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EP0447916A1 - Engine oil composition - Google Patents

Engine oil composition Download PDF

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Publication number
EP0447916A1
EP0447916A1 EP91103711A EP91103711A EP0447916A1 EP 0447916 A1 EP0447916 A1 EP 0447916A1 EP 91103711 A EP91103711 A EP 91103711A EP 91103711 A EP91103711 A EP 91103711A EP 0447916 A1 EP0447916 A1 EP 0447916A1
Authority
EP
European Patent Office
Prior art keywords
weight
oil
sulfide
alkaline
composition
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
EP91103711A
Other languages
German (de)
French (fr)
Other versions
EP0447916B1 (en
Inventor
Kiyoshi Inoue
Jiichi Igarashi
Mituaki Ishimaru
Mineo Kagaya
Masakuni Hirata
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
Original Assignee
Nippon Oil Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Publication of EP0447916A1 publication Critical patent/EP0447916A1/en
Application granted granted Critical
Publication of EP0447916B1 publication Critical patent/EP0447916B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
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    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
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    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • 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
    • C10M2227/061—Esters derived from boron
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • 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
    • C10N2040/251—Alcohol-fuelled 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
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • This invention relates to an engine oil composition, and more particularly to an engine oil composition useful as a lubricating oil for gasoline engine, diesel engine, and the like.
  • Addition of friction modifiers to lubricating oil is indispensable especially in latest fuel-saving lubricating oil, and many compounds have been heretofore been found to be useful. However, it has been observed that even though these compounds possess a high fuel-saving effect on the fresh lubricating oil, they gradually lose said effect in the aged lubricatng oil due to degradation during engine operation. While many antioxidants have widely been used heretofore and proved to be effective to some extent for preventing the degradation, they could not necessarily provide satisfactory results in view of their lubricating performance.
  • the present invention is based on a discovery whereby excellent fuel-saving effect can be attained employing an overbasic metallic detergent prepared by use of an alkaline-earth metal borate as an additional component of an engine oil composition containing a friction modifier and an antioxidant.
  • the present invention provides an engine oil composition having a specific combination of lubricating additives and excellent fuel-saving effect over a long period of time.
  • It is an object of the subject invention to provide a fuel-saving engine oil composition comprising a lubricating base oil and
  • Either mineral oils or synthetic oils may be used as the lubricating base oils of the instant invention.
  • Any paraffinic or naphthenic lubricating base oils may be acceptable wherein said base oils are manufactured by a process consisting mainly of topping crude oil followed by vacuum distillation to give a lubricating oil fraction, and refining said lubricating fraction by a process selected from the group consisting of solvent deasphalting, solvent extraction, hydro-cracking, solvent dewaxing, catalytic dewaxing, hydro-refining, sulfuric acid treating, and clay treating.
