) 1993-04-22 1997-12-24 株式会社ジャパンエナジー 省燃費型潤滑油
JP4076634B2 (ja) 1998-09-09 2008-04-16 新日本石油株式会社 二輪車用４サイクルエンジン油組成物
US6333298B1 (en) 1999-07-16 2001-12-25 Infineum International Limited Molybdenum-free low volatility lubricating oil composition
US7067049B1 (en) * 2000-02-04 2006-06-27 Exxonmobil Oil Corporation Formulated lubricant oils containing high-performance base oils derived from highly paraffinic hydrocarbons
WO2007114132A1 (fr) * 2006-03-31 2007-10-11 Nippon Oil Corporation Huile de graissage de base, son procede de fabrication et composition d'huile lubrifiante
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