EP1676902B1 - Schmiermittelzusammensetzung mit verbesserter Oxidationsstabilität bei hohen Temperaturen - Google Patents

Schmiermittelzusammensetzung mit verbesserter Oxidationsstabilität bei hohen Temperaturen Download PDF

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EP1676902B1
EP1676902B1 EP05258039.6A EP05258039A EP1676902B1 EP 1676902 B1 EP1676902 B1 EP 1676902B1 EP 05258039 A EP05258039 A EP 05258039A EP 1676902 B1 EP1676902 B1 EP 1676902B1
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lubricating oil
oil composition
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expressed
total amount
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EP1676902A1 (de
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Hiroyuki Nagamatsu
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Chevron Japan Ltd
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ChevronTexaco Japan Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • 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

Definitions

  • the present invention relates to a lubricating oil composition. More particularly, the present invention relates to a lubricating oil composition having improved oxidation stability at high temperatures when employed in an internal combustion engines.
  • Diesel engines particularly four stroke trunk piston diesel engines, are generally employed as internal combustion engines for generation of electric power and operation of marine vessels. These internal combustion engines are operated smoothly using a lubricating oil composition which contains various additives.
  • metal-containing detergents Specifically, an over-based metal-containing detergent which neutralizes sulfur oxide produced by the combustion of fuel and disperses combustion deposits such as sludge is generally employed. Particularly, a lubricating oil composition for marine diesel engines which is operated using high sulfur content fuel such as A-heavy oil or C-heavy oil should contain over-based metal-containing detergents. Most metal-containing detergents are alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates. An ashless dispersant such as succinimide is also generally employed. Examples of other generally employable additives include a zinc dialkyldithiophosphate compound which serves as an anti-oxidation agent and an extreme-pressure agent and an organic anti-oxidation agent such as phenol compound and amine compound.
  • the lubricating oil is consumed during the operation of engines. Although a fresh lubricating oil is supplemented periodically to compensate the consumed portion, the amount of sulfur oxide compounds and combustion residues produced and deposited in the remaining lubricating oil increases. Therefore, after the engine is operated continuously for a long period of time, the lubricating oil suffers from deterioration and viscosity increase.
  • Japanese Provisional Patent Publication 2000-63867 U.S. Patent 6,262,001 B1 and Japanese Provisional Patent Publication 2000-87066 disclose a metal-containing overbased calcium carboxylate (i.e., overbased calcium hydrocarbyl-salicylate carboxylate) having high thermal stability and high detergency. It canbe prepared with low production costs. These publications describe a variety of compositions for engine lubricating oils.
  • U.S. Patent No. 5,744,430 discloses a composition having therein a base oil with a specified kinematic viscosity and with a specified total amount of aromatics, comprising, in specified amounts based on the total weight of the composition: (b) an alkaline earth metal salicylate detergent; (c) a zinc dialkyldithiophosphate; (d) a succinimide ashless dispersant containing a polybutenyl group having a specified number-average molecular weight; (e) a phenol ashless antioxidant; (f) a molybdenum dithiocarbamate friction modifier; and (g) a viscosity index improver in such an amount that the kinematic viscosity of said composition ranges from 5.6 to 12.5 mm 2 /s at 100°C.
  • EP 1016706 A discloses a lubricating oil composition for internal combustion engines comprising a base oil of lubricating viscosity having a kinematic viscosity of 22 to 300 mm 2 /s at 40°C, an overbased alkyloxybenzenesulfonate detergent, a neutral or basic salicylate detergent, an ashless dispersant, a zinc dialkyldithiophosphate, and a nonmetallic oxidation inhibitor.
  • the present invention relates to a lubricating oil composition having high thermal oxidation stability at high temperatures which are favorably employable for lubricating various internal combustion engines such as diesel engines and gasoline engines.
  • the lubricating oil composition of the present invention is very favorably employed in four stroke trunk piston diesel engines.
  • the present invention relates to a lubricating oil composition having a TBN, as determined by ASTM D2896, in the range of 5 to 55 mg KOH/g comprising a base oil of lubricating viscosity and
  • the present invention relates to a method of operating an internal combustion engine, particularly a four stroke trunk piston diesel engine, with the lubricating oil composition of the present invention.
  • the present invention is based on the surprising discovery that a certain lubricating oil composition provides improved high temperature oxidation stability when employed in internal combustion engines such as diesel engines and gasoline engines.
  • the present invention relates to a lubricating oil composition as set out in claim 1.
  • the base oil of lubricating viscosity employed in the lubricating oil composition of the present invention generally is a mineral oil or a synthetic oil having a dynamic viscosity in the range of 22 to 300 mm 2 /s at 40°C.
  • the sulfur content of the base oil is preferably not less than 0.1 wt %, more preferably less than 0.03 wt %, most preferably less than 0.005 wt %.