  • the synthetic oils of the present invention include, ⁇ -olefin polymers (polybutenes, octene-1 oligomers, decene-1 oligomers, and the like), alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-3-ethylhexyl sebacate, and the like), polyol esters (trimethylolpropane caprilate, trimethylolpropane pelargonate, pentaerythritol- 2-ethyl hexanoate, pentaerythritol pelargonate, and the like), polyoxyalkylene glycol, polyphenyl ether, silicon oils, perfluoroalkyl ethers, and mixtures thereof.
  • Preferred kinematic viscosity of these lubricating base oils is in a range of about 3 to 20 cSt at 100°C.
  • the overbasic oil-soluble metal salts (a) of the present invention are prepared by a reaction of an oil-soluble metal salt such as an oil-soluble alkaline-earth metal sulfonate, alkaline-earth metal saricylate, alkaline-earth metal pheneate, alkaline-earth metal phosphonate with an oxide or hydroxide of an alkaline-metal in the presence of boric acid or boric acid anhydride.
  • an oil-soluble metal salt such as an oil-soluble alkaline-earth metal sulfonate, alkaline-earth metal saricylate, alkaline-earth metal pheneate, alkaline-earth metal phosphonate with an oxide or hydroxide of an alkaline-metal in the presence of boric acid or boric acid anhydride.
  • oil-soluble metal salts alkaline-earth metal saricylates are most appropriate.
  • the overbaic oil-soluble metal salts (a) of the present invention have a total base number of about 100 or more, and preferably 170 or more, and a particle size of less than about 0.1 ⁇ m, and preferably less than about 0.05 ⁇ m.
  • any methods for preparing the overbasic metal salts may be acceptable.
  • a method which comprises reacting an oil-soluble metal salt aforesaid, a hydroxide or an oxide of alkaline-earth metal, and boric acid or boric acid anhydride in the presence of water, an alcohol such as methanol, ethanol, propanol, or butanol, and a diluent such as benzene, toluene or xylene at a temperature of about 20 to 200 °C for about 2 to 8 hours, heating the mixture at about 100 to 200 °C to remove water, followed by removing the alcohol and the diluent if necessary, to give a overbasic metal salt.
  • an alcohol such as methanol, ethanol, propanol, or butanol
  • a diluent such as benzene, toluene or xylene
  • reaction conditions may be employed suitably depending on raw material type, the amount of reactants and the like. Typical of such prior art practices are those disclosed in Japanese patent Publication Nos. 116688 /60 and 204298 /61 and the disclosures of which are incorporated by reference.
  • a content of the overbasic metal salt prepared by use of an alkaline-earth metal borate of the present invention is in an amount of about 0.01 to 30 % by weight, and preferably about 0.05 to 5 % by weight, on the basis of the total amount of the composition.
  • the content of less than about 0.01 % by weight is not preferable because of the insufficient display of the fuel-saving effect of the overbasic metal salt wherein the effect can not be maintained over a long period of time. Inversely, when it is in excess of about 30 % by weight, there is no additional merits due to the excessive addition.
  • Other overbasic oil-soluble metal salts such as those prepared by use of alkaline-earth-metal carbonates can not provide an engine oil composition which can persistently maintain the fuel-saving effect throughout the engine operation.
  • Any friction modifiers (b) which have been used in conventional engine oils may be employed in the present invention.
  • Such modifiers include molibdenum dithiophosphates, molibdenum dithiocarbamates, molibdenum disulfides, fluorocarbons, boric acid esters, alkylamines, higher alcohols, higher fatty acids, fatty acid esters, fatty acid amides and the like.
