EP2569404B1 - Schmierölzusammensetzung für dieselmotoren - Google Patents

Schmierölzusammensetzung für dieselmotoren Download PDF

Info

Publication number
EP2569404B1
EP2569404B1 EP11718753.4A EP11718753A EP2569404B1 EP 2569404 B1 EP2569404 B1 EP 2569404B1 EP 11718753 A EP11718753 A EP 11718753A EP 2569404 B1 EP2569404 B1 EP 2569404B1
Authority
EP
European Patent Office
Prior art keywords
mass
zinc
lubricating oil
amount
oil 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.)
Active
Application number
EP11718753.4A
Other languages
English (en)
French (fr)
Other versions
EP2569404A1 (de
Inventor
Kiyoshi Hanyuda
Tetsuo Wakizono
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.)
Shell Lubricants Japan KK
Original Assignee
Shell Lubricants Japan KK
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
Application filed by Shell Lubricants Japan KK filed Critical Shell Lubricants Japan KK
Publication of EP2569404A1 publication Critical patent/EP2569404A1/de
Application granted granted Critical
Publication of EP2569404B1 publication Critical patent/EP2569404B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C10M2205/0225—Ethene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/17—Fisher Tropsch reaction products
    • C10M2205/173—Fisher Tropsch reaction products used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/066—Arylene diamines
    • 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
    • C10M2215/086—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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • 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
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/44—Boron free or low content boron 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2040/252—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

