EP2133406B1 - Composition d'huile lubrifiante pour moteur à combustion interne - Google Patents

Composition d'huile lubrifiante pour moteur à combustion interne Download PDF

Info

Publication number
EP2133406B1
EP2133406B1 EP09162272A EP09162272A EP2133406B1 EP 2133406 B1 EP2133406 B1 EP 2133406B1 EP 09162272 A EP09162272 A EP 09162272A EP 09162272 A EP09162272 A EP 09162272A EP 2133406 B1 EP2133406 B1 EP 2133406B1
Authority
EP
European Patent Office
Prior art keywords
mass
content
composition
component
oil
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
EP09162272A
Other languages
German (de)
English (en)
Other versions
EP2133406A1 (fr
Inventor
Hideki Kamano
Toyoharu Kaneko
Minoru Yamashita
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.)
Idemitsu Kosan Co Ltd
Toyota Motor Corp
Original Assignee
Idemitsu Kosan Co Ltd
Toyota Motor 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
Application filed by Idemitsu Kosan Co Ltd, Toyota Motor Corp filed Critical Idemitsu Kosan Co Ltd
Publication of EP2133406A1 publication Critical patent/EP2133406A1/fr
Application granted granted Critical
Publication of EP2133406B1 publication Critical patent/EP2133406B1/fr
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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2215/28—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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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
    • 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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/40—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
    • C10N2030/45—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
    • C10N2040/12—Gas-turbines
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to a lubricating oil composition used in an internal combustion engine such as a diesel engine or a gasoline engine.
  • An important problem in diesel engines has been how to reduce environment pollution caused by such emission gas components as particulate matters (PM) and NO x .
  • An effective solution is to mount such an exhaust purifying device as a particulate filter or an exhaust purifying catalyst (oxidization or reduction catalyst) on an automobile.
  • an exhaust purifying device as a particulate filter or an exhaust purifying catalyst (oxidization or reduction catalyst)
  • soot adhered to the particulate filter can be eliminated by oxidation or combustion.
  • the filter may be clogged by metal oxides, phosphoric salts, sulfate salts, carboxylate salts and the like that are generated by combustion.
  • the used engine oil is partially combusted to be exhausted as exhaust gas. Accordingly, the less metal components and sulfur components are contained in the lubricating oil, the more preferable the lubricating oil becomes.
  • phosphorus components and sulfur components in the lubricating oil are required to be reduced.
  • the content of sulfate ash content is 1.0 weight% or less
  • the content of sulfur content is 0.3 weight% or less
  • the content of molybdenum is 100 ppm or more (see, for instance, document 1: JP-A-2002-060776 ).
  • the lowering of the viscosity of the engine oil may cause portions of the engine to be more easily worn.
  • additives such as friction modifiers and extreme pressure agents are added to the engine oil so as to reduce friction damages and wear of the engine entailed by lowered viscosity of the engine oil.
  • the extreme pressure agents typically used are phosphorus-containing compounds.
  • the phosphorus-containing compounds are known to degrade the catalysts for purifying exhaust gas, the content of the phosphorus-containing compounds in the engine oil is preferably reduced as much as possible. When this is applied, however, it may become difficult to maintain the wear prevention of the engines for a long time, so that a method of maintaining the wear prevention is required.
  • engine oil compositions are formed by adding mineral oil or synthetic oil with boron compound derivatives of alkenylsuccinimide, organic molybdenum compounds, specific alkylthiadiazole and specific fatty acid ester (see, for instance, document 2: JP-A-11-269476 ).
  • succinimide having a specific structure is used as ashless dispersants in place of or in combination with metal-based detergents (see, for instance, document 4: JP-A-2001-226381 , document 5: JP-A-2001-247623 ).
  • Such ashless dispersants can finely disperse the diesel soots generated during the combustion and sludge generated by oxidation degradation of the engine oil and can prevent these diesel soots and sludge from adhering to the engine parts, thereby enhancing detergency for the pistons.
  • An object of the invention is to provide a lubricating oil composition for use in internal combustion engines such as gasoline engines, diesel engines and gas engines, the lubricating oil composition capable of maintaining such a high level of friction modification as exhibited when the composition is new oil for a long time even when contents of metal contents and phosphorus contents are suppressed to lower levels, and also capable of maintaining such friction modification even when diesel soots are mixed in a diesel engine.
  • lubricating oil compositions for internal combustion engines as follows are provided:
  • composition contains: base oil; (A) a boronated product of a succinimide compound; (B) molybdenum dithiocarbamate (hereinafter may also be referred to as “MoDTC”); and (C) zinc dialkyldithiophosphate (hereinafter may also be referred to as "ZnDTP”).
  • base oil a boronated product of a succinimide compound
  • MoDTC molybdenum dithiocarbamate
  • ZnDTP zinc dialkyldithiophosphate
  • mineral oil and/or synthetic oil is used for the base oil of the composition.
  • the mineral oil and synthetic oil are not particularly limited but may be suitably selected from any mineral oil and synthetic oil that have been conventionally used as base oil of the lubricating oil for internal combustion engines.
  • Examples of the mineral oil are mineral oil refined by processing lubricating oil fractions by at least one of solvent-deasphalting, solvent-extracting, hydrocracking, solvent-dewaxing, catalytic-dewaxing and hydrorefining (the lubricating oil fractions are obtained by vacuum-distilling atmospheric residual oil obtained by atmospherically distilling crude oil) and mineral oil manufactured by isomerizing wax and GTL (gas-to-liquid) WAX.
  • examples of the synthetic oil are polybutene, polyolefin ( ⁇ -olefin homopolymer or copolymer such as ethylene- ⁇ -olefin copolymer), various esters (such as polyol ester, diacid ester and phosphoric ester), various ethers (such as polyphenylether), polyglycol, alkylbenzene, alkyl naphthalene and the like.
  • polyolefin and polyol ester are particularly preferable in perspective of viscosity characteristics, solubility of additives and compatibility with seal rubber.
  • one of the above mineral oil may be singularly used or a combination of two or more thereof may be used as the base oil.
  • one of the above synthetic oil may be singularly used or a combination of two or more thereof may be used.
  • a combination of at least one of the above mineral oil and at least one of the above synthetic oil may be used.
  • kinematic viscosity of base oil at 100 degrees C is preferably 2 to 30 mm 2 /s, more preferably 3 to 15 mm 2 /s, further more preferably 4 to 10 mm 2 /s.
  • kinematic viscosity at 100 degrees C is 2 mm 2 /s or more, evaporation loss is small.