  • the mineral oil is preferably prepared by processing a mineral oil of lubricating oil distillate by an appropriate combination of solvent purification and hydrogenation processing.
  • a mineral oil having been subjected to high hydrogenation processing i.e., hydrogenation cracking
  • the above-identified most preferred mineral oil can be a high viscosity index base oil which is prepared by processing synthetic wax by isomerization and hydrogenation cracking.
  • the synthetic wax was prepared by mineral slack was (crude wax) or natural gas.
  • the synthetic oil can be poly- ⁇ -olefin (polymer prepared from ⁇ -olefin having 3 to 12 carbon atoms), a sebacic acid compound such as dioctyl sebacate, a dialkyl diester prepared from a dibasic acid such as azelaic acid or adipic acid and an alcohol having 4 to 18 carbon atoms, a polyol ester prepared from 1-trimethylolpropane or pentaerythritol and a monobasic acid, or an alkylbenzene having alkyl of 9 to 40 carbon atoms.
  • the synthetic oil generally contains no sulfur compound and shows high thermal stability and high heat resistance. Moreover, the synthetic oil produces little soot and carbonaceous deposit. Therefore, the synthetic oil is preferred as the base oil for the lubricating oil composition of the present invention.
  • each of the mineral base oil and synthetic base oil can be employed singly. However, if desired, two or more of mineral base oils or two or more of synthetic base oils can be employed in combination. Further, if desired, one or more mineral base oils and one or more synthetic base oils can be employed in combination.
  • a major amount of base oil of lubricating viscosity as defined herein comprises 40 wt % or more.
  • Preferred amounts of base oil comprise 40 wt % to 97 wt %, preferably greater than 50 wt % to 97 wt %, more preferably 60 wt % to 97 wt % and most preferably 80 wt % to 95 wt % of the lubricating oil composition. (When weight percent is used herein, it is referring to weight percent of the lubricating oil composition unless otherwise specified.)
  • the overbased calcium carboxylate employed in the lubricating oil of the present invention has a TBN of 100 mg KOH/g or more and can be prepared in the manner described in the aforementioned references cited in the Background of the Invention.
  • the overbased calcium carboxylate will be in the amount of 0.19 to 2.10 wt %, preferably 0.38 to 1.15 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the calcium content.
  • the overbased calcium carboxylate comprises a relatively large amount (more than 50 wt %) of the following compound A and a relatively small amount (less than 50 wt %) of the following compound B: in which R is an alkyl group having 12 to 28 carbon atoms.
  • the lubricating oil composition of the present invention can contain other metal-containing detergents in addition to the overbased calcium carboxylate.
  • other metal-containing detergents employable in combination with the overbased calcium carboxylate include sulfurized phenate (e.g., sulfurized calcium phenate), petroleum sulfonates or synthetic sulfonates (e.g., calcium sulfonate), and salicylate (e.g., calcium salicylate).
  • the lubricating oil composition of the present invention contains a bis-succinimide compound (i.e., succinimide or its derivatives) in the amount of 0.002 to 0.06 wt %, preferably 0.014 to 0.02 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the nitrogen content.
  • the bis-succinimide compound preferably is an alkenylsuccinimide or an alkylsuccinimide derived from a polyolefin compound or its derivatives.
  • the bis-succinimide can be prepared, for example, by a reaction between succinic anhydride and a high molecular weight alkenyl or alkyl, followed by further reaction with a polyalkylenepolyamine containing 4 to 10, preferably 5 to 7, nitrogen atoms per molecule.
  • the bis-succinimide compound can be prepared by a thermal reaction between a polybutene compound containing 50% or more methylvinylidene structure and maleic anhydride, followed by reaction of the resulting polybutenyl succinic anhydride with a polyalkylenepolyamine containing 4 to 10, preferably 5 to 7, nitrogen atoms per molecule.
  • the high molecular weight alkenyl or alkyl group preferably is polybutene having a number-average molecular weight in the range of approximately 900 to 5,000.
  • the bis-succinimide can be employed in the form of a modified succinimide which is obtained by reacting succinimide with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate (e.g., ethylene carbonate), or an organic acid.
  • a modified succinimide which is obtained by reacting succinimide with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate (e.g., ethylene carbonate), or an organic acid.
  • a boron-containing alkenyl- or alkylsuccinimide which is obtained by reaction with boric acid or a boron compound.
  • the resulting modified succinimide compound exhibits high thermal stability and high anti-oxidation property.
  • the lubricating oil composition of the present invention can contain other ashless dispersants such as nitrogen-containing ashless dispersants (e.g., mono-structure type alkenyl- or alkylsuccinimide, and an alkenylbenzylamine) and/or dispersants containing no nitrogen atoms such as an alkenyl succinic ester in addition to the bis-structure alkenyl or alkyl succinimide.
  • nitrogen-containing ashless dispersants e.g., mono-structure type alkenyl- or alkylsuccinimide, and an alkenylbenzylamine
  • dispersants containing no nitrogen atoms such as an alkenyl succinic ester in addition to the bis-structure alkenyl or alkyl succinimide.