  • Typical friction modifiers include molybdenum sulfide diethyldithiophosphate, molybdenum sulfide dipropyldithiophosphate, molybdenum sulfide dibutyldithiophosphate, molybdenum sulfide dipentyldithiophosphate, molybdenum sulfide dihexyldithiophosphate, molybdenum sulfide dioctyldithiophosphate, molybdenum sulfide didecyldithiophosphate, molybdenum sulfide didodecyldithiophosphate, molybdenum sulfide di(butylphenyl) dithiophosphate, Molybdenum sulfide di(nonylphenyl) dithiophosphate, oxymolybdenum sulfide diethyldithiophosphate,
  • a content of the friction reducer (b) of the present invention is in an amount of about 0.01 to 5 % by weight, and preferably about 0.05 to 2 % by weight, on the basis of the total amount of the composition.
  • the content of less than about 0.01 % by weight is not preferable because of the insufficient display of the friction reducing effect. Inversely, when it is in excess of about 5 % by weight, there is no additional merits due to the excessive addition.
  • antioxidants may be employed which have been used in conventional engine oils.
  • Such antioxidants include phenol type, amine type, sulfur type, zinc thiophosphate type, phenothiazine type antioxidants, and the like.
  • they include diphenylamine, p,p'-dioctyl diphenylamine, p,p'-dinonyl diphenylamine, p,p' -didodecyl diphenylamine, phenyl- ⁇ -naphthylamine, p-octylpenyl- ⁇ -naphthylamine, p-nonylphenyl- ⁇ -naphthylamine, p-dodecylpheny- ⁇ -naphthylamine, 2,6-di-tert.-butylphenol, 2,6-di-tert.-butyl-p-cresol, 2,6-di-tert.
  • a content of the antioxidant (c) of the present invention is in an amount of about 0.01 to 5 % by weight, and preferably about 0.1 to 2 % by weight, on the basis of the total amount of the composition.
  • the content of less than about 0.01 % by weight is not preferable because of the display of the antioxidation effect for a short period of time. Inversely, when the amount is in an excess of about 5 % by weight, there is no additional merits due to the excessive addition.
  • the following conventional lubricating oil additives can be additionally used to improve further the performance of the present composition if necessary, in so far as they do not deviate from the gist of the present invention.
  • these additives include extreme pressure additives such as tricresyl phosphate, triphenyl phosphate, zinc dithiophosphates,; rust preventives such as petroleum sulfonates, dinonyl naphthalene sulfonates and the like; metal deactivating agents such as benzotriazole and the like; metal-based detergents such as alkaline-earth metal sulfonates, alkaline-earth metal salicylates, alkaline-earth metal pheneates, alkaline-earth metal phosphonates and the like; ashless dispersants such as succinimide, succinic esters, benzylamine and the like; deformers such as silicon oils and the like; viscosity index improvers and pour point depressants such
  • a content of the viscosity index improver is in an amount of about 1 to 30 % by weight
  • the deformer is in an amount of about 0.0005 to 1 % by weight
  • the metal deactivating agent is in an amount of about 0.005 to 1 % by weight
  • other additives are in amounts of about 0.1 to 15 % by weight respectively on the basis of the total amount of the composition.
  • the engine oil compositions of the present invention are suitable for two cycle and four cycle gasoline engine oils, diesel engine oil for land use, marine diesel engine oil, and the like.
  • the engine oil compositions of the present invention were prepared. Performance tests were conducted with respect to these compositions by the following method.
  • the oxidation degraded sample oils were prepared by oxidizing new sample oils under the following conditions on the basis of "the method for testing oxidaton stability of lubricating oil" prescribed by JIS K 2514 3.1:
  • Table 1 shows the test results.
  • the engine oil compositions according to the present invention have excellent performance as an engine oil in which the fuel-saving effect can be maintained persistently throughout the engine operation because of the synergism of each component.

