EP2636725B1 - Composition d'huile lubrifiante pour la lubrification d'un moteur automobile - Google Patents

Composition d'huile lubrifiante pour la lubrification d'un moteur automobile Download PDF

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Publication number
EP2636725B1
EP2636725B1 EP13157940.1A EP13157940A EP2636725B1 EP 2636725 B1 EP2636725 B1 EP 2636725B1 EP 13157940 A EP13157940 A EP 13157940A EP 2636725 B1 EP2636725 B1 EP 2636725B1
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Prior art keywords
lubricating oil
viscosity
oil composition
mass
base oil
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German (de)
English (en)
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EP2636725A1 (fr
Inventor
Andoh Hiroki
Morikuni Nakazato
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Chevron Japan Ltd
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Chevron Japan Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/24Compounds containing phosphorus, arsenic or antimony
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/20Compounds containing nitrogen
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/06Mixtures of thickeners and additives
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating 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
    • C10M171/02Specified values of viscosity or viscosity index
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • C10M2203/1025Aliphatic fractions used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022Ethene
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/16Paraffin waxes; Petrolatum, e.g. slack wax
    • C10M2205/163Paraffin waxes; Petrolatum, e.g. slack wax used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17Fisher Tropsch reaction products
    • C10M2205/173Fisher Tropsch reaction products used as base material
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/12Groups 6 or 16
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54Fuel economy
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/68Shear stability
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74Noack Volatility
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/255Gasoline engines

Definitions

  • the present invention relates to an excellent fuel-efficient, low-viscosity lubricating oil composition for an automobile engine, and in particular, relates to a lubricating oil composition for automobile engine lubrication that, while being an excellent fuel-efficient, low-viscosity lubricating oil composition for engine lubrication, also shows high wear resistance.
  • the present invention relates to a low-viscosity lubricating oil composition that is particularly suitable for lubricating a motorcycle four-cycle gasoline engine or a diesel engine having an exhaust gas after-treatment device.
  • engine oil lubricating oil composition
  • engine oils that have an SAE viscosity grade of 5W20 and a high-temperature high-shear viscosity (value measured at 150°C when the shear velocity or shear rate is 10 6 s -1 ) of 2.6 mPa ⁇ s are already being used for practical purposes as fuel-efficient lubricating oil compositions for gasoline engines in four-wheel drive vehicles.
  • the engine oil is also used to lubricate the transmission system and there is a chance that wear of the energy-transmission devices, such as the transmission gears, will increase (wear resistance will decrease) as a result of a reduction in viscosity of the engine oil.
  • JASO T903-2006 stipulates that the engine oils for motorcycle four-cycle gasoline engines have a high-temperature, high-shear (10 6 s -1 ) viscosity of 2.9 mPa ⁇ s or greater.
  • ACEA C1-08 and C2-08 which are the European standards for engine oils appropriate for lubrication of diesel engine vehicles having diesel particulate filters, set the lower limit of high-temperature, high-shear (10 6 s -1 ) viscosity of engine oils at 2.9 mPa ⁇ s and, in order to limit evaporation loss of engine oils, the upper limit of NOACK evaporation loss at 13%.
  • Patent Document JP (Kokai) 6-306384 describes a fuel-efficient lubricating oil for an internal combustion engine wherein a predetermined amount of an organic molybdenum compound is added to a mineral oil base oil having a dynamic viscosity at 100°C of 3 to 5 cSt, a viscosity index of 135 or higher, and a paraffin to total carbon ratio (%Cp) of 90% or higher.
  • Patent Document JP (Kohyo) 2003-505533 describes a lubricating oil composition that, as a molybdenum additive-free, fuel-efficient, low-volatility lubricating oil composition having a NOACK volatility of 15 wt% or less, contains a predetermined amount of a calcium detergent and a predetermined amount of an oil-soluble organic wear-improving agent, as well as a base oil comprising at least 50 wt% of mineral oil; has a dynamic viscosity at 100°C of 4.0 to 5.5 mm 2 /s; contains 95 wt% or more of saturated product and 25 wt% or less of naphthenes; has a viscosity index of at least 120; and has an NOACK volatility of 15.5 wt% or less.