  • the zinc dialkyldithiophosphate employed in the lubrication oil composition of the present invention has a secondary alkyl group and will be in the amount of 0.007 to 0.15 wt %, preferably 0.036 to 0.072 wt %, based on the total amount of the lubricating oil composition and expressed in terms of the phosphorus content.
  • the alkyl group preferably contains 3 to 18 carbon atoms. All of the two alkyl groups of the zinc dialkyldithiophosphate can be secondary alkyl groups. Otherwise, a portion (e.g., a relatively small portion such as less than 48 mole %) of the alkyl groups of the zinc dialkyldithiophosphate can be a primary alkyl group.
  • the secondary-alkyl type zinc dialkyldithiophosphate can be employed in combination with a zinc dialkyldithiophosphate having a primary alkyl group.
  • the former zinc dialkyldithiophosphate is generally employed in an amount of 52 to 98 mole %, and the latter zinc dialkyldithiophosphate can be employed in an amount of 2 to 48 mole %.
  • the lubricating oil composition of the present invention can further contain other oxidation inhibitors, such as phenol oxidation inhibitors and/or amine oxidation inhibitors, in an amount of 0.01 to 5 wt %, preferably 0.1 to 3 wt %.
  • oxidation inhibitors such as phenol oxidation inhibitors and/or amine oxidation inhibitors
  • the lubrication oil composition of the present invention can further contain a multi-functional molybdenum-containing compound in an amount of 0.01 to 5 wt %, preferably 0.1 to 3 wt %.
  • the molybdenum-containing compound mainly serves as friction-modifier, oxidation inhibitor and anti-wear agent in the lubricating oil composition of the present invention.
  • the molybdenum-containing compound further provides effective high temperatures detergency.
  • the molybdenum-containing compound can be incorporated into the lubricating oil composition of the present invention in an amount of 10 to 2,500 ppm in terms of the molybdenum metal content.
  • molybdenum-containing compounds include, but not limited to, a sulfur-containing molybdenum complex compound of succinimide, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, an amine-molybdenum complex compound, oxymolybdenum diethylateamide, and oxymolybdenum monoglyceride.
  • the sulfur-containing molybdenum complex compound of succinimide is particularly effective to increase detergency at high temperatures.
  • the lubricating oil composition of the present invention can further contain a viscosity index improver in an amount of less than 20 wt %, preferably in an amount of 1 to 20 wt %.
  • a viscosity index improver examples include polymers as poly(alkyl methacrylate), ethylene-propylene copolymer, styrenebutadiene copolymer, and polyisoprene.
  • Dispersant-type viscosity index improvers and multi-functional viscosity index improvers which are obtained by adding dispersancy to the above-mentioned polymers are also employable.
  • the viscosity index improvers can be employed singly or in combination.
  • the lubricating oil composition of the present invention can further contain a variety of subsidiary additives.
  • the subsidiary additives include, but not limited to, oxidation inhibitors/anti-wear agents (e.g., zinc dithiocarbamate, methylene-bis(dibutyldithiocarbamate), oil-soluble copper compounds, sulfur-containing compounds such as sulfurized olefins, sulfurized esters and polysulfides, phosphate esters, phosphite esters, and organic amide compounds such as oleylamide.
  • Metal-deactivating compounds such as benzotriazol compounds and thiaziazol compounds also can be employed.
  • Anti-rust agents and de-emulsifiers such as nonionic surfactants (e.g., polyoxyethylene alkylphenyl ether, and copolymer of ethylene oxide and propylene oxide) also can be employed.
  • Friction modifiers such as amines, amides, amine salts, their derivatives, and fatty acid esters of polyhydric alcohols and their derivatives also can be employed.
  • Anti-foaming agents and pour point depressants also can be employed.
  • Each of the subsidiary additives is generally contained in the lubricating oil composition of the present invention in an amount of less than 3 wt %, preferably in the range of 0.001 to 3 wt %.
  • a lubricating oil composition (TBN: 30 mg•KOH/g, SAE viscosity grade: SAE 40) was prepared using the following additives and base oil:
  • a lubricating oil composition having the same composition of Example 1 except for containing no bis-succinimide (component b) was prepared.
  • a lubricating oil composition having the same composition of Example 1 except for replacing the zinc di(secondary)alkyldithiophosphate (component c) with a zinc di(primary)alkyldithiophosphate was prepared.
  • the phosphorus content of the latter di(primary)alkyldithiophosphate was the same as that of the former zinc di(secondary)alkyldithiophosphate.
  • a lubricating oil composition having the same composition of Example 1 except for replacing the bis-succinimide (component b) with a mono-succinimide dispersant was prepared.
  • the thermal stability of the lubrication oil compositions at high temperatures was evaluated using the JIS (Japanese Industrial Standard) K2514 ISOT (Indiana Stirred Oxidation Test). This test is used to determine the oxidation stability of a lubricating oil composition in the presence of copper, steel and heat.
  • JIS Japanese Industrial Standard
  • K2514 ISOT Indiana Stirred Oxidation Test
  • Example 1 Comparative Example A B C D Viscosity increase 0.97 1.21 1.19 1.18 1.16 TBN retention (HCl) 65.0 61.5 60.7 60.5 60.8 TBN retention (ASTM D2896) 92.4 89.9 86.3 87.1 88.8
  • the lubricating oil composition of the present invention provides low viscosity increase and shows high TBN retention. Accordingly, it is clear that the lubricating oil composition of the present invention has high anti-thermal oxidation property at high temperatures.

