EP1111028A1 - Composition d'huile moteur - Google Patents

Composition d'huile moteur Download PDF

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Publication number
EP1111028A1
EP1111028A1 EP00850216A EP00850216A EP1111028A1 EP 1111028 A1 EP1111028 A1 EP 1111028A1 EP 00850216 A EP00850216 A EP 00850216A EP 00850216 A EP00850216 A EP 00850216A EP 1111028 A1 EP1111028 A1 EP 1111028A1
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EP
European Patent Office
Prior art keywords
engine oil
mass
viscosity index
oil composition
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00850216A
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German (de)
English (en)
Other versions
EP1111028A9 (fr
EP1111028B1 (fr
Inventor
Isao Nippon Mitsubishi Oil Corporation Kurihara
Jinichi Nippon Mitsubishi Oil Corp. Igarashi
Kiyoshi Nippon Mitsubishi Oil Corp. Inoue
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
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Nippon Mitsubishi Oil Corp
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Publication of EP1111028A1 publication Critical patent/EP1111028A1/fr
Publication of EP1111028A9 publication Critical patent/EP1111028A9/fr
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    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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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
    • 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
    • C10N2040/26—Two-strokes or two-cycle 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
    • C10N2040/28—Rotary engines

Definitions

  • This invention relates to engine oil compositions, and more particularly to engine oil compositions which provide excellent fuel efficiency and viscosity at low temperatures and are less in evaporation loss.
  • the fuel consumption reduction of automobiles has been put into practice by reducing the body weight of an automobile, improving combustion efficiency, and reducing the occurrence of friction in an engine.
  • the reduction of fiction in engines has been implemented by improving the movable valve structures, reducing the number of piston rings, smoothing the abrasive surfaces of sliding parts, and using fuel efficient engine oils.
  • Japanese Patent Laid-Open Publication No. 8302378 discloses an engine oil composition which comprises a specific base oil, an alkaline earth metal salicylate-based detergent, zinc dialkyldithiophosphate, a polybutenylsuccinimidebased ashless dispersant, a phenol-based ashless oxidation inhibitor, a molybdenumdithiocarbamatebased friction modifier, a viscosity index improves, in a specific amount, respectively.
  • An object of the present invention is to provide an engine oil composition which is reduced more in viscosity than conventional fuel efficient engine oils and provide excellent fuel efficiency and viscosity characteristics at low temperatures with less evaporation loss by blending suitable additives.
  • an engine oil composition which is reduced more in viscosity than conventional fuel efficient engine oils and provide excellent fuel efficiency and viscosity characteristics at low temperatures and is less in evaporation loss can be obtained by blending a specific base oil with an specific amount of a polymethacrylate-based viscosity index improver.
  • an engine oil composition which comprises (A) a lubricant base oil having a kinematic viscosity at 100 ° C of 2 to 6 mm 2 /S, a viscosity index of 120 or more and a total aromatic content of 15 percent by mass or less and (B) a polymethacrylate-based viscosity index improver blended in such an amount that the composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3 mm 2 /s.
  • an engine oil composition which comprises (A) a lubricant base oil having a kinematic viscosity at 100 ° C of 2 to 6 mm 2 /S, a viscosity index of 120 or more and a total aromatics content of 15 percent by mass or less; (B) a polymethacrylate-based viscosity index improver blended in such an amount that the composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3 mm 2 /s; and (C) molybdenumdithiocarbamate.
  • the polymethacrylate-based viscosity index improver have preferably have an weight-average molecular weight of 180,000 or more.
  • a lubricating base oil referred to as Component (A) in an engine oil composition according to the present invention has a kinematic viscosity at 100 ° C of which upper limit is 6 mm 2 /s, preferably 5 mm 2 /s and lower limit is 2 mm 2 /s, preferably 3 mm 2 /s.
  • Lubricant base oils in excess of the upper limit would lead to increased fluid resistance resulting in increased loss caused by wear occurring at engine parts to be lubricated, while those of less than the lower limit would lead to insufficient oil-film formation, resulting in less lubricity and increased evaporation loss.