  • Patent Document JP (Kokai) 2000-87070 describes an excellent fuel-efficient motorcycle four-cycle engine composition having an oil consumption-lowering effect that contains a hydrocarbon lubricating oil base oil having a dynamic viscosity at 100°C of 3 to 10 mm 2 /s and a viscosity index of 120 or higher, or a mixed base oil containing at least 15 mass% of this base oil, a zinc dialkyl dithiophosphate, a metal detergent, an ash-free dispersant, a wear regulator, and a viscosity index-improving agent that brings dynamic viscosity at 100°C of this composition to 9.3 to 16.5 mm 2 /s.
  • it describes a motorcycle four-cycle engine composition having an SAE viscosity grade of 10W30 or 10W40.
  • US2009/163393 A1 discloses lubricating oil for high performance engines comprising a Group III base oil and a combination of ester base stocks.
  • a lubricating oil composition that has an SAE viscosity grade of 5W20 and yet a viscosity index within a range of 140 to 230, a high-shear (10 6 s -1 ) viscosity at 150°C of 2.9 mPa ⁇ s or higher, a NOACK evaporation loss of 13% or less, and excellent wear resistance by using a base oil such as has been recently supplied to the market and is primarily isoparaffin, has an ultrahigh viscosity index wherein the viscosity index is within a range of approximately 133 to 160, and is obtained by hydrogenation and isomerization of a slack wax or a synthetic wax produced by the Fischer-Tropsch method and distillation and dewaxing treatment, and by optimizing the combination of additive components added to the base oil and the amount of each lubricant component.
  • SAE viscosity grade 5W20 are already known
  • the present invention is a lubricating oil composition for automobile engine lubrication, which is a lubricating oil composition comprising a base oil and the following additive components and having an SAE viscosity grade of 5W20, wherein the viscosity index is within a range of 140 to 230, the high-shear viscosity at 150°C is 2.9 mPa ⁇ s or higher, and the NOACK evaporation loss is 13% or less, further comprising:
  • lubricating oil composition having an SAE viscosity grade of 5W20 of the present invention refers to a lubricating oil composition that satisfies the viscosity property of "5W20" described in “SAE viscosity grades for engine oils” of the American Petroleum Institute (revised in 2007).
  • high-shear viscosity refers to the measured value (shear viscosity) when the shear speed or shear rate is 10 6 s -1 .
  • the present invention also is a method for lubricating a motorcycle four-cycle gasoline engine or a diesel engine having an exhaust gas after-treatment device.
  • the lubricating oil composition for lubricating an automobile engine provided by the present invention is a lubricating oil composition having an SAE viscosity grade that is low at 5W20, while having a high-temperature, high-shear viscosity of 2.9 mPa ⁇ s or higher, and shows excellent fuel efficiency and wear resistance.
  • the lubricating oil compositor of the present invention therefore is an excellent fuel-efficient, wear-resistant lubricating oil that is particularly suitable for lubricating a motorcycle four-cycle gasoline engine or a diesel engine having an exhaust gas after-treatment device.
  • the base oil of the lubricating oil composition of the present invention is preferably a mineral oil. It can also be a mixture of a relatively large amount (at least 50 mass%) of a mineral oil and a relatively small amount (less than 50 mass%) of a synthetic oil.
  • the base oil used in the lubricating oil composition of the present invention is a base oil that is primarily an isoparaffin and has a kinematic viscosity at 100°C of 2 to 9 mm 2 /s, a saturated component content of 95 mass% or higher (particularly 98 mass% or higher), and a viscosity index of 133 or higher (particularly 135 or higher, further 145 or higher).