Landscapes

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

Abstract

The invention provides an engine oil composition characterized by containing a major amount of lubricating base oil and
  • (a) about 0.01 to 30 % by weight of an overbasic oil-soluble metal salt prepared by use of an alkaline-earth metal borate,
  • (b) about 0.01 to 5 % by weight of a friction modifier,
  • (c) about 0.01 to 5 % weight of an antioxidant as essential components, on the basis of the total amount of the composition.

Description

    2. Background of the Invention (1) Field of the Invention
  • This invention relates to an engine oil composition, and more particularly to an engine oil composition useful as a lubricating oil for gasoline engine, diesel engine, and the like.
    • (2) Description of the Prior Art
  • Because of increased concern regarding the energy-saving measures to counter oil shocks, the research for a fuel-saving internal combustion engine lubricating oil has been recently intensified. As measures for fuel-saving by use of lubricating oil to meet such situation, the following measures are now under review among business circles: (a) Lowering viscosity of lubricating oil with the intension of reducing engine friction loss under hydrodynamic lubricating conditions, and (b) Addition of friction reducers with the intension of reducing engine friction loss under mixed and boundary lubrication.
  • Addition of friction modifiers to lubricating oil is indispensable especially in latest fuel-saving lubricating oil, and many compounds have been heretofore been found to be useful. However, it has been observed that even though these compounds possess a high fuel-saving effect on the fresh lubricating oil, they gradually lose said effect in the aged lubricatng oil due to degradation during engine operation. While many antioxidants have widely been used heretofore and proved to be effective to some extent for preventing the degradation, they could not necessarily provide satisfactory results in view of their lubricating performance.
  • The present invention is based on a discovery whereby excellent fuel-saving effect can be attained employing an overbasic metallic detergent prepared by use of an alkaline-earth metal borate as an additional component of an engine oil composition containing a friction modifier and an antioxidant.
  • The present invention provides an engine oil composition having a specific combination of lubricating additives and excellent fuel-saving effect over a long period of time.
    • 3. Summary of the Invention
  • It is an object of the subject invention to provide a fuel-saving engine oil composition comprising a lubricating base oil and
    • (a) about 0.01 to 30 % by weight of an overbasic oil-soluble metal salt,
    • (b) about 0.01 to 5 % by weight of a friction modifier,
    • (c) about 0.01 to 5 % weight of an antioxidant as essential components, on the basis of the total amount of the composition.
    4. Detailed Description of the Invention
  • Either mineral oils or synthetic oils may be used as the lubricating base oils of the instant invention. Any paraffinic or naphthenic lubricating base oils may be acceptable wherein said base oils are manufactured by a process consisting mainly of topping crude oil followed by vacuum distillation to give a lubricating oil fraction, and refining said lubricating fraction by a process selected from the group consisting of solvent deasphalting, solvent extraction, hydro-cracking, solvent dewaxing, catalytic dewaxing, hydro-refining, sulfuric acid treating, and clay treating.
  • The synthetic oils of the present invention include, α-olefin polymers (polybutenes, octene-1 oligomers, decene-1 oligomers, and the like), alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-3-ethylhexyl sebacate, and the like), polyol esters (trimethylolpropane caprilate, trimethylolpropane pelargonate, pentaerythritol- 2-ethyl hexanoate, pentaerythritol pelargonate, and the like), polyoxyalkylene glycol, polyphenyl ether, silicon oils, perfluoroalkyl ethers, and mixtures thereof.
  • Preferred kinematic viscosity of these lubricating base oils is in a range of about 3 to 20 cSt at 100°C.
  • The overbasic oil-soluble metal salts (a) of the present invention are prepared by a reaction of an oil-soluble metal salt such as an oil-soluble alkaline-earth metal sulfonate, alkaline-earth metal saricylate, alkaline-earth metal pheneate, alkaline-earth metal phosphonate with an oxide or hydroxide of an alkaline-metal in the presence of boric acid or boric acid anhydride. Among oil-soluble metal salts, alkaline-earth metal saricylates are most appropriate. Generally, the overbaic oil-soluble metal salts (a) of the present invention have a total base number of about 100 or more, and preferably 170 or more, and a particle size of less than about 0.1 µm, and preferably less than about 0.05 µm.