  • Component (A) has necessarily a viscosity index of 120 or more. Such a viscosity index value is contributive to the production of an engine oil composition having excellent low-temperature viscosity characteristics. Base oils having a viscosity index of less than 120 would lead to a necessity to bring it down lower viscosity, resulting in the increased evaporation loss and viscosity of the resulting engine oil.
  • the upper limit of aromatic content of Component (A) is 15 percent by mass, preferably 10 percent by mass, and most preferably 5 percent by mass. Base oils in excess of the upper limit would fail to achieve synergistic effects with each additive to be used in the present invention. No particular limitation is imposed on the lower limit of aromatic content. However, Component (A) has preferably a total aromatic content of 2 percent by mass or more because that having a total aromatic content of less than 2 percent by mass would not possibly exhibit solubility to various additives.
  • total aromatic content used herein denotes an aromatic fraction content measured in accordance with ASTM D2549. Incorporated by the aromatic fraction are generally alkylbenzenes, alkylnaphthalenes, anthracene, phenanthrene, alkylated products thereof, compounds in which 4 or more benzene rings are condensed, and compounds having hetero-aromatics, such as pyridines, quinolines, phenols, and naphthols.
  • Eligible base oils for the present invention are mineral lubricating oils, synthetic lubricating oils, and mixtures of two or more of these oils mixed in a suitable ratio.
  • the base oils are exemplified by mineral lubricating oils, mixtures of mineral lubricating oils and non-aromatic containing synthetic lubricating oils, and mixtures of aromatic-containing synthetic lubricating oils and non-aromatics containing synthetic lubricating oils.
  • mineral lubricating oil used herein denotes not only a single mineral lubricating oil but also a mixture of two or more mineral lubricating oils. Therefore, when using two more mineral lubricating oils as the base oil, there may be used not only a mixture of mineral lubricating oils each having a total aromatic content of 15 percent by mass or less but also a mixture of a mineral lubricating oil having a total aromatic content of 15 percent by mass and a mineral lubricating oil having a total aromatic content exceeding 15 percent by mass as long as the resulting base oil has a total aromatic content of 15 percent by mass or less.
  • a mineral lubricating oil having a total aromatic content exceeding 15 percent by mass as long as the resulting base oil has a total aromatic content of 15 percent by mass or less.
  • the mineral lubricating oil are those obtained by subjecting a lubricant fraction obtained by vacuum-distilling an atmospheric residue derived from the atmospheric distillation of crude oil to one or more refining processes such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, and hydrorefining.
  • aromatic-containing synthetic lubricating oil examples include alkylnaphthalenes and alkylbenzenes.
  • non-aromatic containing synthetic lubricating oil examples include polybutens and hydrides thereof; poly- ⁇ -olefins such as 1-octene oligomer and 1-decene oligomer, and hydrides thereof; diesters such as ditridecylglutarate, di-2-ethylhexyladipate, disodecyladipate, and di-2-ethylhexylcebacate; polyolesters such as trimethylolpropanecaprylate, trimethylolpropanepelargonate, pentaerythritol-2-ehylhexyanoate, and pentaerythritolpelargonate; and mixtures thereof.
  • Each of these lubricating oil exhibits its peculiar viscosity-temperature characteristics, i.e., viscosity index.
  • a lubricating oil used as a base oil of the present invention has a viscosity index of 120 or more, even though a lubricating base selected from the above has a viscosity index of less than 120, it may be used in combination with those having a viscosity index of 120 or more.
  • Component (B) of an engine oil composition according to the present invention is a polymethacrylate-based viscosity index improver blended in such an amount that the resulting composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3 mm 2 /s.
  • the kinematic viscosity at 100 ° C of the resulting composition in excess of 9.3 mm 2 /S would not provide sufficient fuel efficiency, while that of less than 4.0 mm 2 /s would improve fuel efficiency caused by the reduced viscosity of the composition and viscosity at low temperatures but fail to have sufficient lubricity as an engine oil.
  • the combination of a base oil with such a polymethacrylate-based viscosity index improver in an engine oil composition according to the present invention results in enhanced viscosity index improving effects, less thickening effects, and excellent pour point reduction effects.
  • the polymethacrylate-based viscosity index improver is indispensable in an engine oil composition according to the present invention in order to provide it with excellent low temperature characteristics.