  • a base oil having such properties and composition can be used alone, or a combination of two or more types can be used.
  • the base oil composition after mixing will still have the above-mentioned properties and composition.
  • the base oil having the above-mentioned properties and composition preferably has an evaporation loss (ASTM D5800) of 16% or less (particularly 15% or less, further 13% or less).
  • ASTM D5800 evaporation loss
  • base oil there are no particular restrictions to the type of base oil showing the above-mentioned properties and composition, but when the base oil is a mineral oil, preferably it is a high-viscosity index base oil (base oil having a viscosity index between 133 and 160) the primary component of which is isoparaffin obtained by subjecting the slack wax that is the by-product of dewaxing during the production of mineral oil lubricating base oils, or synthetic wax synthesized using natural gas as the starting material (by the Fischer-Tropsche method), to hydrogenation and isomerization and then distillation and dewaxing.
  • base oil is a mineral oil
  • base oil base oil having a viscosity index between 133 and 160
  • base oil base oil having a viscosity index between 133 and 160
  • isoparaffin obtained by subjecting the slack wax that is the by-product of dewaxing during the production of mineral oil lubricating base oils, or synthetic wax synthesized using natural gas as the
  • Such a high viscosity index base oil has a relatively high dynamic viscosity at 100°C, but has good low-temperature viscosity properties and therefore, can have a reduced evaporation loss and is ideal as the base oil of the lubricating oil composition of the present invention.
  • the high-viscosity-index base oil which is the above-mentioned mineral oil
  • a synthetic oil can be used together with a synthetic oil.
  • the synthetic oil has the above-mentioned properties and composition.
  • the preferred synthetic oil can be selected from a variety of conventional synthetic oils, and examples of such synthetic oils are various esters, alkylbenzenes, and polyalphaolefins (PAO). Polyalphaolefins (PAOs) are particularly preferred.
  • the lubricating oil composition of the present invention comprises a nitrogen-containing ash-free dispersant (component a) in an amount within a range of 0.01 to 0.3 mass% in terms of the nitrogen content.
  • a nitrogen-containing ash-free dispersant component a
  • the mass-average molecular weight of the nitrogen-containing ash-free dispersant is within a range of 4,500 to 20,000.
  • the phrase "mass-average molecular weight" used in the present specification is the molecular weight determined by GPC analysis with polystyrene as the standard substance.
  • Typical examples of the nitrogen-containing ash-free dispersant used in the lubricating oil composition of the present invention are alkenyl and alkyl succinimides derived from polyolefins and derivatives of these succinimides. The amount added is within a range of 0.01 to 0.3 mass% in terms of the nitrogen content based on the total mass of the lubricating oil composition.
  • Typical succinimides are obtained by reacting a succinic anhydride substituted by alkenyl or alkyl groups and having a high molecular weight and a polyalkylene polyamine containing an average of four to ten (preferably five to seven) nitrogen atoms per molecule.
  • the succinimide anhydride that is substituted by alkenyl or alkyl groups and has a high molecular weight is preferably a polyolefin having a number-average molecular weight of approximately 900 to 5,000, particularly polybutene.
  • chlorination by chlorine is used during the step for obtaining a polybutenyl succinimide by reacting polybutene and maleic anhydride.
  • reactivity is good by this method, it has the effect of a large amount of chlorine (for instance, approximately 2,000 ppm) remaining in the succinimide final product.
  • thermal reaction that does not use chlorine is employed, the residual chlorine contained in the final product can be kept to a very low level (for instance, 30 ppm or less).
  • the succinimide that is used is produced by obtaining a polybutenyl succinimide anhydride by thermal reaction using highly reactive polybutene and then reacting this polybutenyl succinic anhydride with a polyalkylene polyamine having an average of four to ten nitrogen atoms (per one molecule).
  • This succinimide can be further reacted with boric acid or an alcohol, aldehyde, ketone, alkyl phenol, cyclic carbonate, organic acid, and the like and used as a so-called modified succinimide.