  • the kinematic viscosity at 100 degrees C is 30 mm 2 /s or less, power loss due to viscosity resistance is not so large, thereby improving fuel efficiency.
  • the base oil oil whose %CA measured by a ring analysis is 3.0 or less and whose sulfur content is 50 ppm by mass or less is preferably usable.
  • the %CA measured by the ring analysis means a proportion (percentage) of aromatic content calculated by the n-d-M ring analysis method.
  • the sulfur content is measured based on Japanese Industrial Standard (hereinafter referred to as JIS) K 2541.
  • the base oil whose %CA is 3.0 or less and whose sulfur content is 50 ppm by mass or less exhibits favorable oxidation stability. Such base oil can restrict an increase of acid number and a generation of sludge, thereby providing a lubricating oil composition that is less corrosive to metal.
  • the %CA is more preferably 1.0 or less, much more preferably 0.5 or less while the sulfur content is more preferably 30 ppm by mass or less.
  • viscosity index of the base oil is preferably 70 or more, more preferably 100 or more, much more preferably 120 or more. In the base oil whose viscosity index is 120 or more, a viscosity change due to temperature change is small.
  • the component (A) used in the aspect of the invention is a boronated product of a polyalkenyl succinimide compound represented by the following formula (1).
  • the polyalkenyl succinimide compound is obtained by reacting (a) succinimide or its anhydride substituted by a polyalkenyl group having a number average molecular weight of 500 to 5000 with (b) polyalkylene polyamine of which mol% or more of the entirety contains a piperazinyl ring structure at its terminal.
  • R 1 represents a polyalkenyl group having a number average molecular weight of 500 to 5000
  • R 2 , R 3 , R 4 and R 5 each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms
  • q represents an integer of 2 to 4
  • n represents an integer of 0 to 3
  • r represents an integer of 2 to 4
  • A represents an amino group or a group having the same piperazinyl ring structure as the terminal of the polyalkylene polyamine.
  • the number average molecular weight of the polyalkenyl group is less than 500 in the component (a)
  • the boronated product of the succinimide compound represented by the formula (1) may not be sufficiently soluble in the base oil of the lubricating oil.
  • the number average molecular weight of the polyalkenyl group is more than 5000, the polyalkenyl succinimide compound may have high viscosity, thereby deteriorating the handleability. Accordingly, the number average molecular weight of the polyalkenyl group is preferably 500 to 5000, more preferably 800 to 3000.
  • the polyalkenyl group having such a molecular weight a polymer or a copolymer of monoolefin and diolefin having 2 to 16 carbon atoms is typically used.
  • the monoolefin are ethylene, propylene, butene, butadiene, decene, dodecene, hexadecene and the like.
  • butene is particularly preferable in the aspect of the invention because of its enhanced high-temperature detergency for the engine parts and its easy availability.
  • a polybutenyl group (a polymer of the butene) are also preferable.
  • the polyalkenyl-substituted succinic acid or its anhydride is obtainable by reacting a substance such as polybutene having the molecular weight equivalent to that of the polyalkenyl group with a substance such as maleic anhydride by a known method.
  • the polyalkylene polyamine as the component (b) may be polyalkylene polyamine entirely having a piperazinyl ring structure at its terminal, or may alternatively be a mixture of polyalkylene polyamine having a piperazinyl ring structure at its terminal and polyalkylene polyamine having no ring structure at its terminal.
  • the content of the polyalkylene polyamine having a piperazinyl ring structure at its terminal is less than 5 mol%, the high-temperature detergency and oxidation stability may become insufficient.
  • the content is 10 mol% or more or 20 mol% or more, the high-temperature detergency and oxidation stability are enhanced.
  • the upper limit on the content of the polyalkylene polyamine having a piperazinyl ring structure at its terminal is preferably 95 mol% or less, more preferably 90 mol% or less.
  • the content of the polyalkylene polyamine having a ring structure at its terminal is preferably 5 to 95 mol%, more preferably 10 to 90 mol%.
  • the terminal ring structure of the polyalkylene polyamine having a piperazinyl at its terminal is represented by a formula (1') where both p1 and p2 are 2.
  • a representative example of the polyalkylene polyamine having this ring structure at its terminal is aminoalkyl piperazine having a piperazinyl structure at its terminal such as aminoethyl piperazine, aminopropyl piperazine, aminobutyl piperazine, amino(diethylenediamino) piperazine, amino(dipropyldiamino) piperazine and the like.
  • aminoethyl piperazine is particularly preferable in view of its easy availability.
  • the polyalkylene polyamine having no ring structure at its terminal means polyalkylene polyamine having no ring structure or polyalkylene polyamine having a ring structure at any site other than its terminal.
  • polyalkylene polyamine having no ring structure are polyethylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, propylenediamine, dibutylenetriamine, tributylenetriamine and the like.
  • a representative example of the polyalkylene polyamine having a ring structure at any site other than its terminal is di(aminoalkyl) piperazine such as di(aminoethyl) piperazine.
  • polyalkylene polyamine that may have a ring structure
  • a mixture of polyalkylene polyamine and polyethylene polyamine such as triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine is particularly preferable because of its enhanced high-temperature detergency for engine-parts and its easy availability.
  • the component (A) according to the aspect of the invention is a boronated product of the polyalkenyl succinimide compound obtained from the above-described component (a) and component (b).
  • the boronated product is obtainable by reacting the polyalkenyl succinimide compound obtained from the component (a) and component (b) with a boron compound (component (c)).
  • the boron compound are boracic acid, boric anhydride, borate ester, boric oxide and boron halogenide.
  • boracic acid is particularly preferable.
  • any known methods of reacting can be used.
  • the target substance can be obtained.
  • the components (a) and (b) are initially reacted with each other, then its reaction product is reacted with the component (c).
  • a mixing ratio of the components (a) to (b) in the reaction of the components (a) and (b) is preferably 0.1-to-10 to 1 (mole ratio), more preferably 0.5-to-2 to 1 (mole ratio).
  • a reaction temperature of the components (a) and (b) is preferably approximately 80 to 250 degrees C, more preferably approximately 100 to 200 degrees C.
  • solvents such as an organic solvent exemplified by hydrocarbon oil may be used as necessary.
  • a mixing ratio of polyalkylene polyamine to the boron compound as the component (c) is typically 1 to 0.05-to-10, preferably 1 to 0.5-to-5 (mole ratio).
  • a reaction temperature thereof is preferably approximately 50 to 250 degrees C, more preferably 100 to 200 degrees C.
  • solvents such as an organic solvent exemplified by hydrocarbon oil may be used for the reaction product.
  • a boronated product of the succinimide compound substituted by the polyalkenyl group having a number average molecular weight of 200 to 5000 i.e., the component (A)