  • polymethacrylate-based viscosity index improvers which may be used in the present invention are any type of non-dispersion type or dispersion type polymethacrylate compounds which are used as viscosity index improvers for a lubricating oil.
  • the non-dispersion type polymethacrylate-based viscosity index improver may be a polymer of a compound represented by the formula
  • R 1 is a straight or branched alkyl group such as methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
  • dispersion type polymethacrylate-based viscosity index improver are copolymers obtained by copolymerizing one or more monomers selected from compounds represented by formula (1) with one or more nitrogen-containing monomers selected from compounds represented by formulae (2) and (3)
  • R 2 and R 4 are each independently hydrogen or methyl.
  • R 3 is a straight or branched alkylene group having 1 to 18 carbon atoms, such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, and octadecylene groups.
  • e is an integer of 0 or 1.
  • X1 and X2 are each independently an amino- or heterocyclic- residue having 1 or 2 nitrogen and 0 to 2 oxygen. Specific examples of X1 and X2 are dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pyrolyl, pyridyl, methylpydidyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino, and pyrazino groups.
  • nitrogen-containing monomer represented by formula (2) or (3) are dimethylaminomethylmethacrylate, diethylaminomethylmethacrylate, dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, 2-methyl-5-vinylpyridine, morpholinomethylmethacrylate, morpholinoethylmethacrylate, N-vinylpyrrolidone, and mixtures thereof.
  • the lower limit of the weight-average molecular weight of the polymethacrylate-based viscosity index improver which is effective in improving the performance of an engine oil, is preferably 180,000, more preferably 190,000.
  • Polymethacrylate-based viscosity index improvers having a weight-average molecular weight of 180,000 or more can decrease the amount of other viscosity index improvers to be added so as to further improve low temperature viscosity, not only leading to an advantage in terms of cost but also an improvement in shear stability such that the initial performances of the resulting engine oil can be maintained.
  • No particular limitation is imposed on the upper limit. When consideration is given to an easy treatment of the composition, it is preferably 500,000 or less and more preferably 400,000 or less.
  • an engine oil composition according to the present invention contains the polymethacrylate-based viscosity index improver in such an amount that the composition has a kinematic viscosity at 100 ° C of 4.0 to 9.3 mm 2 /s.
  • the content of a polymethacrylate-based viscosity index improver may be arbitrary selected. However, the content is preferably from 0.5 to 10 percent by mass based on the total weight of the composition.
  • an engine oil composition according to the present invention may be blended with molybdenumdithiocarbamate represented by formula (4) or mixtures thereof
  • R 5 , R 6 , R 7 , and R 8 may be the same or different and are each independently an alkyl or alkylaryl group having 2 to 18 carbon atoms.
  • Y 1 , Y 2 , Y 3 , and Y 4 are each independently sulfur or oxygen.
  • the alkyl group includes primary, secondary, and tertiary alkyl groups which may be straight or branched. Specific examples of the alkyl group are ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and tridecyl groups.
  • molybdenumdithiocarbamate examples include molybdenumdiethyldithiocarbamate sulfide, molybudenumdipropyldithiocarbamate sulfide, molybdenumdibutyldithiocarbamate sulfide, molybdenumdipentyldithiocarbamate sulfide, molybdenumdihexyldithiocarbamate sulfide, molybdenumdioctyldithiocarbamate sulfide, molybdenumdidecyldithiocarbamate sulfide, molybdenumdidodecyldithiocarbamate sulfide, molybdenumditridecyldithiocarbamate sulfide, molybdenumdi(butylphenyl)dithiocarbamate sulfide
  • the upper limit molybdenum content is 0.15 percent by mass, preferably 0.10 percent by mass, in terms of molybdenum concentration, based on the total mass of the composition.
  • the content in excess of the upper limit would cause the formation of sludge when the engine oil is deteriorated.
  • No particular limitation is imposed on the lower limit molybdenum content.
  • the lower limit is preferably 0.02 percent by mass, more preferably 0.04 percent by mass in terms of molybdenum concentration, based on the total mass of the composition in order to obtain a sufficient friction reduction effect.