  • a boric acid-containing alkenyl (or alkyl) succinimide obtained by reaction with boric acid or a boron compound can be used in order to efficiently increase thermal and oxidation stability.
  • this succinimide are mono-types, bis-types, and poly-types in accordance with the number of imide structures per molecule, but the bis-type or poly-type is preferred as the succinimide used for the purpose of the present invention.
  • nitrogen-containing ash-free dispersants examples include polymeric succinimide dispersants derived from ethylene- ⁇ -olefin copolymer (having a molecular weight of 1,000 to 15,000, for instance) and alkenyl benzylamine ash-free dispersants.
  • Nitrogen-containing dispersion-type viscosity index improvers can also be used in place of the nitrogen-containing ash-free dispersant.
  • a nitrogen-containing olefin polymer or a nitrogen-containing polymethacrylate having a mass-average molecular weight of 90,000 or greater is used as the nitrogen-containing dispersion-type viscosity index-improving agent. Taking thermal stability into consideration, the former nitrogen-containing olefin copolymer is effective.
  • the lubricating oil composition of the present invention contains a nitrogen-containing ash-free dispersant and/or nitrogen-containing dispersion-type viscosity index-improving agent as an active ingredient. These can also be used in combination with another ash-free dispersant, such as an alkenyl succinic acid ester ash-free dispersant.
  • the lubricating oil composition of the present invention contains, as a metal-containing detergent, an alkaline earth metal-containing detergent (component (b)) in an amount within a range of 0.08 to 0.4 mass%.
  • alkaline earth metals are calcium, barium, and magnesium, but calcium is preferred.
  • a sulfonate or phenate of the alkaline earth metal is used as the metal-containing detergent.
  • a combination of a sulfonate of an alkaline earth metal and a phenate of an alkaline earth metal can also be used. It is also possible to use a combination of these metal-containing detergents and a metal-containing detergent such as an alkyl salicylate and/or alkyl carboxylate of an alkaline earth metal (particularly calcium).
  • Examples of calcium sulfonates are perbasic calcium sulfonate having a total base value of 150 to 500 mgKOH/g and low-basic calcium sulfonate having a total base value of 5 to 60 mgKOH/g.
  • the perbasic calcium sulfonate is perbasic alkylated calcium benzene sulfonate or alkylated calcium toluene sulfonate having alkyl groups with 10 or more carbon atoms (usually the degree of perbasic conversion is within a range of 5 to 25).
  • the low-basic calcium sulfonate is alkylated calcium benzene sulfonate or alkylated calcium toluene sulfonate having alkyl groups with ten or more carbon atoms and is usually one that is nearly a neutral salt subjected to virtually no perbasic conversion (preferably the degree of perbasic conversion is within a range of 0.1 to 1.5).
  • a combination of a perbasic calcium sulfonate and a low-basic calcium sulfonate is used.
  • the sulfonate can be a synthetic sulfonate as described above, or it can be a petroleum sulfonate obtained by sulfonating a lubricating oil fraction of a mineral oil to a calcium salt. Consequently, a petroleum low-basic calcium sulfonate/perbasic calcium sulfonate such as described above is preferred for the purpose of the present invention.
  • Perbasic sulfurized calcium phenate having a total base value of 120 to 350 mgKOH/g is known as a calcium phenate.
  • a perbasic sulfurized alkyl phenol calcium having alkyl groups with ten or more carbon atoms is preferred.
  • the lubricating oil composition of the present invention contains a phosphorus-containing anti-wear agent (component c) in an amount within a range of 0.05 to 0.12 mass% in terms of the amount of phosphorus.
  • Preferred phosphorus-containing anti-wear agents are zinc dihydrocarbyl dithiophosphate, zinc dihydrocarbyl monothiophate, and zinc dihydrocarbyl phosphate, which are known as lubricating oil additives that are multiperformance in that they have antioxidant performance and anti-wear performance.