  • Any methods for preparing the overbasic metal salts may be acceptable. For example, a method has been known which comprises reacting an oil-soluble metal salt aforesaid, a hydroxide or an oxide of alkaline-earth metal, and boric acid or boric acid anhydride in the presence of water, an alcohol such as methanol, ethanol, propanol, or butanol, and a diluent such as benzene, toluene or xylene at a temperature of about 20 to 200 °C for about 2 to 8 hours, heating the mixture at about 100 to 200 °C to remove water, followed by removing the alcohol and the diluent if necessary, to give a overbasic metal salt. The reaction conditions may be employed suitably depending on raw material type, the amount of reactants and the like. Typical of such prior art practices are those disclosed in Japanese patent Publication Nos. 116688 /60 and 204298 /61 and the disclosures of which are incorporated by reference.
  • A content of the overbasic metal salt prepared by use of an alkaline-earth metal borate of the present invention is in an amount of about 0.01 to 30 % by weight, and preferably about 0.05 to 5 % by weight, on the basis of the total amount of the composition.
  • The content of less than about 0.01 % by weight is not preferable because of the insufficient display of the fuel-saving effect of the overbasic metal salt wherein the effect can not be maintained over a long period of time. Inversely, when it is in excess of about 30 % by weight, there is no additional merits due to the excessive addition. Other overbasic oil-soluble metal salts, such as those prepared by use of alkaline-earth-metal carbonates can not provide an engine oil composition which can persistently maintain the fuel-saving effect throughout the engine operation.
  • Any friction modifiers (b) which have been used in conventional engine oils may be employed in the present invention. Such modifiers,for example, include molibdenum dithiophosphates, molibdenum dithiocarbamates, molibdenum disulfides, fluorocarbons, boric acid esters, alkylamines, higher alcohols, higher fatty acids, fatty acid esters, fatty acid amides and the like.
  • Typical friction modifiers include molybdenum sulfide diethyldithiophosphate, molybdenum sulfide dipropyldithiophosphate, molybdenum sulfide dibutyldithiophosphate, molybdenum sulfide dipentyldithiophosphate, molybdenum sulfide dihexyldithiophosphate, molybdenum sulfide dioctyldithiophosphate, molybdenum sulfide didecyldithiophosphate, molybdenum sulfide didodecyldithiophosphate, molybdenum sulfide di(butylphenyl) dithiophosphate, Molybdenum sulfide di(nonylphenyl) dithiophosphate, oxymolybdenum sulfide diethyldithiophosphate, oxymolybdenum sulfide dipropyldithiophosphate, oxyolybdenum sulfide dibutyldithiophosphate, oxymolybdenum sulfide dipentyldithiophosphate, oxymolybdenum sulfide dihexyldithiophosphate, oxymolybdenum sulfide dioctyldithiophosphate, oxymolybdenum sulfide didecyldithiophosphate, oxymolybdenum sulfide didodecyldithiophosphate, oxymolybdenum sulfide di(butylphenyl) dithiophosphate, oxymolybdenum sulfidedi(nonylphenyl) dithiophosphate, molybdenum sulfide diethyldithiocarbamate, molybdenum sulfide diethyldithiocarbamate, molybdenum sulfide dipropyldithiocarbamate, molybdenum sulfide dibutyldithiocarbamate, molybdenum sulfide dipentyldithiocarbamate, molybdenum sulfide dihexyldithiocarbamate, molybdenum sulfide dioctyldithiocarbamate, molybdenum sulfide didecyldithiocarbamate, molybdenum sulfide didocecyldithiocarbamate, molybdenum sulfide di(butylphenyl) dithiocarbamate, molybdenum sulfide di(nonylphenyl) dithiocarbamate, oxymolybdenum sulfide diethyldithiocarbamate, oxy molybdenum sulfide diethyldithiocarbamate, oxymolybdenum sulfide dipropyldithiocarbamate, oxymolybdenum sulfide dibutyldithiocarbamate, oxymolybdenum sulfide dipentyldithiocarbamate, oxymolybdenum sulfide dihexyldlthiocarbamate, oxymolybdenum sulfide dioctyldithiocarbamate, oxymolybdenum sulfide didecyldithiocarbamate, molybdenum sulfide didocecyldithiocarbamate, oxymolybdenum sulfide di(butylphenyl) dithiocarbamate, oxymolybdenum sulfide di(nonylphenyl) dithiocarbamate, lauryl amine, myristyl amine, palmitic amine, stearyl amine, oleyl amine, lauryl alcohol, myristyl alcohol, palmitic alcohol, stearyl alcohol, oleyl alcohol, lauric acid, myristic acid, palmitic acid, stearic aid, oleic acid, methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, lauryl amide, myristyl amide, palmitic amide, stearyl amide, oleyl amide.
  • A content of the friction reducer (b) of the present invention is in an amount of about 0.01 to 5 % by weight, and preferably about 0.05 to 2 % by weight, on the basis of the total amount of the composition.
  • The content of less than about 0.01 % by weight is not preferable because of the insufficient display of the friction reducing effect. Inversely, when it is in excess of about 5 % by weight, there is no additional merits due to the excessive addition.