Definitions

  • This invention relates to a lubricating oil composition for diesel engines, and in particular relates to a lubricating oil composition for diesel engines having excellent engine (piston) detergency while being extra low ash despite not incorporating metallic detergents.
  • a diesel particulate filter (hereafter DPF), which is regarded as an effective way of cleaning the particulate matter (hereafter PM) in the exhaust gases of diesel engines, may be subject to clogging of the filter because of metal constituents in the engine oil used.
  • DPF diesel particulate filter
  • PM particulate matter
  • a low ash engine oil composition that contains no metallic additives can be considered, but if the metallic component is simply reduced compared to engine oil compositions of the prior art, the result will be a reduction in important functions, namely engine detergency, anti-wear performance and oxidative stability of the engine oil composition.
  • Patent Reference 1 Japanese Laid-open Patent 2007-254559 (Patent Reference 1) has as its objective a low-ash diesel engine oil composition, but the sulphated ash is still considerable at up to 0.6% by mass, and it further contains a metallic detergent, so that so long as it uses a small amount of metallic detergent, the situation is that it is continuing the prior art even with the objective of a low-ash engine oil.
  • Patent Reference 2 Japanese Laid-open Patent 2006-176672 (Patent Reference 2) has as its objective a lubricating oil for internal combustion engines with superior oxidative stability because of a low-ash component. It attempts to offer an increased viscosity and acid number in this low-ash oil, but it does not specially focus on piston detergency. Furthermore, the sulphated ash in the examples is extremely large, at 0.99 to 1.01% by mass.
  • This invention is intended to obtain a lubricating oil composition for use in diesel engines such that excellent engine (piston) detergency is maintained while clogging of the DPF is prevented and wear on valve trains is reduced, even without the inclusion of a metallic detergent.
  • This invention without the inclusion of a metallic detergent, maintains excellent engine piston detergency while preventing clogging of the DPF and wear on valve trains, by creating a balance between zinc dithiophosphates, succinimides and amine-based anti-oxidants added to the base oil.
  • a lubricating oil composition for use in diesel engines which comprises, in the base oil, not more than 0.3% by mass of sulphated ash, 0.01 to 0.2% by mass of nitrogen in succinimides, 0.05 to 0.12% by mass of zinc in zinc dithiophosphates, 0.02 to 0.3% by mass of nitrogen in amine-based anti-oxidants, and 0.01 to 0.08% by mass of boron, which further has a total value of zinc amount in zinc dithiophosphate x (succinimide nitrogen amount + amine-based anti-oxidant nitrogen amount) as defined above of from 0.015 to 0.06, preferably 0.015 to 0.04 and more preferably 0.015 to 0.04, and which does not contain salicylate, phenate or sulphonate metallic detergents, and wherein the boron is derived from boron-modified forms of alkenyl or alkyl succinimides.
  • the aforementioned base oil is preferably one that is a base oil or a base oil mixture selected from Group II, Group III, Group IV and Group V and where the sulphur component of the base oil is not more than 50 ppm.
  • this lubricating oil composition for use in diesel engines is such that the TGF in JASO M336:1998 Detergency Test Procedure is not more than 30%, and the cam nose wear in JASO M354:1998 Valve-train Wear Test Procedure is not more than 95 ⁇ m.
  • base oil used in the lubricating oil composition for diesel engines of the present invention it is possible in particular to use as appropriate mineral oils, synthetic oils and mixtures thereof as normally used for lubricating oils.
  • mineral oils synthetic oils and mixtures thereof as normally used for lubricating oils.
  • Group II base oils include, for example, paraffinic mineral oils obtained by appropriate use of a suitable combination of refining processes such as hydrocracking and dewaxing in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil.
  • Group II base oils refined by hydrorefining methods such as the Gulf Company method have a total sulphur content of less than 10 ppm and an aromatic content of not more than 5% and so can be used for this invention.
  • the viscosity of these base oils is not specially limited, but the viscosity index should be 80 to 120 and preferably 100 to 120.
  • the kinematic viscosity at 40°C should preferably be 2 to 680 mm 2 /s and more preferably 8 to 220 mm 2 /s.
  • the total sulphur content should be less than 300 ppm, preferably less than 100 ppm and more preferably less than 10 ppm.
  • the total nitrogen content should also be less than 10 ppm and preferably less than 1 ppm.
  • oils with an aniline point of 80 to 150°C and preferably 100 to 135°C should be used.
  • Group 2 Plus base oils which possess the viscosity index higher than 115, can be specified as a preferable Group 2 base oil.
  • Group III base oils include, for example, paraffinic mineral oils manufactured by a high degree of hydrorefining in respect of lubricating oil fractions obtained by atmospheric distillation of crude oil, base oils refined by Isodewaxing which dewaxes and substitutes with isoparaffins waxes produced by dewaxing processes, and base oils refined by the Mobil wax isomerisation process. These are also suitable for use in this invention.