  • a primary or secondary alkyl group-type zinc dialkyl dithiophosphate is usually used as the zinc dihydrocarbyl dithiophosphate.
  • a zinc dialkyl dithiophosphate having secondary alkyl groups derived from a C 3-18 secondary alcohol is effective in terms of anti-wear performance.
  • a zinc dialkyl dithiophosphate having primary alkyl groups derived from a C 3-18 primary alcohol has a tendency toward being superior in terms of heat resistance and wear-reducing activity.
  • a combination of a secondary alkyl group-type zinc dialkyl dithiophosphate and a primary alkyl group-type zinc dialkyl dithiophosphate can be used.
  • a zinc dialkylaryl dithiophosphate (such as a zinc dialkylaryl dithiophosphate derived from dodecyl phenol) can also be used as the phosphorus-containing anti-wear agent.
  • phosphoric acid ester phosphorus acid ester, or thiophosphoric acid ester
  • phosphorus-containing anti-wear agent it is also possible to use a phosphoric acid ester, phosphorus acid ester, or thiophosphoric acid ester as the phosphorus-containing anti-wear agent.
  • the lubricating oil composition of the present invention further contains, in an amount that is within a range of 0.1 to 7 mass%, at least one antioxidant (component d) selected from the group consisting of phenol compounds (phenol antioxidants), amine compounds (amine antioxidants), and molybdenum compounds (molybdenum antioxidants).
  • at least one antioxidant selected from the group consisting of phenol compounds (phenol antioxidants), amine compounds (amine antioxidants), and molybdenum compounds (molybdenum antioxidants).
  • a hindered phenol compound is generally used as the phenol antioxidant, and a diaryl amine compound is generally used as the amine antioxidant.
  • Hindered phenol antioxidants and diaryl amine antioxidants are both also effective in improving high-temperature detergency.
  • Diaryl amine antioxidants in particular have a base value derived from nitrogen and are effective in improving high-temperature detergency.
  • hindered phenol antioxidants are effective in preventing oxidative degradation by NO x .
  • hindered phenol antioxidants are 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'-isoropylidenebis(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-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and oc
  • amine antioxidants are C 4-9 mixed alkyl diphenyl amines, p,p'-dioctyldiphenylamine, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, alkylated- ⁇ -naphthylamine, and alkylated-phenyl- ⁇ -naphthylamine.
  • molybdenum antioxidants are oxymolybdenum complexes of basic nitrogen compounds.
  • preferred oxymolybdenum complexes of basic nitrogen compounds are oxymolybdenum complexes of succinimide and oxymolybdenum complexes of carbonamide.
  • Oxymolybdenum complexes of basic nitrogen compounds can be produced using the following method, for instance.
  • a molybdenum complex is produced by reacting an acidic molybdenum compound or salt thereof with a basic nitrogen compound, such as a succinimide, carbonamide, hydrocarbon monoamine, hydrocarbon polyamine, Mannich hydrochloric acid, phosphonamide, thiophosphonamide, phosphoric amide, dispersion-type viscosity index-improving agent (or a mixture thereof), while maintaining the reaction temperature at 120°C or lower.
  • a basic nitrogen compound such as a succinimide, carbonamide, hydrocarbon monoamine, hydrocarbon polyamine, Mannich hydrochloric acid, phosphonamide, thiophosphonamide, phosphoric amide, dispersion-type viscosity index-improving agent (or a mixture thereof).
  • molybdenum-containing compound other than an oxymolybdenum complex of a basic nitrogen compound in place of the oxymolybdenum complex of the basic nitrogen compound, or in combination with the oxymolybdenum complex of a basic nitrogen compound.
  • molybdenum-containing compounds that can be used are sulfurized oxymolybdenum dithiocarbamates and sulfurized oxymolybdenum dithiophosphates.