  • the component (A) a boronated product of the succinimide compound substituted by the polyalkenyl group having a number average molecular weight of 200 to 5000.
  • one of the components (A) may be singularly used or a combination of two or more thereof may be used.
  • the component (A), which is a boronated product of the polyalkenyl succinimide compound having the structure represented by the formula (1) as described above, may be used together with a non-boron-containing polyalkenyl succinimide compound.
  • the polyalkenyl succinimide compound used at this time may be monoimide or bisimide.
  • polybutenyl succinic acid bisimide which is a polybutene of an alkenyl group having a number average molecular weight of 1500 to 3000, is particularly preferable.
  • the content of the component (A) contained in the composition is preferably 0.01 to 0.1 mass% of the total amount of the composition in terms of boron (atoms), more preferably 0.01 to 0.05 mass%, much more preferably 0.01 to 0.03 mass%. Since a predetermined amount or more of boron is contained in the component (A), pistons can be favorably cleaned in the high-temperature internal combustion engine. When the content of boron is less than 0.01 mass%, sufficient high-temperature detergency is not obtained. When the content of boron exceeds 0.1 mass%, no further improvement is made on the high-temperature detergency, which is of little practical use.
  • a mass ratio (B/N) of boron (B) to nitrogen (N) contained in the component (A) is preferably 0.5 or more, more preferably 0.6 or more, much more preferably 0.8 or more.
  • B/N is 0.5 or more, high-temperature detergency for engine parts is greatly enhanced.
  • a boronated product of the succinimide compound is obtainable by initially reacting the materials (a) and (b) and subsequently reacting the reaction product thereof with the material (c), the reaction order may be changed such that the materials (a) and (c) are initially reacted and the reaction product thereof is subsequently reacted with the material (b). With this reaction order, the target boronated product of the polyalkenyl succinimide compound may also be likewise obtained.
  • the component (B) contained in the composition is molybdenum dithiocarbamate (MoDTC) represented by the following formula (2).
  • MoDTC molybdenum dithiocarbamate
  • R 6 to R 9 each independently represent a hydrocarbyl group having 4 to 22 carbon atoms
  • X 1 to X 4 each represent a sulfur atom or an oxygen atom.
  • R 6 to R 9 each preferably represent a hydrocarbon group having 4 to 22 carbon atoms, examples of which are an alkyl group, alkenyl group, alkylaryl group, cycloalkyl group and cycloalkenyl group.
  • R 6 to R 9 each preferably represent a branched or linear alkyl group or alkenyl group having 4 to 18 carbon atoms, more preferably an alkyl group having 8 to 13 carbon atoms.
  • R 6 to R 9 may be mutually the same or different, but the solubility in the base oil, storage stability and duration of friction modification can be enhanced when R 6 and R 7 and R 8 and R 9 represent different alkyl groups.
  • X 1 to X 4 each represent a sulfur atom or an oxygen atom. All of X 1 to X 4 may be sulfur atoms or oxygen atoms.
  • a ratio of sulfur atoms to oxygen atoms is preferably 1/3 to 3/1, more preferably 1.5/2.5 to 3/1 because the corrosion resistance and solubility in the base oil can be enhanced.
  • one of the components (B) may be singularly used or a combination of two or more thereof may be used.
  • the lubricating oil composition is prepared such that the content of the component (B) in the lubricating oil composition is 0.01 to 0.08 mass% of the total amount of the composition in terms of molybdenum, preferably 0.03 to 0.08 mass%. When the content is less than 0.01 mass%, sufficient friction modification is not obtained. When the content is more than 0.08 mass%, the solubility in the base oil and the corrosion resistance may be deteriorated.
  • the composition further contains zinc dialkyldithiophosphate (ZnDTP) as the component (C).
  • ZnDTP zinc dialkyldithiophosphate
  • the structure of ZnDTP is exemplarily represented by the following formula (3).
  • R 10 , R 11 , R 12 and R 13 each represent a primary or secondary alkyl group having 3 to 22 carbon atoms or a substituent selected from alkylaryl groups substituted by an alkyl group having 3 to 18 carbon atoms.
  • R 10 , R 11 , R 12 and R 13 may be mutually the same or different.
  • one of the ZnDTP may be singularly used or two or more thereof may be used in combination.
  • ZnDTP containing zinc dithiophosphate of a secondary alkyl group as the main component is preferable for enhancing wear resistance.
  • ZnDTP examples include 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, zinc didodecylphenyl dithiophosphate and zinc didodecylphenyl dithiophosphate.
  • the content of the ZnDTP as the component (C) in the lubricating oil composition according to the aspect of the invention is preferably 0.01 to 0.09 mass% of the total amount of the composition in terms of phosphorus, more preferably 0.02 to 0.08 mass%.
  • the content of phosphorus in the composition is less than 0.01 mass%, the wear resistance is not sufficient, and MoDTC of the component (B) cannot sufficiently provide the friction modification.
  • the content of phosphorus exceeds 0.09 mass%, poisoning on the purifying catalysts for exhaust gas becomes unfavorably worsened.
  • composition is preferably further added with a phenol-based antioxidant and/or an amine-based antioxidant.
  • phenol-based antioxidant examples include: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 4,4'-methylenebis(2,6-di-t-butylphenol); 4,4'-bis(2,6-di-t-butylphenol); 4,4'-bis(2-methyl-6-t-butylphenol); 2,2'-methylenebis(4-ethyl-6-t-butylphenol); 2,2'-methylenebis(4-methyl-6-t-butylphenol); 4,4'-butylidenebis(3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis(2,6-di-t-butylphenol); 2,2'anethylenebis(4-methyl-6-nonylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); 2,
  • amine-based antioxidant examples include: an antioxidant based on monoalkyl diphenylamine such as monooctyl diphenylamine and monononyl diphenylamine; an antioxidant based on dialkyl diphenylamine such as 4,4-dibutyl diphenylamine, 4,4'-dipentyl diphenylamine, 4,4'-dihexyl diphenylamine, 4,4'-diheptyl diphenylamine, 4,4'-dioctyl diphenylamine and 4,4'-dinonyl diphenylamine; an antioxidant based on polyalkyl diphenylamine such as tetrabutyl diphenylamine, tetrahexyl diphenylamine, tetraoctyl diphenylamine and tetranonyl diphenylamine; and an antioxidant based on naphthylamine, specifically alkyl-substituted phenyl-a
  • the composition may be further added with a molybdenum-amine-based antioxidant as another oxidant.
  • a molybdenum-amine-based antioxidant a hexahydric molybdenum compound, an example of which is a reaction product obtained by reacting molybdenum trioxide and/or molybdenum acid with an amine compound, may be used.
  • the reaction product may be, for example, a compound obtained by the manufacturing method disclosed in JP-A-2003-252887 .
  • the anime compound to be reacted with the hexahydric molybdenum compound is subject to no particular limitation, and examples thereof are monoamine, diamine, polyamine and alkanolamine.