  • Any antioxidants (c) may be employed which have been used in conventional engine oils. Such antioxidants, for example, include phenol type, amine type, sulfur type, zinc thiophosphate type, phenothiazine type antioxidants, and the like. Typically, they include diphenylamine, p,p'-dioctyl diphenylamine, p,p'-dinonyl diphenylamine, p,p' -didodecyl diphenylamine, phenyl- α-naphthylamine, p-octylpenyl- α-naphthylamine, p-nonylphenyl-α-naphthylamine, p-dodecylpheny- α-naphthylamine, 2,6-di-tert.-butylphenol, 2,6-di-tert.-butyl-p-cresol, 2,6-di-tert.-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-tert.-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert.-butylphenol), 4,4'-methylenebis (2,6-di-tert.-butylphenol), 4,4'-bis (2,6-di-tert.-butylphenol), 4,4'-thiobis (6-tert.-butyl-o-dresol, zinc dialkyl dithiophosphate, phenotiazine, and mixtures thereof.
  • A content of the antioxidant (c) of the present invention is in an amount of about 0.01 to 5 % by weight, and preferably about 0.1 to 2 % by weight, on the basis of the total amount of the composition.
  • The content of less than about 0.01 % by weight is not preferable because of the display of the antioxidation effect for a short period of time. Inversely, when the amount is in an excess of about 5 % by weight, there is no additional merits due to the excessive addition.
  • In the present invention, the following conventional lubricating oil additives can be additionally used to improve further the performance of the present composition if necessary, in so far as they do not deviate from the gist of the present invention. Examples of these additives include extreme pressure additives such as tricresyl phosphate, triphenyl phosphate, zinc dithiophosphates,; rust preventives such as petroleum sulfonates, dinonyl naphthalene sulfonates and the like; metal deactivating agents such as benzotriazole and the like; metal-based detergents such as alkaline-earth metal sulfonates, alkaline-earth metal salicylates, alkaline-earth metal pheneates, alkaline-earth metal phosphonates and the like; ashless dispersants such as succinimide, succinic esters, benzylamine and the like; deformers such as silicon oils and the like; viscosity index improvers and pour point depressants such as polymethacrylates, polyisobutylenes and polystyrenes and the like; and mixture thereof.
  • Generally, a content of the viscosity index improver is in an amount of about 1 to 30 % by weight, the deformer is in an amount of about 0.0005 to 1 % by weight, the metal deactivating agent is in an amount of about 0.005 to 1 % by weight, and other additives are in amounts of about 0.1 to 15 % by weight respectively on the basis of the total amount of the composition.
  • The engine oil compositions of the present invention are suitable for two cycle and four cycle gasoline engine oils, diesel engine oil for land use, marine diesel engine oil, and the like.
  • While the advantages of the compositions according to the present invention will be described in detail hereinbelow in conjunction with the following examples, it is to be noted that the scope of the present invention should not be limited to these examples.
    • Examples and Comparative Examples
  • According to the composition indicated in Table 1, the engine oil compositions of the present invention were prepared. Performance tests were conducted with respect to these compositions by the following method.
    • (LFW friction test)
  • LFW friction test is carried out on both oxidation degraded samples and freshly prepared samples. The test conditions are as follows:
    Figure imgb0001
  • The oxidation degraded sample oils were prepared by oxidizing new sample oils under the following conditions on the basis of " the method for testing oxidaton stability of lubricating oil" prescribed by JIS K 2514 3.1:
    • Temperature
    150 °C
    Duration
    72 hours
  • Table 1 shows the test results.
  • As is apparent from the results shown in Table 1, the engine oil compositions according to the present invention have excellent performance as an engine oil in which the fuel-saving effect can be maintained persistently throughout the engine operation because of the synergism of each component.
  • On the contrary, when the compositions of Comparative Examples 1 and 2 in which an overbasic oil-soluble metal salt prepared by use of calcium carbonate instead of an overbasic oil-soluble metal salt (a) prepared by use of an alkaline-earth metal borate is used, or an antioxidant of component (c) of the present invention is omitted, are compared with those of Example respectively, the friction coefficient increases after oxidation degradation in both cases, and the time during which the fuel-saving effect may be maintained is shorter in both cases.
    Figure imgb0002