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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)
  • Lubricants (AREA)

Claims (8)

  1. Schmierölzusammensetzung mit einer Gesamtbasenziffer, bestimmt nach ASTM D2896, im Bereich von 5 bis 55 mg KOH/g, umfassend eine größere Menge eines Grundöls mit Schmierviskosität und
    a) 0,19 bis 2,10 Gew.-%, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung, eines überbasierten Calciumcarboxylats mit einer Gesamtbasenziffer, bestimmt nach ASTM D2896, von 100 mg KOH/g oder mehr, wobei der Gew.-% ausgedrückt ist nach Calciumgehalt, und wobei das überbasierte Calciumcarboxylat mit einer Gesamtbasenziffer von 100 mg KOH/g oder mehr mehr als 50 Gew.-% der folgenden Verbindung A und weniger als 50 Gew.-% der folgenden Verbindung B umfasst
    Figure imgb0008
    Figure imgb0009
     worin R eine Alkylgruppe mit 12 bis 28 Kohlenstoffatomen ist;
    b) 0,002 bis 0,06 Gew.-%, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung, einer Bissuccinimidverbindung, wobei der Gew.-% ausgedrückt ist nach Stickstoffgehalt; und
    c) 0,007 bis 0,15 Gew.-%, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung, eines Zinkdialkyldithiophosphats mit einer sekundären Alkylgruppe, wobei der Gew.-% ausgedrückt ist nach Phosphorgehalt.
  2. Schmierölzusammensetzung gemäß Anspruch 1, wobei die Menge des überbasierten Calciumcarboxylats mit einer Gesamtbasenziffer von 100mg·KOH/g oder mehr im Bereich von 0,38 bis 1,15 Gew.-% ist, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung und ausgedrückt nach Calciumgehalt.
  3. Schmierölzusammensetzung gemäß Anspruch 1, wobei die Menge der Bissuccinimidverbindung im Bereich von 0,014 bis 0,02 Gew.-% ist, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung und ausgedrückt nach Stickstoffgehalt.
  4. Schmierölzusammensetzung gemäß Anspruch 1, wobei die Menge des Zinkdialkyldithiophosphats mit einer sekundären Alkylgruppe im Bereich von 0,036 bis 0,072 Gew.-% ist, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung und ausgedrückt nach Phosphorgehalt.
  5. Schmierölzusammensetzung gemäß Anspruch 1, wobei die Bissuccinimidverbindung hergestellt wird durch eine thermische Reaktion zwischen einer Polybutenverbindung, enthaltend 50% oder mehr einer Methylvinylidenstruktur und Maleinanhydrid, gefolgt von weiterer Reaktion des erhaltenen Polybutenyls, Bernsteinsäurenahydrid mit einem Polyalkylenpolyamin, enthaltend 4 bis 10 Stickstoffatome pro Molekül.
  6. Schmierölzusammensetzung gemäß Anspruch 1, wobei das Zinkdialkyldithiophosphat mit einer sekundären Alkylgruppe Alkylgruppen mit unabhängig 3 bis 8 Kohlenstoffatomen umfasst.
  7. Verfahren zum Betreiben des Verbrennungsmotors mit einer Schmierölzusammensetzung mit einer Gesamtbasenziffer, bestimmt nach ASTM D2896, im Bereich von 5 bis 55 mg KOH/g, umfassend eine größere Menge eines Grundöls mit Schmierviskosität und
    a) 0,19 bis 2,10 Gew.-%, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung, eines überbasierten Calciumcarboxylats mit einer Gesamtbasenziffer, bestimmt nach ASTM D2896, von 100 mg KOH/g oder mehr, wobei der Gew.-% ausgedrückt ist nach Calciumgehalt, und wobei das überbasierte Calciumcarboxylat mit einer Gesamtbasenziffer von 100 mg KOH/g oder mehr mehr als 50 Gew.-% der folgenden Verbindung A und weniger als 50 Gew.-% der folgenden Verbindung B umfasst
    Figure imgb0010
    Figure imgb0011
     worin R eine Alkylgruppe mit 12 bis 28 Kohlenstoffatomen ist;
    b) 0,002 bis 0,06 Gew.-%, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung, einer Bissuccinimidverbindung, wobei der Gew.-% ausgedrückt ist nach Stickstoffgehalt; und
    c) 0,007 bis 0,15 Gew.-%, auf Grundlage der Gesamtmenge der Schmierölzusammensetzung, eines Zinkdialkyldithiophosphats mit einer sekundären Alkylgruppe, wobei der Gew.-% ausgedrückt ist nach Phosphorgehalt
  8. Verfahren gemäß Anspruch 7, wobei der Verbrennungsmotor ein Viertakt-Tauchkolbendieselmotor ist.
EP05258039.6A 2004-12-28 2005-12-23 Schmiermittelzusammensetzung mit verbesserter Oxidationsstabilität bei hohen Temperaturen Active EP1676902B1 (de)