  • an engine oil composition according to the present invention excels in fuel efficiency and low temperature viscosity and is less in evaporation loss by blending a specific base oil with a polymethacrylate-based viscosity index improver so as to obtain a specific viscosity. Furthermore, the use of a polymethacrylate-based viscosity index improver having a weight average molecular weight of 180,000 or more can further improve fuel efficiency and low temperature viscosity. Higher level of fuel efficiency can be provided in an engine oil by adding thereto molybdenumdithiocarbamate.
  • engine oil additives may be used singlely or in combination.
  • additives which may be used in the present invention are alkaline earth metal-based detergents, ashless dispersants, corrosion inhibitors, ashless oxidation inhibitors, friction modifiers other than molybdenumdithiocarbamate, corrosion inhibitors, demulsifying agents, metal deactivators, and antifoamers.
  • Eligible alkaline earth metal-based detergents are alkaline earth metal compounds which are added in a lubricating oil.
  • Specific examples of such a detergent are one or more metallic detergents selected from alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates.
  • Preferred alkaline earth metal sulfonates are alkaline earth metal salts, preferably magnesium salt and/or calcium salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weigh of 300 to 1,500, preferably 400 to 700. The latter is more preferred.
  • the above-mentioned alkyl aromatic sulfonic acid may be a petroleum sulfonic acid and a synthetic sulfonic acid.
  • the petroleum sulfonic acid may be mahogany acid obtained by sulfonating the alkyl aromatic compound contained in the lubricant fraction of mineral oil or by-produced upon the production of white oil.
  • the synthetic sulfonic acid may be those obtained by sulfonating alkyl benzene having a straight or branched alkyl group, which may be by-produced from a plant for producing alkyl benzene used as material of detergents, or sulfonating dinonylnaphthalene.
  • fuming sulfuric acid and sulfuric acid as a sulfonating agent.
  • the alkaline earth metal phenate may be an alkaline earth metal salt, preferably magnesium salt and/or calcium salt of alkylphenol, alkylphenolsulfide, or a product resulting from Mannich reaction of the alkylphenol.
  • R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 may be the same or different and are each independently a straight or branched alkyl group having 4 to 30, preferably 6 to 18 carbon atoms
  • M 1 , M 2 , and M 3 are each independently an alkaline earth metal, preferably calcium and/or magnesium
  • x is an integer of 1 or 2.
  • R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups, all of which may be straight or branched and primary, secondary or tertiary alkyl groups.
  • the alkaline earth metal salicylate may be an alkaline earth metal salt, preferably magnesium salt and/or calcium salt of an alkyl salicylate. Specific examples are those represented by the formula wherein R 15 is a straight or branched alkyl group having 4 to 30, preferably 6 to 18 carbon atoms, and M 4 is an alkaline earth metal, preferably calcium and/or magnesium.
  • R 15 are butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups, all of which may be straight or branched and primary, secondary or tertiary alkyl groups.
  • the alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate may be a neutral alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate obtained by directly reacting a compound such as the above-mentioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide and the Mannich reaction product thereof, and alkyl salicylic acid with an alkaline earth metal oxide or hydroxide of magnesium and/or calcium, or obtained by converting the compound into an alkali metal salt such as sodium salt or potassium salt and then substituting the alkali metal salt with an alkaline earth metal salt.
  • a neutral alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate obtained by directly reacting a compound such as the above-mentioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol s
  • the alkaline earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate may also be a basic alkaline earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate obtained by heating a neutral alkaline earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate in water containing an excess amount of an alkaline earth metal salt or an alkaline earth metal base; or an overbased alkaline earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate obtained by reacting a neutral alkaline earth metal sulfonate, alkaline earth metal phenate or alkaline earth metal salicylate with the carbonic acid salt or boric acid salt of an alkaline earth metal in the presence of carbon dioxide.
  • neutral alkaline earth metal salt there may be used the above-described neutral alkaline earth metal salt, basic alkaline earth metal salt, overbased alkaline earth metal salt, and mixtures thereof.
  • metallic detergents are usually diluted with a light lubricating base oil. It is preferred to use metallic detergents containing metal in an amount of 1.0 to 20 percent by mass, preferably 2.0 to 16 percent by mass.