Claims (1)

  1. An engine oil composition comprising a major amount of lubricating base oil and
    (a) about 0.01 to 30 % by weight of an overbasic oil-soluble metal salt prepared by use of an alkaline-earth metal borate,
    (b) about 0.01 to 5 % by weight of a friction modifier,
    (c) about 0.01 to 5 % weight of an antioxidant as essential components, on the basis of the total amount of the composition.
EP91103711A 1990-03-16 1991-03-11 Engine oil composition Revoked EP0447916B1 (en)

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JP2066315A JP2617807B2 (en) 1990-03-16 1990-03-16 Engine oil composition
JP66315/90 1990-03-16

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EP0447916B1 EP0447916B1 (en) 1994-06-01

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Cited By (17)

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EP0544298A1 (en) * 1991-11-27 1993-06-02 Nippon Oil Co., Ltd. Method for the lubrication of the automatic transmission of a motorcar
EP0552892A1 (en) * 1992-01-24 1993-07-28 Ethyl Petroleum Additives, Inc. Low ash lubricating oil compositions
EP0562172A1 (en) * 1991-12-12 1993-09-29 Idemitsu Kosan Company Limited Engine oil composition
WO1995002027A1 (en) * 1992-01-09 1995-01-19 Exxon Research & Engineering Company Lubricating oil composition containing friction modifier and corrosion inhibitor
WO1995007963A1 (en) * 1993-09-13 1995-03-23 Exxon Chemical Patents Inc. Mixed antioxidant composition
EP0696636A4 (en) * 1993-04-30 1996-07-24 Tonen Corp LUBRICATING OIL COMPOSITION
WO1996037585A1 (en) * 1995-05-26 1996-11-28 The Lubrizol Corporation Lubricants with molybdenum containing compositions and methods of using the same
EP0758016A1 (en) * 1995-08-09 1997-02-12 Exxon Research and Engineering Company, (a Delaware corp.) Lubricant composition containing antioxidant additive combination
US5840672A (en) * 1997-07-17 1998-11-24 Ethyl Corporation Antioxidant system for lubrication base oils
WO2000008120A1 (en) * 1998-08-04 2000-02-17 Exxon Research And Engineering Company Lubricant formulations with dispersancy retention capability
WO2003031543A3 (en) * 2001-10-05 2003-08-28 Unichema Chemie Bv Lubricant or fuel composition comprising an amide as friction-reducing additive
EP1369469A1 (en) * 2002-05-30 2003-12-10 Ethyl Corporation An antioxidant additives combination for lubricants containing a molybdenum complex and an alkylated phenothiazine
EP1878784A4 (en) * 2005-04-20 2010-04-28 Japan Energy Corp OIL COMPOSITION FOR A LONG-LIFE ENGINE AND FOR SAVING FUEL
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
EP2522710A4 (en) * 2010-01-07 2013-11-13 Jx Nippon Oil & Energy Corp LUBRICANT COMPOSITION
WO2020038737A1 (en) 2018-08-23 2020-02-27 Klueber Lubrication Muenchen Se & Co. Kg Lubricant composition
RU2721712C2 (en) * 2015-07-16 2020-05-21 Эфтон Кемикал Корпорейшн Lubricants with molybdenum and their use for reduction of premature ignition of mixture at low rpm

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JP2001187891A (en) * 1995-04-21 2001-07-10 Hitachi Ltd Lubricating oil composition and lubricating grease composition
JP4643030B2 (en) * 2001-01-29 2011-03-02 日産自動車株式会社 Diesel engine oil composition
JP4643087B2 (en) * 2001-09-25 2011-03-02 日産自動車株式会社 Lubricating oil composition for internal combustion engines
US10421922B2 (en) * 2015-07-16 2019-09-24 Afton Chemical Corporation Lubricants with magnesium and their use for improving low speed pre-ignition
US11155764B2 (en) 2016-05-05 2021-10-26 Afton Chemical Corporation Lubricants for use in boosted engines