  • the viscosity of these base oils is not specially limited, but the viscosity index should be 120 to 160 and preferably 120 to 150.
  • the kinematic viscosity at 40°C should preferably be 2 to 680 mm 2 /s and more preferably 8 to 220 mm 2 /s.
  • the total sulphur content should be less than 300 ppm, preferably less than 100ppm and more preferably less than 10 ppm.
  • the total nitrogen content should also be less than 10 ppm and preferably less than 1 ppm.
  • oils with an aniline point of 80 to 150°C and preferably 110 to 135°C should be used.
  • Group 3 Plus base oils which possess the viscosity index higher than 130, can be specified as a preferable Group 3 base oil.
  • synthetic oils mention may be made of polyolefins, alkylbenzenes, alkylnaphthalenes, esters, polyoxyalkylene glycols, polyphenyl ethers, dialkyldiphenyl ethers, fluorine-containing compounds (perfluoropolyethers, fluorinated polyolefins and so on), and silicones.
  • the aforementioned polyolefins include polymers of various olefins or hydrides thereof. Any olefin may be used, and as examples mention may be made of ethylene, propylene, butene and ⁇ -olefins with five or more carbons. In the manufacture of polyolefins, one kind of the aforementioned olefins may be used singly or two or more kinds may be used in combination. Particularly suitable are the polyolefins called poly- ⁇ -olefins (PAO). These are base oils of Group IV.
  • PAO poly- ⁇ -olefins
  • the viscosity of these synthetic oils is not specially limited, but the kinetic viscosity at 40°C should preferably be 2 to 680 mm 2 /s and more preferably 8 to 220 mm 2 /s.
  • GTLs gas to liquid synthesised by the Fischer-Tropsch method of converting natural gas to liquid fuel have a very low sulphur content and aromatic content compared with mineral oil base oils refined from crude oil and have a very high paraffin constituent ratio, and so have excellent oxidative stability, and because they also have extremely small evaporation losses, they are suitable as base oils for this invention.
  • the viscosity characteristics of GTL base oils are not specially limited, but normally the viscosity index should be 120 to 180, preferably 130 to 175, and more preferably 140 to 175. Also, the kinematic viscosity at 40°C should be 2 to 680 mm 2 /s and preferably 5 to 120 mm 2 /s. Normally the total sulphur content is also less than 10 ppm and the total nitrogen content less than 1 ppm.
  • a commercial example of such a GTL base oil is Shell XHVI (registered trademark).
  • Base oils specified above can be used singly or as mixtures, and their sulphur content should be less than 50ppm, preferably less than 10ppm and more preferably less than 1ppm.
  • zinc dialkyl dithiophosphates As examples of the aforementioned zinc dithiophosphates, mention may be made in general of zinc dialkyl dithiophosphates, zinc diaryl dithiophosphates and zinc arylalkyl dithiophosphates.
  • zinc dialkyl dithiophosphates where the alkyl groups of the zinc dialkyl dithiophosphates have primary or secondary alkyl groups of 3 to 22 carbons or alkylaryl groups substituted with alkyl groups of 3 to 18 carbons may be used.
  • zinc dialkyl dithiophosphates where the alkyl groups of the zinc dialkyl dithiophosphates have primary or secondary alkyl groups of 3 to 12 carbons or zinc diaryl dithiophosphates where the aryl groups are phenyl or alkylaryl groups substituted with alkyl groups of 1 to 18 carbons may be used.
  • the zinc dithiophosphates with secondary alkyl groups having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms and more preferably 3 to 6 atoms are preferred.
  • zinc dialkyl dithiophosphates mention may be made of zinc dipropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc dipentyl dithiophosphate, zinc dihexyl dithiophosphate, zinc diisopentyl dithiophosphate, zinc diethylhexyl dithiophosphate, zinc dioctyl dithiophosphate, zinc dinonyl dithiophosphate, zinc didecyl dithiophosphate, zinc didodecyl dithiophosphate, zinc dipropylphenyl dithiophosphate, zinc dipentylphenyl dithiophosphate, zinc dipropylmethylphenyl dithiophosphate, zinc dinonylphenyl dithiophosphate and zinc didodecylphenyl dithiophosphate.
  • Zinc dithiophosphates are incorporated so that the amount of zinc is 0.05 to 0.12% by mass, but preferably 0.06 to 0.12% by mass, of the lubricating oil composition.
  • Zinc dithiophosphates are, as mentioned above, effective anti-wear additives, but they contain phosphorus (P). Phosphorus compounds are said to poison exhaust-gas catalysts, and if the phosphorus content in the composition increases, there is a heightened possibility of a deleterious effect on the exhaust-gas cleaning catalyst. For this reason, if the zinc dithiophosphate is incorporated so that the amount of zinc exceeds 0.12% by mass, there will be a concomitant increase in the amount of phosphorus in the composition, which is not desirable.
  • the effect of being a wear additive will be saturated, so that an effect matching the expenditure will not be obtained and this will not be efficient.
  • the amount is less than 0.05% by mass, the result in terms of being an anti-wear additive may not be effectual.