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US9175237B2 (en) * 2007-12-12 2015-11-03 Chevron Oronite Technology B.V. Trunk piston engine lubricating oil compositions
WO2012112658A1 (en) * 2011-02-17 2012-08-23 The Lubrzol Corporation Lubricants with good tbn retention
US20130157910A1 (en) * 2011-12-16 2013-06-20 Chevron Oronite Company Llc Diesel engine oils

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220597A (ja) * 2001-01-29 2002-08-09 Nissan Motor Co Ltd ディーゼルエンジン油組成物
EP1736529A1 (de) * 2004-03-19 2006-12-27 Nippon Oil Corporation Schmierölzusammensetzung für dieselmotor

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3941889B2 (ja) * 1995-06-15 2007-07-04 新日本石油株式会社 エンジン油組成物
US5744430A (en) * 1995-04-28 1998-04-28 Nippon Oil Co., Ltd. Engine oil composition
JP3615267B2 (ja) * 1995-04-28 2005-02-02 新日本石油株式会社 エンジン油組成物
DE69812873T2 (de) * 1998-01-30 2004-01-22 Chevron Chemical S.A. Schwefel- und alkalimetalfreie Schmieröladditive
DE69827625T2 (de) * 1998-09-09 2005-12-08 Chevron Chemical S.A. Verfahren zur Herstellung von Erdalkalimetall-Salzen mit hoher Basizität, insbesondere von einem an einem Ring gebundenen Hydrocarbylsalicylat-carboxylat
JP2000192069A (ja) * 1998-12-28 2000-07-11 Oronite Japan Ltd ディ―ゼル内燃機関用潤滑油組成物及び添加剤組成物
JP3722472B2 (ja) * 2000-06-02 2005-11-30 シェブロンテキサコジャパン株式会社 潤滑油組成物
JP4185307B2 (ja) * 2001-09-20 2008-11-26 新日本石油株式会社 内燃機関用潤滑油組成物
JP4643087B2 (ja) * 2001-09-25 2011-03-02 日産自動車株式会社 内燃機関用潤滑油組成物
JP4017514B2 (ja) * 2002-12-27 2007-12-05 コスモ石油ルブリカンツ株式会社 エンジン油

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002220597A (ja) * 2001-01-29 2002-08-09 Nissan Motor Co Ltd ディーゼルエンジン油組成物
EP1736529A1 (de) * 2004-03-19 2006-12-27 Nippon Oil Corporation Schmierölzusammensetzung für dieselmotor

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SG123779A1 (en) 2006-07-26
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JP2006182987A (ja) 2006-07-13
CA2531433C (en) 2014-02-18
JP5198719B2 (ja) 2013-05-15

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