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DE2028703A1 (en) * 1969-06-18 1971-04-08 Esso Research and Engineering Co , Linden, NJ (V St A ) Anüoxidantien additive mixture
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Cited By (25)

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EP0544298A1 (en) * 1991-11-27 1993-06-02 Nippon Oil Co., Ltd. Method for the lubrication of the automatic transmission of a motorcar
US5958286A (en) * 1991-11-27 1999-09-28 Nippon Oil Company, Ltd. Automatic transmission fluid composition
US5458807A (en) * 1991-12-12 1995-10-17 Idemitsu Kosan Co., Ltd. Engine oil composition
EP0562172A1 (en) * 1991-12-12 1993-09-29 Idemitsu Kosan Company Limited Engine oil composition
WO1995002027A1 (en) * 1992-01-09 1995-01-19 Exxon Research & Engineering Company Lubricating oil composition containing friction modifier and corrosion inhibitor
US5326485A (en) * 1992-01-24 1994-07-05 Ethyl Petroleum Additives, Inc. Low ash lubricating oil compositions
EP0552892A1 (en) * 1992-01-24 1993-07-28 Ethyl Petroleum Additives, Inc. Low ash lubricating oil compositions
EP0696636A4 (en) * 1993-04-30 1996-07-24 Tonen Corp LUBRICATING OIL COMPOSITION
WO1995007963A1 (en) * 1993-09-13 1995-03-23 Exxon Chemical Patents Inc. Mixed antioxidant composition
AU680553B2 (en) * 1993-09-13 1997-07-31 Exxon Chemical Patents Inc. Mixed antioxidant composition
WO1996037585A1 (en) * 1995-05-26 1996-11-28 The Lubrizol Corporation Lubricants with molybdenum containing compositions and methods of using the same
EP0758016A1 (en) * 1995-08-09 1997-02-12 Exxon Research and Engineering Company, (a Delaware corp.) Lubricant composition containing antioxidant additive combination
US5840672A (en) * 1997-07-17 1998-11-24 Ethyl Corporation Antioxidant system for lubrication base oils
WO2000008120A1 (en) * 1998-08-04 2000-02-17 Exxon Research And Engineering Company Lubricant formulations with dispersancy retention capability
US6150309A (en) * 1998-08-04 2000-11-21 Exxon Research And Engineering Co. Lubricant formulations with dispersancy retention capability (law684)
WO2003031543A3 (en) * 2001-10-05 2003-08-28 Unichema Chemie Bv Lubricant or fuel composition comprising an amide as friction-reducing additive
EP1369469A1 (en) * 2002-05-30 2003-12-10 Ethyl Corporation An antioxidant additives combination for lubricants containing a molybdenum complex and an alkylated phenothiazine
US7960321B2 (en) 2004-10-20 2011-06-14 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
EP1878784A4 (en) * 2005-04-20 2010-04-28 Japan Energy Corp OIL COMPOSITION FOR A LONG-LIFE ENGINE AND FOR SAVING FUEL
EP2522710A4 (en) * 2010-01-07 2013-11-13 Jx Nippon Oil & Energy Corp LUBRICANT COMPOSITION
US9637703B2 (en) 2010-01-07 2017-05-02 Jx Nippon Oil & Energy Corporation Lubricant composition
RU2721712C2 (en) * 2015-07-16 2020-05-21 Эфтон Кемикал Корпорейшн Lubricants with molybdenum and their use for reduction of premature ignition of mixture at low rpm
WO2020038737A1 (en) 2018-08-23 2020-02-27 Klueber Lubrication Muenchen Se & Co. Kg Lubricant composition
US11248188B2 (en) 2018-08-23 2022-02-15 Klueber Lubrication Muenchen Se & Co. Kg Lubricant composition

Also Published As

Publication number Publication date
DE69102172D1 (en) 1994-07-07
JPH03269094A (en) 1991-11-29
EP0447916B1 (en) 1994-06-01
JP2617807B2 (en) 1997-06-04
DE69102172T2 (en) 1994-09-22

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