  • an alkenyl succinimide or an alkyl succinimide and/or a boron-modified derivative thereof is used for the aforementioned succinimide. It has the function of being an ashless dispersant.
  • alkenyl or an alkyl succinimide mention may be made of the alkenyl or alkyl succinic monoimides represented by General Formula (1) and the alkenyl or alkylsuccinic bisimides represented by General Formula (2).
  • R 1 , R 3 and R 4 each denote an alkenyl group or an alkyl group with a weight-average molecular weight of from 500 to 3,000, and R 3 and R 4 may be the same or different.
  • R 2 , R 5 and R 6 each denote an alkylene group having from 2 to 5 carbons, and R 5 and R 6 may be the same or different.
  • m is an integer of from 1 to 10 and n is 0 or an integer of from 1 to 10.
  • the weight-average molecular weight of each of R 1 , R 3 and R 4 in General Formulae (1) and (2) is, as aforementioned, from 500 to 3,000, but preferably from 1,000 to 3,000. If the weight-average molecular weight is less than 500, solubility in the base oil will be reduced, and if it exceeds 3,000 detergency will decrease, so that there will be a risk that the target functions will not be achieved.
  • m is an integer of from 1 to 10, but preferably from 2 to 5, and more preferably from 3 to 4. If m exceeds 2, there will be good detergency. If m is less than 5 solubility in the base oil will be good.
  • n is 0 or an integer of from 1 to 10, but preferably from 1 to 4 and more preferably from 2 to 3. If n exceeds 1, there will be good detergency, and if n is less than 4 solubility in the base oil will be good.
  • alkenyl groups in General Formulae (1) and (2) mention may be made of polybutenyl groups, polyisobutenyl groups, and ethylene-propylene copolymers.
  • Alkyl groups include hydrogenated forms thereof.
  • suitable alkenyl groups mention may be made of polybutenyl groups and polyisobutenyl groups. These polybutenyl groups are obtained by polymerising mixtures of 1-butene and isobutene or highly refined isobutene.
  • alkenyl or alkyl succinimides can normally be prepared by reacting with a polyamine an anhydrous alkenyl succinimide obtained by a reaction between a polyolefin and maleic anhydride, or an anhydrous alkyl succinimide obtained by hydrogenating same.
  • the aforementioned succinic monoimides and bisimides may be prepared by varying the reaction proportions of anhydrous alkenyl succinic acids or anhydrous alkyl succinic acids and polyamines.
  • olefin monomer that forms the aforementioned polyolefin it is possible to use mixtures of one or two or more kinds of ⁇ -olefins having from 2 to 8 carbons, and it is possible to use satisfactorily mixtures of isobutene and butene-1.
  • polyamines As examples of the aforementioned polyamines, mention may be made of unitary diamines such as ethylene diamine, propylene diamine, butylene diamine and pentylene diamine, and of polyalkylene polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, di(methylethylene) triamine, dibutylene triamine, tributylene tetramine and pentapentylene hexamine.
  • unitary diamines such as ethylene diamine, propylene diamine, butylene diamine and pentylene diamine
  • polyalkylene polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, di(methylethylene) triamine, dibutylene triamine, tributylene tetramine and pentapentylene hexamine.
  • boron-modified derivatives of alkenyl or alkyl succinimides it is possible to use those prepared by the usual methods. For example, they can be obtained after making the aforementioned polyolefins into anhydrous alkenyl succinimides by reacting them with maleic acid, by further imidification through reacting them with an intermediate obtained by reacting the aforementioned polyamines and a boron compound such as boron oxide, a boron halide, a boric acid, a boric anhydride, a boric ester or an ammonium salt of a boric acid.
  • a boron compound such as boron oxide, a boron halide, a boric acid, a boric anhydride, a boric ester or an ammonium salt of a boric acid.
  • the lubricating oil composition of this invention contains, in terms of the composition, from 0.01 to 0.2% by mass, calculated in terms of nitrogen content, of an alkenyl or alkyl succinic monoimide or bisimide and/or a boron-modified derivative thereof as an ashless dispersant, but preferably contains from 0.05 to 0.15% by mass.
  • the content of the alkenyl or alkyl succinic monoimide or bisimide and/or boron-modified derivative thereof is less than 0.01% by mass, the effect as an ashless dispersant will not be satisfactorily displayed, and if it exceeds 0.2% by mass, deleterious influence on rubber parts such as elastomers used in engines can be seen.
  • the content of a boron-modified derivative of an alkenyl or alkyl succinic monoimide in said ashless dispersant will be, calculated in terms of boron, from 0.01 to 0.08% by mass and preferably from 0.04 to 0.07% by mass.
  • the boron-converted content of the alkenyl or alkyl succinic monoimide and/or boron-modified derivative thereof in the ashless dispersant is less than 0.01% by mass the effect of the anti-wear and high temperature detergency performance is not enough and if it exceeds 0.08% by mass, that effective performance will be saturated and the economic efficiency will decrease.