  • examples of the amine compound are: alkyl amine having an alkyl group of 1 to 30 carbon atoms (the alkyl group may be linear or branched), exemplified by methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, methylpropylamine and the like; alkenyl amine having an alkenyl group of 2 to 30 carbon atoms (the alkenyl group may be linear or branched), exemplified by ethenylamine, propenylamine, butenylamine, octenylamine and oleylamine; alkanol amine having an alkanol group of 1 to 30 carbon atoms (the alkanol group may be linear or branched), exemplified by methanolamine, ethanolamine, methanolethanolamine and methanolpropanolamine; alkylenediamine having an alkylene group of 1 to 30 carbon atoms, exemplified
  • a content of the antioxidant is preferably 0.3 mass% or more of the total amount of the composition, more preferably 0.5 mass% or more.
  • the antioxidant may not be dissolved in the base oil of the lubricating oil. Accordingly, the contents of the antioxidant is preferably in a range from 0.3 to 2 mass% of the total amount of the composition.
  • the lubricating oil composition for internal combustion engines according to the aspect of the invention may be added as necessary with other additives such as a viscosity index improver, a metal-based detergent, an ashless friction modifier (friction modifier), a pour point depressant, a rust inhibitor, a metal deactivator, a surfactant and antifoaming agent as long as advantages of the invention are not hampered.
  • additives such as a viscosity index improver, a metal-based detergent, an ashless friction modifier (friction modifier), a pour point depressant, a rust inhibitor, a metal deactivator, a surfactant and antifoaming agent as long as advantages of the invention are not hampered.
  • the viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, an olefin-based copolymer (such as an ethylene-propylene copolymer), a dispersed olefin-based copolymer, a styrene-based copolymer (such as a styrene-diene copolymer and a styrene-isoprene copolymer) and the like.
  • a content of the viscosity index improver is approximately 0.5 to 15 mass% of the total amount of the composition, preferably I to 10 mass%.
  • the metal-based detergent may be any alkyl earth metal-based detergent usable in the lubricating oil.
  • any one of alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate and a mixture of two or more selected therefrom are usable.
  • An example of the alkaline earth metal sulfonate is alkaline earth metal salt of alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 to 1500 (preferably 400 to 700).
  • the alkaline earth metal salt is exemplified by magnesium salt and/or calcium salt and the like, among which calcium salt is preferably used.
  • alkaline earth metal phenate is alkaline earth metal salt of alkylphenol, alkylphenol sulfide and a Mannich reaction product of alkylphenol.
  • the alkaline earth metal salt is exemplified by magnesium salt and/or calcium salt and the like, among which calcium salt is preferably used.
  • alkaline earth metal salicylate is alkaline earth metal salt of alkyl salicylic acid.
  • the alkaline earth metal salt is exemplified by magnesium salt and/or calcium salt and the like, among which calcium salt is preferably used.
  • An alkyl group for forming the alkaline earth metal-based detergent preferably has 4 to 30 carbon atoms.
  • the alkyl group is more preferably a linear or branched alkyl group having 6 to 18 carbon atoms, in which 6 to 18 carbon atoms may be in a linear chain or in a branched chain.
  • the alkyl group may be a primary alkyl group, a secondary alkyl group or a tertiary alkyl group.
  • alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate may be neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate obtained by: directly reacting the above-described alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, a Mannich reaction product of alkylphenol, alkyl salicylic acid or the like with alkaline earth metal base exemplified by an oxide or a hydroxide of alkaline earth metal such as magnesium and/or calcium; or converting the above-described substance into alkali metal salt such as sodium salt or potassium salt and subsequently substituting the alkali metal salt with alkaline earth metal salt.
  • alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate may be: basic alkaline earth metal sulfonate, basic alkaline earth metal phenate and basic alkaline earth metal salicylate obtained by heating neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate with excess alkaline earth metal salt or alkaline earth metal base under the presence of water; or overbased alkaline earth metal sulfonate, overbased alkaline earth metal phenate and overbased alkaline earth metal salicylate obtained by reacting neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate and neutral alkaline earth metal salicylate with carbonate or borate of alkaline earth metal under the presence of carbon dioxide gas.
  • the metal-based detergent may be the neutral salt, the basic salt, the overbased salt or a mixture thereof.
  • a mixture of at least one of the overbased salicylate, the overbased phenate and the overbased sulfonate with the neutral sulfonate is preferable in terms of detergency for the interior of the engines and wear resistance.
  • the metal-based detergent which is diluted with light lubricant base oil and the like to be commercially available, preferably has a metal content of 1.0 to 20 mass%, more preferably 2.0 to 16 mass%.
  • the total base number of the metal-based detergent is typically 10 to 500 mg KOH/g, preferably 15 to 450 mg KOH/g. One or two selected therefrom is usable.
  • the total base number herein means the total base number measured by potentiometer titration (base number perchloric acid method) based on the Item 7 of "Petroleum Products and Lubricating Oil - Examining Method of Neutralization Value" of JIS K2501.
  • the metal-based detergent in the aspect of the invention is typically one of or a mixture of two or more of detergents having the metal ratio of 20 or less.
  • the metal-based detergent especially preferably contains as the main component a metal-based detergent that has the metal ratio of 3 or less, more preferably the metal ratio of 1.5 or less, particularly preferably the metal ratio of 1.2 or less.
  • the metal ratio herein is represented by (valence of metal element in the metal-based detergent) ⁇ (content of metal element (mol%)) / (content of soap base (mol%)), and the metal element means calcium, magnesium and the like while the soap base means a sulfonate group, phenol group, salicylic acid group and the like.
  • the content of the metal-based detergent is 1 mass% or less of the total amount of the composition in terms of metal element, more preferably 0.5 mass% or less. Further, in order to reduce the sulfate ash content of the composition down to 0.8 mass% or less, the content of the metal-based detergent is preferably 0.2 mass% or less. On the other hand, the content of the metal-based detergent is preferably 0.005 mass% or more in terms of metal element, more preferably 0.01 mass% or more. In order to further enhance oxidation stability, base number maintainability and high-temperature detergency, the content of the metal-based detergent is further preferably 0.05 mass% or more.
  • the obtained compound can favorably maintain the base number and the high-temperature detergency for a long time.
  • the sulfate ash content herein refers to a value measured by a method defined in "Experiment Method of Sulfate Ash", Item 5 of JIS K2272.
  • the sulfate ash content is mainly originated from metal-containing additives.