  • total base number of the alkaline earth metal detergent used in the present invention.
  • preferred metallic detergents are those having a total base number of 30 to 400 mgKOH/g, preferably 150 to 300 mgKOH/g.
  • total base number used herein denotes a total base number measured by the perchloric acid potentiometric titration method in accordance with section 7 of JIS K2501 "Petroleum products and lubricants-Determination of neutralization number"
  • the content of the alkaline earth metal detergent is within the range of 1.0 to 10.0 percent by mass, preferably 1.0 to 8.0 percent by mass, more preferably 1.5 to 5.0 percent by mass, based on the total mass of the composition.
  • Preferred ashless dispersant are any type of polybutenylsuccinimides used in a lubricating oil.
  • Specific examples of such dispersants are mono-type imides represented by formula (9), bis-type imides represented by formula (10), and those modified with organic acid or boric acid
  • R 16 , R 17 , and R 18 are each independently a polybutenyl group having a number-average molecular weight of 900 to 3,500, preferably 1,000 to 3,000, and c is an integer of 2 to 5.
  • the polybutenylsuccinimides may be obtained by reacting polybutenylsuccinate resulting from the reaction of a polybutene or chlorinated polybutene having a number-average molecular weight of 900 to 3,500, with maleic anhydride.
  • the polyamine are diethyltriamine, triethylenetetraamine, tetraethylenepentamine, and pentaethylenehexamine.
  • the upper limit content of the polybutenylsuccinimide is 0.20 percent by mass, preferably 0.10 percent by mass, in terms of nitrogen concentration, based on the total mass of the composition. Contents in excess of the upper limit would adversely affect rubber-made sealing materials of an engine. No particular limitation is imposed on the lower limit content of the polybutenylsuccinimide. However, the lower limit is preferably 0.05 percent by mass, more preferably 0.06 percent by mass, in terms of nitrogen concentration, based on the total mass of the composition such that a more sufficient fuel efficiency can be achieved.
  • an engine oil composition may be blended with one or more of other ashless dispersants such as a long chain polyalkylamine, and an amide of a long chain fatty acid and a polyamine or with those in combination with the above-described polybutenylsuccinimide ashless dispersant.
  • other ashless dispersants such as a long chain polyalkylamine, and an amide of a long chain fatty acid and a polyamine or with those in combination with the above-described polybutenylsuccinimide ashless dispersant.
  • Wear inhibitors used in the present invention may be one or more dialkyldithio zinc phosphate selected from compounds represented by formula (11)
  • R 19 , R 20 , R 21 , and R 22 are each independently a primary alkyl group having 2 to 18, preferably 4 to 12 carbon atoms or a secondary alkyl group having 3 to 18, preferably 3 to 10 carbon atoms.
  • the primary alkyl group having 2 to 18 carbon atoms are those represented by the formula R 23 -CH 2 -
  • R 23 is a straight or branched alkyl group having 1 to 17, preferably 3 to 11 carbon atoms.
  • R 23 are straight or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and heptadecyl groups.
  • the secondary alkyl group having 3 to 18 carbon atoms are those represented by the formula
  • R 24 and R 25 are each independently a straight or branched alkyl group having 1 to 16, preferably 1 to 8 carbon atoms to be selected such that the total carbon number of R 24 and R 25 is 2 to 17, preferably 2 to 9 carbon atoms.
  • R 24 and R 25 are straight or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl groups.
  • the upper limit content of the dialkyldithio zinc phosphate is 0.10 percent by mass, preferably 0.09 percent by mass, on an elementary basis, based on the total mass of the composition.
  • the content in excess of the upper limit would accelerate the poisoning of a ternary catalyst adversely affecting exhaust gas.
  • No particular limitation is imposed on the lower limit content of the dialkyldithio zinc phosphate.
  • the lower limit is preferably 0.04 percent by mass, more preferably 0.06 percent by mass, on an elementary basis, based on the total mass of the composition.
  • An engine oil composition may be blended with one or more of other friction modifies such as organic phosphates, fatty acids, fatty acid esters, aliphatic alcohols, or with those in combination with the above-described dialkyldithio zinc phosphates.