  • boron derives from boron-modified forms of succinimides, and for the amount of succinimide added to be within the aforementioned range, it is often not desirable if the boron component is added in excess, because the excess of the boron component may cause the DPF clogging by increasing the sulphated ash derived by increased boron in the formulation.
  • amine-based anti-oxidants used in this invention those used generally for lubricating oils are preferred for practical use, and it is possible to use them singly or in plural combinations in the lubricating oil composition within the range of from 0.02 to 0.3% by mass in terms of the nitrogen content.
  • Amine-based anti-oxidants structurally are prone to surface adsorption, and because the zinc dithiophosphate, the anti-wear agent, decomposes and the acidic intermediates are adsorbed on the surface, an excess added amount is again not desirable, so that it is best to control the upper limit.
  • dialkyldiphenylamines such as p,p'-dioctyldiphenylamine (Nonflex OD-3, made by Seiko Chemical Ltd), p,p'-di- ⁇ -methylbenzyldiphenylamine and N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and monooctyldiphenylamine, bis(dialkylphenyl)amines such as di(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine, alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and N-t-dodecylphenyl-1-naphth
  • phenolic anti-oxidants Apart from the amine-based anti-oxidants used in this invention, it is possible to use phenolic anti-oxidants.
  • phenolic anti-oxidants and amine-based anti-oxidants are used in combination. These anti-oxidants may be used singly or in plural combinations within the range of from 0.01 to 5% by mass in the lubricating oil composition.
  • dialkyl sulphides such as didodecyl sulphide, thiodipropionate esters such as dioctadecyl thiodipropionate, dimyristyl thiodipropionate and dodecyloctadecyl thiodipropionate, and 2-mercaptobenzoimidazole.
  • Phenolic anti-oxidants include 2-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone (Antage DBH, made by Kawaguchi Chemical Industry Co.
  • 2,6-di-t-butylphenol 2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butyl-4-methylphenol and 2, 6-di-t-butyl-4-ethylphenol
  • 2,6-di-t-butyl-4-alkoxyphenols such as 2,6-di-t-butyl-4-methoxyphenol and 2,6-di-t-butyl-4-ethoxyphenol.
  • alkyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionates such as n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (Yoshinox SS, made by Yoshitomi Fine Chemicals Ltd.), n-dodecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate and 2'-ethylhexyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, benzenepropanoic acid 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C 7 -C 9 side-chain alkyl ester (Irganox L135, made by Ciba Specialty Chemicals Ltd.), 2,6-
  • bisphenols such as 4,4'-butylidenebis(3-methyl-6-t-butylphenol) (Antage W-300, made by Kawaguchi Chemical Industry Ltd.), 4,4'-methylenebis(2,6-di-t-butylphenol) (Ionox 220AH, made by Shell Japan Ltd.), 4,4'-bis(2,6-di-t-butylphenol), 2,2-(di-p-hydroxyphenyl)propane (Bisphenol A, made by Shell Japan Ltd.), 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 4,4'-cyclohexylidenebis(2,6-t-butylphenol), hexamethylene glycol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (Irganox L109, made by Ciba Specialty Chemicals Ltd.), triethylene glycol bis[3-(3-t-butylphenol
  • Metal deactivators that can be used together with the lubricating oil composition for diesel engines of this invention include benzotriazole and benzotriazole derivatives which are 4-alkyl-benzotriazoles such as 4-methyl-benzotriazole and 4-ethyl-benzotriazole, 5-alkyl-benzotriazoles such as 5-methyl-benzotriazole and 5-ethyl-benzotriazole, 1-alkyl-benzotriazoles such as 1-dioctylaminomethyl-2,3-benzotriazole and 1-alkyl-tolutriazoles such as 1-dioctylaminomethyl-2,3-tolutriazole, and benzoimidazole and benzoimidazole derivatives which are 2-(alkyldithio)-benzoimidazoles such as 2-(octyldithio)-benzoimidazole, 2-(decyldithio)-benzoimidazole and 2-(dode
  • indazole indazole derivatives which are toluindazoles such as 4-alkyl-indazoles and 5-alkyl-indazoles
  • benzothiazole and benzothiazole derivatives which are 2-mercaptobenzothiazole derivatives (Thiolite B-3100, made by Chiyoda Chemical Industries Ltd.)
  • 2-(alkyldithio)benzothiazoles such as 2-(hexyldithio)benzothiazole and 2-(octyldithio)benzothiazole
  • 2-(alkyldithio)toluthiazoles such as 2-(hexyldithio)toluthiazole and 2-(octyldithio)toluthiazole
  • 2-(N,N-dialkylydithiocarbamyl)-benzothiazoles such as 2-(N,N-diethyldithiocarbamyl)-benzothiazole, 2-(N,
  • benzooxazole derivates which are 2-(alkyldithio)benzooxazoles such as 2-(octyldithio)benzooxazole, 2-(decyldithio)benzooxazole and 2-(dodecyldithio)benzooxazole or which are 2-(alkyldithio)toluoxazoles such as 2-(octyldithio)toluoxazole, 2-(decyldithio)toluoxazole and 2-(dodecyldithio)toluoxazole, thiadiazole derivatives which are 2,5-bis(alkyldithio)-1,3,4-thiadiazoles such as 2,5-bis(heptyldithio)-1,3,4-thiadiazole, 2,5-bis(nonyldithio)-1,3,4-thiadiazole
  • metal deactivators may be used singly or in plural combinations within the range of from 0.01 to 0.5% by mass in the lubricating oil composition.