  • any compounds generally used as the ashless friction modifier for lubricating oil may be used, examples of which are fatty acid, aliphatic alcohol, aliphatic ether, aliphatic ester, aliphatic amine and aliphatic amide that have at least one alkyl or alkenyl group of 6 to 30 carbon atoms in the molecule.
  • the additive amount of the ashless friction modifier is preferably 0.2 to 1.0 mass%, more preferably 0.25 to 0.8 mass%, further preferably 0.3 to 0.6mass%.
  • the friction modification is not sufficiently provided. Even when the additive amount exceeds 1.0 mass%, no incremental friction modification comparative thereto is additionally provided.
  • pour point depressant examples include a copolymer of ethylene and vinyl acetate, a condensation product of paraffin chloride with naphthalene, a condensation product of paraffin chloride with phenol, polymethacrylate, polyalkylstyrene and the like.
  • polymethacrylate having a mass-average molecular weight of approximately 5,000 to 50,000 is preferable.
  • the pour point depressant is contained with a content of 0.1 to 5 mass% of the total amount of the composition.
  • rust inhibitor examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic ester, multivalent alcohol ester and the like.
  • a content of the viscosity index improver is approximately 0.01 to 1 mass% of the total amount of the composition, preferably 0.05 to 0.5 mass%.
  • the metal deactivator (copper corrosion inhibitor) are benzotriazole-based compounds, tolyltriazole-based compounds, thiadiazole-based compounds and imidazole-based compounds. Among the above, the benzotriazole-based compounds are preferable.
  • a content of the metal deactivator is preferably 0.01 to 0.1 mass% of the total amount of the composition, more preferably 0.03 to 0.05 mass%.
  • a content of the antifoaming agent is preferably approximately 0.005 to 0.1 mass% of the total amount of the compound.
  • Sulfur content of the lubricating oil composition according to the aspect of the invention is preferably 0.3 mass% or less of the total amount of the composition, more preferably 0.2 mass% or less, much more preferably 0.1 mass% or less.
  • sulfur content is 0.3 mass% or less, deterioration of the catalyst performance for purifying exhaust gas can be effectively prevented.
  • Sulfate ash content of the lubricating oil composition according to the aspect of the invention is preferably 0.8 mass% or less, more preferably 0.6 mass% or less.
  • the sulfate ash content means ash content obtained by adding sulfuric acid to carbonized residue generated by combustion of samples for heating so that the residue has a constant mass.
  • the sulfate ash is generally used for knowing a rough amount of metal-based additives contained in the lubricating oil composition. Specifically, the sulfate ash is measured by a method defined in "5. Experiment Method of Sulfate Ash" of JIS K 2272.
  • the lubricating oil composition for internal combustion engines according to the aspect of the invention can maintain such a high level of friction modification as exhibited when the composition is new oil for a long time.
  • the lubrication oil composition is favorably applicable to internal combustion engines such as gasoline engines, diesel engines and gas engines. Further, even when diesel soots are mixed, the lubricating oil composition can maintain the above effects, which is particularly preferable in diesel engines.
  • Lubricating oil compositions composed as in Table 1 were prepared, and then the friction coefficients of the compositions when being new oil and the friction coefficients of the compositions after NOx degradation were measured. In accordance with the results, the compositions were evaluated in terms of performance as the lubricating oil for internal combustion engines.
  • the characteristics and properties of the base oil, additives and compositions were measured in the following manner.
  • a proportion (percentage) of aromatic content was calculated by the n-d-M ring analysis method.
  • testing machine for JSOT test JIS K2514
  • nitrogen gas containing 8000 volume ppm of NO and air were blown to the sample oil under the presence of copper and iron catalysts, respectively at flow rate of 100 mL/minite, and NOx degradation test was conducted.
  • the test temperature was 140 degrees C and testing time was 24 hours.
  • the friction coefficients were measured with an SRV testing machine (manufactured by Optimol Ltd.) under the following conditions.
  • the components used for preparing the lubricating oil compositions are as follows.
  • the above boronated polybutenyl succinic monoimide A was manufactured by the following method.
  • An yield of the obtained polybutenyl succinimide was 750 g and its base number was 51 mg KOH/g (by a perchloric acid method).
  • 150 g of the obtained polybutenyl succinimide and 20 g of boric acid were put into a separable flask of 500 milliliter and reacted with each other in nitrogen gas stream at 150 degrees C for four hours. After generated water was distilled away therefrom under a low pressure at 150 degrees C, the temperature was lowered to 140 degrees C and filtration was conducted.
  • An yield of the generated boronated polybutenyl succinic monoimide A was 165 g and its boron content was 2.1 mass%.
  • Polyalkylene polyamine having a ring structure at its terminal was approximately 40 mol% of the total polyalkylene polyamine.
  • the boronated polybutenyl succinic monoimide B was manufactured through the same reactions as the boronated polybutenyl succinic monoimide A, except that the additive amount of boric acid was 13 g. An yield of the generated boronated polybutenyl succinic monoimide B was 161 g. Polyalkylene polyamine having a ring structure at its terminal was approximately 40 mol% of the total polyalkylene polyamine.
  • Boronated Polybutenyl Succinic Monoimide C number average molecular weight of the polybutenyl group being 980; nitrogen content of 2.30 mass%; boron content of 1.90 mass%; B/N ratio of 0.83; and chlorine content of 0.01 mass% or less.
  • the boronated polybutenyl succinic monoimide C was manufactured through the same reactions as the boronated polybutenyl succinic monoimide A, except that 18 g (0.17 mol) of diethylene triamine (DETA) and 25 g (0.17 mol) of triethylene tetramine (TETA) were used without use of aminoethyl piperazine (AEP).
  • An yield of the generated boronated polybutenyl succinic monoimide C was 165g. No polyalkylene polyamine having a ring structure at its terminal was contained therein.
  • the boronated polybutenyl succinic monoimide D was manufactured through the same reactions as the boronated polybutenyl succinic monoimide A, except that 18 g (0.17 mol) of diethylene triamine (DETA) and 25 g (0.17 mol) of triethylene tetramine (TETA) were used without use of aminoethyl piperazine (AEP) and that the additive amount of boric acid was 13 g.
  • An yield of the generated boronated polybutenyl succinic monoimide D was 161g. No polyalkylene polyamine having a ring structure at its terminal was contained therein.
  • Comparative 3 In the sample oil of Comparative 3, which was blended with the boronated polybutenyl succinic monoimide D, the oil after the NOx degradation test, the oil added with carbon black and the oil added with carbon black after the NOx degradation test had higher SRV friction coefficients, because the boronated polybutenyl succinic monoimide D did not contain polyalkylene polyamine having a ring structure at its terminal and its B/N ratio was as low as 0.34. Comparative 4, in which no MoDTC was blended, had a high SRV friction coefficient, and no friction modification was provided.