  • other friction modifies such as organic phosphates, fatty acids, fatty acid esters, aliphatic alcohols, or with those in combination with the above-described dialkyldithio zinc phosphates.
  • Preferred ashless oxidation inhibitors are phenolic ashless oxidation inhibitors used as oxidation inhibitors for a lubricating oil.
  • Specific examples of the phenolic ashless oxidation inhibitors are 4,4'-methylenebis(2,6-di-tertbutylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-isopropylidenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidenebis(4,6-dimethylphenol), 2,2'
  • An engine oil composition may be blended with one or more of the above-described ashless dispersants or with one or more of amine-based ashless dispersants such as phenyl- ⁇ -nephtylamine, alkylphenyl-a-nephtylamine, and dialkyldiphenylamine.
  • amine-based ashless dispersants such as phenyl- ⁇ -nephtylamine, alkylphenyl-a-nephtylamine, and dialkyldiphenylamine.
  • the above-described phenolic ashless dispersants may be sued in combination with the amine-based ashless dispersants.
  • the upper limit content of the above-described ashless oxidation inhibitors is 3.0 percent by mass, preferably 2.0 percent by mass. A content in excess of the upper limit would fail to achieve oxidation inhibition that balances the amount. No particular limitation is imposed on the lower limit content. However, the lower limit content of preferably 0.1 percent by mass, more preferably 0.3 percent by mass is contributive to reduce the friction coefficient of an engine oil after being deteriorated.
  • An engine oil composition according to the present invention may be blended with friction modifiers other than the above-described molybdenumdithiocarbamates.
  • friction modifiers may be molybdenumdithiophosphate, molybdenum disulfide, long-chain aliphatic amines, long-chain fatty acids, long-chain fatty acid esters, long-chain aliphatic alcohols.
  • Additives other than those of the above-described which may be used in the present invention are corrosion inhibitors such as petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalene sulfonates, alkenylsuccinates, and polyalcohol esters; demulsifying agent, typical examples of which are polyalkylene glycol-based non-ionic surfactants such as polyoxyethylenealkyl ether, polyoxyethylenealkylphneyl ether, and polyoxyethylenealkylnaphthyl ether; metal diactivators such as imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothizole, benzotriazole and derivatives thereof, 1,3,4-thiadiazolepolysulfide, 1,3,4-thiadizolyl-2,5-bisdialkyldithiocarbamte, 2-(alkyldithio)benzoimidazole, and
  • the corrosion inhibitors and demulsifying agents are each added in an amount of 0.1 to 15 percent by mass, the antifoamers are added in an amount of 0.0005 to 1 percent by mass, and the metal deactivators are added in an amount of 0.005 to 1 percent by mass, based on the total mass of the composition.
  • An engine oil composition according to the present invention may be used preferably in motorcycle engines, automobile engines, diesel engines for land use, and marine diesel engines.
  • the friction torque of the whole of an engine was measured by driving at 1,500 rpm, at an oil temperature of 80 ° C, and at a water temperature of 80 ° C.
  • an engine oil has better fuel efficiency with the smaller value which indicates the smaller friction loss at each parts of the engine.
  • the evaporation loss of each of the engine oils was measured after being heated at a temperature of 250 ° C and under a constant pressure for one hour. An engine oil with the smaller value is less consumed during actual running.
  • Table 1 shows the above performance evaluation test results of the engine oils of Inventive Examples 1 - 3.
  • Each of the engine oils was formulated so as to have the same kinematic viscosity at 100 ° C and high temperature high shear viscosity at 150 ° C. It is apparent from the results in Table 1 that the engine oils of Inventive Examples 1 - 3 had an excellent fuel efficiency, less evaporation loss, and an excellent low temperature viscosity. It was also apparent that these oils exhibited more excellent performances when being blended with a polymethacrylate-based viscosity index improver with a weight-average molecular weight of 250,000 than when being blended with that of a weight-average molecular weight of 150,000. Furthermore, it was apparent that the engine oils blend with molybdenumdithiocarbamate exhibited an excellent fuel efficiency.
  • Table 1 also shows the above performance evaluation test results of the engine oils of Comparative Examples 1 - 3.