  • fatty acids alkenylsuccinic half-esters, fatty acid soaps, alkyl sulphonic acid salts, sulphonates, and naphthenates of alkaline earth metals (calcium (Ca), magnesium (Mg), barium (Ba) and so on), polyhydric alcohol fatty acid esters, fatty acid amines, paraffin oxide, and alkylpolyoxyethylene ethers, and normally the amount thereof in the blend will be within the range of from 0.01 to 5% by mass on the basis of the total amount of the composition.
  • pour-point depressants and viscosity-index improvers can also be added to the lubricating oil composition of this invention.
  • viscosity-index improvers examples include non-dispersant type viscosity-index improvers such as polymethacrylates as well as ethylene-propylene copolymers, styrene-diene copolymers such as styrene-butadiene or olefin polymers such as polyisobutylene and polystyrene, and dispersant type viscosity-index improvers where nitrogen-containing monomers have been copolymerised with these.
  • the amount to be added they may be used within the range of from 0.05 to 20% by mass of the lubricating oil composition.
  • pour-point depressants mention may be made of polymethacrylate-based polymers. As regards the amount to be added, they may be used within the range of from 0.01 to 5% by mass of the lubricating oil composition. A polymethacrylate-based pour-point depressant was incorporated in the examples of this invention.
  • Defoaming agents may also be added in order to impart defoaming characteristics to the lubricating oil composition of this invention.
  • preferred defoaming agents mention may be made of organosilicates such as polydimethylsiloxane, diethylsilicate and fluorosilicone, and non-silicone type defoaming agents such as polyalkylacrylates.
  • organosilicates such as polydimethylsiloxane, diethylsilicate and fluorosilicone
  • non-silicone type defoaming agents such as polyalkylacrylates.
  • the amount to be added they may be used singly or in plural combinations within the range of from 0.0001 to 0.1% by mass in the lubricating oil composition.
  • the component materials were mixed in the proportions shown in Tables 1 and 2, and lubricating oil compositions for use in diesel engine oils were obtained.
  • the proportions shown in Tables 1 and 2 are mass% unless otherwise specified.
  • the TGF will exceed 30% or the amount of cam nose wear will exceed 95 ⁇ m, which is not desirable. If it is between 0.015 and 0.06, both the TGF and the amount of cam nose wear will be small, which means it is possible to achieve desirable results. If the value is more than 0.06, it is not favourable in terms of economic efficiency.
  • TGF value measured after Nissan TD25 engine test
  • Valve-train wear tests were carried out in accordance with JASO M354:1999 (using Mitsubishi 4D34T4 engine). Evaluation criterion: Wear on cam nose 95 ⁇ m or less Acceptable Over 95 ⁇ m Not acceptable
  • the cam nose wear value limit is based on the pass criteria for JASO's DH-2.
  • Example 1 did not contain any metallic detergent.
  • the succinimide-3 ashless dispersant gave a nitrogen amount of 0.15% by mass
  • the amine-based anti-oxidant gave a nitrogen amount of 0.08% by mass
  • the succinimide-based dispersant gave a boron amount of 0.047% by mass
  • the ZnDTP gave a Zn amount of 0.10% by mass, so that the parameter for zinc amount x (succinimide nitrogen amount + amine-based anti-oxidant nitrogen amount) had a value of 0.023
  • the TGF was 12% and the cam nose wear was 7 ⁇ m.
  • the sulphated ash was 0.23% by mass, meeting the criterion, so that satisfactory performance had been obtained.
  • Example 2 did not use a metallic detergent.
  • the main points were that the total nitrogen amount of the mixture of succinimide-1, succinimide-2 and succinmimide-3 gave a total nitrogen amount of 0.12% by mass, and the parameter value was therefore 0.020.
  • the TGF was 12%, and the cam nose wear was 18 ⁇ m, which meant satisfactory performance had been achieved.
  • the nitrogen amount of the succinimides was 0.15% by mass, and it was a mixture of succinimide-1 and succinimide-2.
  • the Zn amount was 0.1% by mass, and the amine-based anti-oxidant gave a nitrogen amount of 0.0396% by mass, which meant that the parameter value was 0.019.
  • the TGF value was 9% and the cam nose wear was 24.7 ⁇ m.
  • the succinimide-based dispersant gave a nitrogen amount of 0.075% by mass. Also, the Zn amount was 0.077% by mass, and no amine-based anti-oxidant was added, so that the parameter value was considerably reduced at 0.006, the TGF value was 47%, and there was a substantial increase in cam nose wear.
  • the nitrogen amount from the succinimide-based dispersant was 0.12% by mass, and the nitrogen amount from the amine-based anti-oxidant was 0.08% by mass, whilst the Zn amount was 0.05% by mass. This meant the parameter value was outside the range at 0.010, and the TGF was 39% but the cam nose wear exceeded 95 ⁇ m at 217 ⁇ m.
  • Comparative Example 3 gave a Zn amount of 0.05% by mass, a succinimide nitrogen amount of 0.10% by mass, an amine-based anti-oxidant nitrogen amount of 0.0792% by mass, and a parameter value of 0.009, which was outside the range.
  • the TGF value was 55 and the valve-train wear deteriorated further to 300 ⁇ m.
  • Comparative Example 4 where the Zn amount was 0.06% by mass, the succinimide nitrogen amount was 0.15% by mass, and the amine-based anti-oxidant nitrogen amount was 0.0396% by mass, the parameter value was 0.011, the TGF was 14% and the cam nose wear exceeded 95 ⁇ m at 130.7 ⁇ m.