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 (2)

  1. Composition d'huile lubrifiante pour moteurs à combustion interne, comprenant :
    une huile de base formée d'une huile minérale et/ou d'une huile synthétique ;
    (A) un produit boré d'un composé de polyalcényle succinimide ;
    (B) un dithiocarbamate de molybdène ; et
    (C) un dialkyldithiophosphate de zinc, dans laquelle
    le composant (A) est un produit boré d'un composé de polyalcényle succinimide obtenu par réaction (a) d'un acide succinique ou de son anhydride substitué par un groupe polyalcényle ayant un poids moléculaire moyen en nombre de 500 à 5 000 avec (b) une polyalkylène polyamine dont 5% en moles ou plus de la totalité a une structure de cycle pipérazinyle à son extrémité, le composé de polyalcényle succinimide étant représenté par une formule (1) suivante, un rapport en masse du bore sur l'azote (rapport B/N) étant 0,5 ou plus, une teneur du composant (A) étant 0,01 à 0,1% en masse de la quantité totale de la composition en termes de bore,
    Figure imgb0011
     où : R1 représente un groupe polyalcényle ayant un poids moléculaire moyen en nombre de 500 à 5 000 ; R2, R3, R4 et R5 représentent chacun indépendamment un hydrogène ou un groupe alkyle ayant 1 à 3 atomes de carbone ; q représente un entier de 2 à 4 ; n représente un entier de 0 à 3 ; r représente un entier de 2 à 4 ; et A représente un groupe amino ou un groupe ayant la même structure de cycle pipérazinyle que l'extrémité de la polyalkylène polyamine,
    le composant (B) est un dithiocarbamate de molybdène représenté par une formule (2) suivante, une teneur du composant (B) étant 0,01 à 0,08% en masse de la quantité totale de la composition en termes de molybdène,
    Figure imgb0012
     où : R6 à R9 représentent chacun indépendamment un groupe hydrocarbyle ayant 4 à 22 atomes de carbone ; et X1 à X4 représentent chacun un atome de soufre ou un atome d'oxygène, et
    une teneur du composant (C) est 0,01 à 0,09% en masse de la quantité totale de la composition en termes de phosphore.
  2. Composition d'huile lubrifiante selon la revendication 1, dans laquelle une teneur en soufre est 0,3% en masse ou moins de la quantité totale de la composition tandis qu'une teneur en cendres de sulfate est 0,8% en masse ou moins de la quantité totale de la composition.
EP09162272A 2008-06-09 2009-06-09 Composition d'huile lubrifiante pour moteur à combustion interne Active EP2133406B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008150903A JP4597223B2 (ja) 2008-06-09 2008-06-09 内燃機関用潤滑油組成物