  • the phenol antioxidant particularly hindered phenol antioxidant
  • amine antioxidant particularly diaryl amine antioxidant
  • molybdenum antioxidant particularly oxymolybdenum complex of basic nitrogen compound
  • the lubricating oil composition of the present invention further comprises a viscosity index-improving agent (component e) in an amount within a range of 0.5 to 20 mass%.
  • a viscosity index-improving agent is polymethacrylate viscosity index-improving agents such as polyalkylmethacrylate, and viscosity index-improving agents based on olefin copolymers, such as ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene.
  • olefin copolymer viscosity index-improving agents have high thermal stability and are effective in terms of the object of the present invention.
  • One having a shear stability index (SSI) of 30 or less (particularly 25 or less) is particularly preferable for the object of the present invention.
  • SSI shear stability index
  • a dispersion-type viscosity index-improving agent or multifunctional viscosity index-improving agent that imparts dispersion performance to these polymer compounds is preferably used.
  • These viscosity index-improving agents can be used alone, or a combination of any two or more viscosity index-improving agents can be used.
  • the lubricating oil composition of the present invention further comprises an organic sulfur compound that is effective in terms of wear resistance and oxidation resistance.
  • organic sulfur compounds having such a property are sulfurized olefins, sulfurized esters, sulfurized oils and fats, polysulfide compound, dimercaptothiadiazoles, dithiophosphoric acid esters, and dithiocarbamates.
  • alkali metal borate hydrate to the lubricating oil composition of the present invention is effective in terms of high-temperature detergency and imparting a base value.
  • the amount of alkali metal borate hydrate is 5 mass% or less, particularly 0.01 to 5 mass%.
  • Alkali metal borate hydrates often have an ash component, sulfur component, and the like, but taking into consideration the properties of the lubricating oil composition of the present invention, an alkali metal borate hydrate can be effectively used by adjusting the amount added.
  • the lubricating oil composition of the present invention can also contain a small amount of various auxiliary additives.
  • auxiliary additives are zinc dithiocarbamate and methylene bis(dibutyl dithiocarbamate), oil-soluble copper compounds, and organic amide compounds (such as oleyl amide) that function as antioxidants or anti-wear agents.
  • compounds such as benzotriazole compounds and thiadiazole compounds that function as metal deactivators.
  • polyoxyalkylene nonionic surfactants such as polyoxyethylene alkylphenyl ethers and copolymers of ethylene oxide and propylene oxide that function as anti-rust agents and demulsifiers.
  • auxiliary additives are each used in an amount that is 3 mass% or less (particularly a range of 0.001 to 3 mass%) in terms of the lubricating oil composition.
  • the lubricating oil composition of the present invention (SAE viscosity grade: 5W20, high-temperature, high-shear viscosity: 2.9 mPa ⁇ s or higher) was produced (Examples 1 and 2) using the following base oil and additives (in the following amounts). Moreover, a lubricating oil composition having an SAE viscosity grade of 5W20 (high-temperature, high-shear viscosity of approximately 2.6 mPa ⁇ s) was produced as a comparative example and a lubricating oil composition having an SAE viscosity grade of 10W30 (high-temperature, high-shear viscosity of 2.9 mPa ⁇ s or higher) was produced as a reference example.
  • Base oil1 Mixture (having viscosity index of 142, a kinematic viscosity at 100°C of 4.9 mm 2 /s, and NOACK evaporation loss of 10.1%) of mineral oil base oil a (having a viscosity index of 137, a kinematic viscosity at 100°C of 4.1 mm 2 /s, and a NOACK evaporation loss of 13.6%) obtained by hydrogenation and isomerization, fractionation, and then dewaxing using slack wax as the starting material and mineral oil base oil b (having a viscosity index of 148, a kinematic viscosity at 100°C of 6.6 mm 2 /s, and NOACK evaporation loss of 5.0%) obtained by hydrogenation and isomerization, fractionation, and then dewaxing using slack wax as the starting material, at a weight ratio of 60:40 (base oil a:base oil b).