Landscapes

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

Claims (4)

  1. Schmierölzusammensetzung zur Verwendung in Dieselmotoren, die, im Basisöl, nicht mehr als 0,3 Masse-% Sulfatasche, 0,01 bis 0,2 Masse-% Stickstoff in Succinimiden, 0,05 bis 0,12 Masse-% Zink in Zinkdithiophosphaten, 0,02 bis 0,3 Masse-% Stickstoff in aminbasierten Antioxidantien und 0,01 bis 0,08 Masse-% Bor umfasst, die ferner einen Gesamtwert der Zinkmenge in Zinkdithiophosphat
    x (Succinimidstickstoffmenge + aminbasierte
    Antioxidantienstickstoffmenge) wie oben definiert von 0,015 bis 0,06 aufweist, und die kein metallisches Salicylat-, Phenat- oder Sulfonat-Tensid enthält, und wobei das Bor aus bormodifizierten Formen von Alkenyl- oder Alkylsuccinimiden abgeleitet ist.
  2. Schmierölzusammensetzung zur Verwendung in Dieselmotoren nach Anspruch 1, wobei das oben genannte Öl ein einzelnes Basisöl oder ein Gemisch aus der Gruppe II, Gruppe III, Gruppe IV und Gruppe V ausgewählt ist, und worin die Schwefelkomponente des Basisöls nicht mehr als 50 ppm beträgt.
  3. Schmierölzusammensetzung zur Verwendung in Dieselmotoren nach Anspruch 1 oder Anspruch 2, sodass das TGF im JASO M336:1998 Reinigungswirkungstestverfahren nicht mehr als 30% beträgt und im JASO M354:1999 Ventiltriebverschleißtest nicht mehr als 95 µm beträgt.
  4. Schmierölzusammensetzung zur Verwendung in Dieselmotoren nach Anspruch 1, Anspruch 2 oder Anspruch 3, wobei das oben genannte Öl sekundäre Alkylzinkdithiophosphate enthält, wobei die Alkylgruppen 3 bis 12 Kohlenstoffatome aufweisen.
EP11718753.4A 2010-05-11 2011-05-11 Schmierölzusammensetzung für dieselmotoren Active EP2569404B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010109425 2010-05-11
JP2011104510A JP5687951B2 (ja) 2010-05-11 2011-05-09 ディーゼルエンジン用潤滑油組成物
PCT/EP2011/057585 WO2011141495A1 (en) 2010-05-11 2011-05-11 Lubricating oil composition for diesel engines

Publications (2)

Publication Number Publication Date
EP2569404A1 EP2569404A1 (de) 2013-03-20
EP2569404B1 true EP2569404B1 (de) 2020-01-22

Family

ID=44119033

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11718753.4A Active EP2569404B1 (de) 2010-05-11 2011-05-11 Schmierölzusammensetzung für dieselmotoren

Country Status (8)