Publications (2)

Publication Number Publication Date
EP2133406A1 EP2133406A1 (fr) 2009-12-16
EP2133406B1 true EP2133406B1 (fr) 2011-08-17

Family

ID=40886310

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09162272A Active EP2133406B1 (fr) 2008-06-09 2009-06-09 Composition d'huile lubrifiante pour moteur à combustion interne

Country Status (3)

Country Link
EP (1) EP2133406B1 (fr)
JP (1) JP4597223B2 (fr)
AT (1) ATE520762T1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107949628A (zh) * 2015-08-06 2018-04-20 道达尔销售服务公司 用于预防或减少发动机中的早燃的润滑组合物

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2550346B1 (fr) 2010-03-25 2020-11-04 Vanderbilt Chemicals, LLC Compositions lubrifiantes à ultrabasse teneur en phosphore
JP2011252073A (ja) * 2010-06-01 2011-12-15 Idemitsu Kosan Co Ltd 低摩擦摺動材料用潤滑油組成物、及びこれを用いた摺動機構
JP5815223B2 (ja) * 2010-11-12 2015-11-17 Ｊｘ日鉱日石エネルギー株式会社 エンジン油組成物
EP2740783A4 (fr) * 2011-08-03 2015-03-18 Idemitsu Kosan Co Composition de lubrifiant pour huile de moteur à combution interne
US20130165357A1 (en) * 2011-12-22 2013-06-27 Exxonmobil Research & Engineering Company Lubricant compositions for SI-AL alloy surfaces and methods for using
US9587200B2 (en) * 2012-07-31 2017-03-07 Idemitsu Kosan Co., Ltd. Lubricant composition for internal combustion engine
WO2014136973A1 (fr) * 2013-03-08 2014-09-12 出光興産株式会社 Composition d'huile lubrifiante
JP6300686B2 (ja) 2014-01-31 2018-03-28 Ｅｍｇルブリカンツ合同会社 潤滑油組成物
JP5950481B2 (ja) * 2015-02-16 2016-07-13 出光興産株式会社 低摩擦摺動材料用潤滑油組成物、及びこれを用いた摺動機構
JP6114330B2 (ja) * 2015-03-31 2017-04-12 出光興産株式会社 潤滑油組成物及び内燃機関の摩擦低減方法
FR3039165B1 (fr) * 2015-07-23 2018-11-30 Total Marketing Services Composition lubrifiante a fuel eco longue duree
CN105733768B (zh) * 2016-02-23 2018-08-14 北京雅士科莱恩石油化工有限公司 一种矿区专用重载爬坡柴油机油及其制备方法
JP6780826B2 (ja) * 2017-03-16 2020-11-04 出光興産株式会社 潤滑油組成物及び内燃機関の摩擦低減方法
WO2021187370A1 (fr) * 2020-03-16 2021-09-23 出光興産株式会社 Composition d'huile lubrifiante, moteur diesel sur lequel est monté un surcompresseur et procédé d'utilisation de la composition d'huile lubrifiante
WO2022168935A1 (fr) * 2021-02-05 2022-08-11 出光興産株式会社 Composition lubrifiante