  • Base oil 2 Hydrocracked mineral oil (having a viscosity index of 128, a kinematic viscosity at 100°C of 4.2 mm 2 /s, and NOACK evaporation loss of 14.2%)
  • Base oil 3 Mixture (having viscosity index of 115, kinematic viscosity at 100°C of 6.7 mm 2 /s, and NOACK evaporation loss of 10.8%) of hydrocracked mineral oil a (having a viscosity index of 122, a kinematic viscosity at 100°C of 5.6 mm 2 /s, and NOACK evaporation loss of 12.4%) and hydrocracked mineral oil b (having a viscosity index of 99, a kinematic viscosity at 100°C of 10.7 mm 2 /s, and NOACK evaporation loss of 6.0%), at a weight ratio of 73:27 (mineral oil a:mineral oil b)
  • Table 1 shows the properties of each of the lubricating oil compositions and the results of the Shell four spheres test of examples 1 and 2, the comparative example, and the reference example.
  • Table 1 Example 1 Example 2 Comparative Example Reference Example Viscosity grade 5W20 5W20 5W20 10W30 Base oil Base oil 1 Base oil 1 Base oil 2 Base oil 3 High-temperature, high-shear viscosity 2.93 2.91 2.62 3.15 Kinematic viscosity (100°C) 9.15 9.05 8.02 10.1 Kinematic viscosity (40°C) 44.1 43.7 36.3 65.7 Viscosity index 196 195 203 139 Cranking viscosity - - - 5815 -25°C -30°C 3630 3590 2800 - Pumping viscosity at -35°C Passed Passed Passed Passed ⁇ NOACK evaporation loss (%) 9.7 9.8 14.0 11.5 Shell four spheres test 0.47 0.47 0.54 0.48 Average abrasion
  • the kinematic viscosity units are mm 2 /s and the cranking viscosity units are mPa ⁇ s.
  • a pumping viscosity that "passed” means that the pumping viscosity satisfied the regulation for pumping viscosity (at a determination temperature of -35°C) for SAE viscosity grade 5W20.
  • the determination temperature was -30°C for pumping viscosity required by 10W30 and the "passed ⁇ " indicates that the determination passed the regulation for pumping viscosity at -30°C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Claims (8)

  1. Composition d'huile lubrifiante pour la lubrification d'un moteur automobile, qui est une composition d'huile lubrifiante comprenant une huile de base ayant un degré de viscosité SAE de 5W20, où l'indice de viscosité de la composition d'huile lubrifiante est dans l'intervalle de 140 à 230, la viscosité à cisaillement élevé à 150°C de la composition d'huile lubrifiante est 2,9 mPa·s ou plus, et la perte en évaporation NOACK de la composition d'huile lubrifiante est 13 % ou moins, comprenant en plus :
    a) un dispersant libre en cendres et contenant de l'azote à 0,01 à 0,3 %-masse en termes de contenu en azote,
    b) un détergent contenant un métal alcalino-terreux à 0,08 à 0,4 %-masse en termes de contenu en métal alcalino-terreux,
    c) un agent anti-usure contenant du phosphore à 0,08 à 0,4 %-poids en termes de contenu en phosphore,
    d) un antioxydant sélectionné parmi le groupe constitué en composés d'amine, composés de phénol, et composé de molybdène à 0,1 à 7 %-masse,
    e) un agent d'amélioration d'indice de viscosité à 0,5 à 20 %-masse, et en plus où
    la quantité de chaque composante d'additif est le 5-masse en termes du poids total de la composition d'huile lubrifiante ;
    où la perte en évaporation NOACK est déterminée par ASTM D5800 ; et où l'expression « viscosité à cisaillement élevé » concerne à la valeur mesurée (viscosité de cisaillement) si la vitesse de cisaillement ou le degré de cisaillement est 106 s-1, et
    où l'huile de base est :
    une huile de base comprenant comme composante d'huile de base au moins 80 %-masse d'une huile de base à base d'une huile minérale ayant une viscosité cinématique à 100°C qui est dans l'intervalle de 2 à 9 mm2/s et un indice de viscosité de 133 à 160 ; ou
    un huile da base ayant un indice de viscosité de à à 160 qui est obtenue par hydrogénation et isomérisation ou bien d'un gatsch ou d'une cire synthétique produite par le procédé Fischer-Tropsch, et ensuite une distillation et un traitement de décirage.