Country Link
US (1) US20130267449A1 (de)
EP (1) EP2569404B1 (de)
JP (1) JP5687951B2 (de)
CN (1) CN102939365B (de)
BR (1) BR112012028762A2 (de)
ES (1) ES2776987T3 (de)
RU (1) RU2560964C2 (de)
WO (1) WO2011141495A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104059715B (zh) * 2013-03-22 2016-12-28 中国石油化工股份有限公司 抗氧剂组合物、润滑油组合物及提高润滑油抗氧性能的方法
CN103740449B (zh) * 2013-12-21 2016-05-11 乌鲁木齐市隆成实业有限公司 高档全合成汽机油及其制备方法
CN104830493A (zh) * 2015-05-29 2015-08-12 马健 一种柴油机用润滑油组合物
KR101578344B1 (ko) 2015-07-13 2015-12-17 화인케미칼 주식회사 사출성형용 고무 조성물
CN107151576A (zh) * 2016-03-04 2017-09-12 雅孚顿（天津）石化产品有限公司 一种全合成汽机油及其制备工艺
CN107434996A (zh) * 2016-05-25 2017-12-05 国际壳牌研究有限公司 润滑流体
US10738262B2 (en) 2017-10-30 2020-08-11 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
CN111944592A (zh) * 2020-08-12 2020-11-17 东风商用车有限公司 一种节能型柴油发动机油及其制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3319487B2 (ja) * 1994-08-09 2002-09-03 出光興産株式会社 潤滑油組成物
ES2169785T3 (es) * 1995-02-01 2002-07-16 Lubrizol Corp Composicion lubricante con bajo contenido en cenizas.
US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
RU2223303C2 (ru) * 2000-12-21 2004-02-10 ООО "Петрохимпром" Пакет присадок к моторным маслам для высокофорсированных дизельных двигателей и моторное масло, его содержащее
WO2005037967A1 (ja) * 2003-10-16 2005-04-28 Nippon Oil Corporation 潤滑油添加剤及び潤滑油組成物
JP4486339B2 (ja) * 2003-10-16 2010-06-23 新日本石油株式会社 潤滑油組成物
GB0326808D0 (en) * 2003-11-18 2003-12-24 Infineum Int Ltd Lubricating oil composition
JP4806528B2 (ja) 2004-12-22 2011-11-02 出光興産株式会社 内燃機関用潤滑油組成物
JP5094030B2 (ja) * 2006-03-22 2012-12-12 Ｊｘ日鉱日石エネルギー株式会社 低灰エンジン油組成物
JP5406433B2 (ja) * 2007-04-27 2014-02-05 東燃ゼネラル石油株式会社 内燃機関用潤滑油組成物
WO2009050287A1 (en) * 2007-10-19 2009-04-23 Shell Internationale Research Maatschappij B.V. Functional fluids for internal combustion engines
US7960322B2 (en) * 2007-10-26 2011-06-14 Chevron Oronite Company Llc Lubricating oil compositions comprising a biodiesel fuel and an antioxidant
JP5377925B2 (ja) * 2008-10-22 2013-12-25 出光興産株式会社 内燃機関用潤滑油組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
WO2011141495A1 (en) 2011-11-17
ES2776987T3 (es) 2020-08-03
RU2560964C2 (ru) 2015-08-20
BR112012028762A2 (pt) 2016-07-19
EP2569404A1 (de) 2013-03-20
RU2012153201A (ru) 2014-06-20
CN102939365B (zh) 2015-11-25
JP2011256374A (ja) 2011-12-22
JP5687951B2 (ja) 2015-03-25
CN102939365A (zh) 2013-02-20
US20130267449A1 (en) 2013-10-10

Similar Documents

Publication Publication Date Title
EP2569404B1 (de) Schmierölzusammensetzung für dieselmotoren
JP4608129B2 (ja) 潤滑油組成物
JP5065044B2 (ja) 潤滑油組成物
JP5465938B2 (ja) 内燃機関用潤滑油組成物
EP3397740B1 (de) Schmierölzusammensetzung für dieselmotoren
JP4806528B2 (ja) 内燃機関用潤滑油組成物
JP5840334B2 (ja) 内燃機関を潤滑する方法
US20110224115A1 (en) Reducing High-Aqueous Content Sludge in Diesel Engines
JP5828756B2 (ja) 自動車用エンジンオイル
EP3688126B1 (de) Schmierölzusammensetzung für brennkraftmaschine
JP6971149B2 (ja) 潤滑用組成物
US20240141250A1 (en) Lubricating Oil Compositions
US20240141156A1 (en) Functionalized C4 to C5 Olefin Polymers and Lubricant Compositions Containing Such

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121207

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20141107

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SHOWA SHELL SEKIYU K.K.

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SHELL LUBRICANTS JAPAN K.K.

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011064725

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10M0141100000

Ipc: C10M0141120000

RIC1 Information provided on ipc code assigned before grant

Ipc: C10M 141/12 20060101AFI20190712BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190902

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1226911

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011064725

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200122

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200614

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20200519

Year of fee payment: 10

Ref country code: DE

Payment date: 20200529

Year of fee payment: 10

Ref country code: ES

Payment date: 20200618

Year of fee payment: 10

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2776987

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200422

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200522

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200423

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20200522

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011064725

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1226911

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200122

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20201023

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200531

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011064725

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210511

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210511

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200122

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210512