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL255193A (fr) * 1959-08-24
US3272746A (en) * 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US4370246A (en) 1981-04-27 1983-01-25 Chevron Research Company Antioxidant combinations of molybdenum complexes and aromatic amine compounds
JPH01269477A (ja) 1988-04-20 1989-10-26 Takenori Kato ビネガー入り食品
JPH11269477A (ja) * 1998-03-20 1999-10-05 Cosmo Sogo Kenkyusho Kk エンジン油組成物
JP3985330B2 (ja) * 1998-03-20 2007-10-03 株式会社コスモ総合研究所 ディーゼルエンジン油組成物
JP2001247623A (ja) * 1999-12-27 2001-09-11 Idemitsu Kosan Co Ltd こはく酸イミド系化合物及びその用途
JP4212751B2 (ja) * 2000-02-16 2009-01-21 出光興産株式会社 ホウ素化こはく酸イミド系化合物及びその用途
JP5231694B2 (ja) 2000-08-22 2013-07-10 出光興産株式会社 ディーゼル微粒子除去装置付きディーゼルエンジン用潤滑油組成物
JP2003252887A (ja) 2002-03-04 2003-09-10 Asahi Denka Kogyo Kk モリブデンアミン化合物の製造方法
US20050181957A1 (en) * 2002-05-30 2005-08-18 Hiroaki Koshima Lubricating oil additive composition for internal combustion engine
US6962896B2 (en) 2002-05-31 2005-11-08 Chevron Oronite Company Llc Reduced color molybdenum-containing composition and a method of making same
JP5203590B2 (ja) * 2006-10-27 2013-06-05 出光興産株式会社 潤滑油組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107949628A (zh) * 2015-08-06 2018-04-20 道达尔销售服务公司 用于预防或减少发动机中的早燃的润滑组合物

Also Published As

Publication number Publication date
ATE520762T1 (de) 2011-09-15
JP4597223B2 (ja) 2010-12-15
JP2009292998A (ja) 2009-12-17
EP2133406A1 (fr) 2009-12-16

Similar Documents

Publication Publication Date Title
EP2133406B1 (fr) Composition d'huile lubrifiante pour moteur à combustion interne
JP5175462B2 (ja) 内燃機関用潤滑油組成物
JP5203590B2 (ja) 潤滑油組成物
JP6302458B2 (ja) 潤滑油組成物
JP6676868B2 (ja) 潤滑油組成物
JP5167140B2 (ja) 潤滑油組成物
US8349775B2 (en) Lubricant composition
JP5431947B2 (ja) 潤滑油組成物
JP5377925B2 (ja) 内燃機関用潤滑油組成物
KR20100087722A (ko) 윤활유 조성물
EP2248876B1 (fr) Utilisation d'une composition lubrifiante dans un moteur courant avec une carburant contenant biodiesel
JP2006176672A (ja) 内燃機関用潤滑油組成物
JPWO2008133327A1 (ja) 潤滑油組成物
WO2013141077A1 (fr) Composition d'huile lubrifiante pour moteur en alliage d'aluminium et procédé de lubrification
JP6247822B2 (ja) アルミ合金製エンジン用潤滑油組成物及び潤滑方法
JP6247820B2 (ja) アルミ合金製エンジン用潤滑油組成物及び潤滑方法
JP2013224404A (ja) アルミ合金製エンジン用潤滑油組成物及び潤滑方法

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: 20090609

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): 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 SE SI SK TR

17Q First examination report despatched

Effective date: 20100730

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAC Information related to communication of intention to grant a patent modified

Free format text: ORIGINAL CODE: EPIDOSCIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

Owner name: TOYOTA JIDOSHA KABUSHIKI KAISHA

Owner name: IDEMITSU KOSAN CO., LTD.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): 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 SE SI SK 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: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602009002160

Country of ref document: DE

Effective date: 20111027

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110817

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110817

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

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: 20110817

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: 20111219

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: 20110817

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: 20111117

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: 20110817

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: 20110817

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: 20111217

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 520762

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110817

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: 20110817

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: 20110817

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: 20110817

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: 20110817

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: 20111118

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: 20110817

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

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

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: 20110817

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: 20110817

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: 20110817

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: 20110817

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: 20110817

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

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

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: 20110817

26N No opposition filed

Effective date: 20120521

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602009002160

Country of ref document: DE

Effective date: 20120521

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

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: 20120404

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 NON-PAYMENT OF DUE FEES

Effective date: 20120630

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: 20110817

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111128

Ref country code: IE

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

Effective date: 20120609

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: 20111117

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

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: 20110817

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

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: 20110817

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: CH

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

Effective date: 20130630

Ref country code: LI

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

Effective date: 20130630

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: 20120609

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

Ref country code: HU

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: 20090609

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: DE

Ref legal event code: R084

Ref document number: 602009002160

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 20160916

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

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

Ref country code: GB

Payment date: 20220617

Year of fee payment: 14

Ref country code: DE

Payment date: 20220518

Year of fee payment: 14

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

Ref country code: TR

Payment date: 20220609

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20220621

Year of fee payment: 14

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230522

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602009002160

Country of ref document: DE

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

Effective date: 20230609

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

Ref country code: DE

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

Effective date: 20240103

Ref country code: GB

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

Effective date: 20230609

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

Ref country code: FR

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

Effective date: 20230630