  2. Composition d'huile lubrifiante selon la revendication 1, dans laquelle l'huile de base est une huile minérale ayant une viscosité cinématique à 100°C qui est dans l'intervalle de 2 à 9 mm2/s et un indice de viscosité de 133 à 160.
  3. Composition d'huile lubrifiante selon la revendication 1, dans laquelle l'agent d'amélioration d'indice de viscosité est un polymère polyméthacrylate ayant un indice de stabilité de cisaillement de 30 ou moins.
  4. Composition d'huile lubrifiante selon la revendication 1, qui comprend en plus un composé de soufre organique comme composante d'additif.
  5. Utilisation de la composition d'huile lubrifiante de la revendication 1 pour lubrifier un moteur de motocyclette à quatre temps.
  6. Utilisation de la composition d'huile lubrifiante de la revendication 1 pour lubrifier le moteur d'un véhicule diesel qui a un dispositif de traitement de gaz d'échappement.
  7. Procédé pour lubrifier un moteur de motocyclette à quatre temps, utilisant la composition d'huile lubrifiante de la revendication 1.
  8. Procédé pour lubrifier le moteur d'un véhicule diesel qui a un dispositif de traitement de gaz d'échappement, utilisant la composition d'huile lubrifiante de la revendication 1.
EP13157940.1A 2012-03-08 2013-03-06 Composition d'huile lubrifiante pour la lubrification d'un moteur automobile Active EP2636725B1 (fr)

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CA2970089A1 (fr) * 2014-03-11 2015-09-17 The Lubrizol Corporation Procede de lubrification d'un moteur a combustion interne
WO2015152143A1 (fr) * 2014-03-31 2015-10-08 出光興産株式会社 Composition d'huile de graissage
CN104031729B (zh) * 2014-07-02 2015-12-09 宝捷润滑油镇江有限公司 一种摩托车引擎专用润滑油及其制备方法
EP3390594B1 (fr) * 2015-12-18 2022-06-29 The Lubrizol Corporation Polymères oléfiniques fonctionnalisés par un azote pour lubrifiants de moteur
JP6927488B2 (ja) 2017-03-30 2021-09-01 出光興産株式会社 二輪車用潤滑油組成物、該潤滑油組成物を用いた二輪車の燃費向上方法、及び該潤滑油組成物の製造方法
JP6936041B2 (ja) * 2017-04-25 2021-09-15 シェルルブリカンツジャパン株式会社 内燃機関用潤滑油組成物
US20180371347A1 (en) * 2017-06-27 2018-12-27 Chevron Oronite Company Llc Lubricating oil composition
JP6744047B2 (ja) * 2018-03-30 2020-08-19 出光興産株式会社 潤滑油組成物、及び潤滑油組成物の使用方法
JP2019206644A (ja) * 2018-05-29 2019-12-05 出光興産株式会社 潤滑油組成物及びその製造方法
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US20130237465A1 (en) 2013-09-12
PH12013000076A1 (en) 2014-11-24
JP5902005B2 (ja) 2016-04-13
PH12013000076B1 (en) 2014-11-24
CN103305318A (zh) 2013-09-18
KR20130103388A (ko) 2013-09-23
SG193720A1 (en) 2013-10-30
KR101968322B1 (ko) 2019-08-13
CA2808765A1 (fr) 2013-09-08

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