  • the engine oil of Comparative Example 1 with the base oil having a viscosity index of 100 was inferior in fuel efficiency, evaporation loss, and low temperature viscosity.
  • the engine oil containing an olefin copolymer-based viscosity index improver (Comparative Examples 2) was inferior in fuel efficiency, evaporation loss, and low temperature viscosity.
  • the engine oil of Comparative Example 3 with a kinematic viscosity of 9.3 or more was inferior in fuel efficiency even though being blended with molybdenumdithiocarbamate.
  • the present invention can provide an engine oil composition which excels in fuel efficiency and low temperature characteristics and encounters less evaporation loss.

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003008522A1 (fr) * 2001-07-12 2003-01-30 Nippon Oil Corporation Composition d'huile pour moteur a combustion interne
WO2003064572A1 (fr) * 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Compositions d'huile lubrifiante a proprietes de reduction du frottement ameliorees
WO2003064573A1 (fr) * 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Compositions d'huiles lubrifiantes aux proprietes de friction ameliorees
WO2006060255A1 (fr) * 2004-12-01 2006-06-08 The Lubrizol Corporation Procede de nettoyage de moteur et composition
EP2112217A1 (fr) * 2007-01-31 2009-10-28 Nippon Oil Corporation Composition d'huile lubrifiante
EP1749876A3 (fr) * 2005-08-05 2010-11-03 TonenGeneral Sekiyu Kabushiki Kaisha Composition d'huile lubrifiante contenant un polymethacrylate comme agent améliorant l'indice de viscosité
EP2439256A4 (fr) * 2009-06-04 2014-09-24 Jx Nippon Oil & Energy Corp Composition d'huile lubrifiante

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JP4507158B2 (ja) * 2003-07-25 2010-07-21 財団法人石油産業活性化センター 環境適合性および省燃費性に優れたガソリンエンジン油組成物
JP2005239840A (ja) * 2004-02-25 2005-09-08 Nof Corp 内燃機関用潤滑油基油およびそれを含有する潤滑油組成物
WO2006043709A1 (fr) 2004-10-22 2006-04-27 Nippon Oil Corporation Formule de lubrifiant pour transmission
JP2006199857A (ja) 2005-01-21 2006-08-03 Showa Shell Sekiyu Kk 低燃費性に優れたガソリンエンジン油組成物
KR100680371B1 (ko) 2005-12-06 2007-02-08 현대자동차주식회사 자동변속기유 조성물
JP5557413B2 (ja) * 2006-02-15 2014-07-23 Ｊｘ日鉱日石エネルギー株式会社 内燃機関用潤滑油組成物
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Cited By (9)

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WO2003008522A1 (fr) * 2001-07-12 2003-01-30 Nippon Oil Corporation Composition d'huile pour moteur a combustion interne
WO2003064572A1 (fr) * 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Compositions d'huile lubrifiante a proprietes de reduction du frottement ameliorees
WO2003064573A1 (fr) * 2002-01-31 2003-08-07 Exxonmobil Research And Engineering Company Compositions d'huiles lubrifiantes aux proprietes de friction ameliorees
WO2006060255A1 (fr) * 2004-12-01 2006-06-08 The Lubrizol Corporation Procede de nettoyage de moteur et composition
EP1749876A3 (fr) * 2005-08-05 2010-11-03 TonenGeneral Sekiyu Kabushiki Kaisha Composition d'huile lubrifiante contenant un polymethacrylate comme agent améliorant l'indice de viscosité
US8691739B2 (en) 2005-08-05 2014-04-08 Exxonmobil Research And Engineering Company Lubricating oil composition
EP2112217A1 (fr) * 2007-01-31 2009-10-28 Nippon Oil Corporation Composition d'huile lubrifiante
EP2112217A4 (fr) * 2007-01-31 2012-02-29 Nippon Oil Corp Composition d'huile lubrifiante
EP2439256A4 (fr) * 2009-06-04 2014-09-24 Jx Nippon Oil & Energy Corp Composition d'huile lubrifiante

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US20010027169A1 (en) 2001-10-04
EP1111028B1 (fr) 2017-11-22
JP2001181664A (ja) 2001-07-03

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