EP1439217B1 - Schmierölzusammensetzung für verbrennungsmotor - Google Patents

Schmierölzusammensetzung für verbrennungsmotor Download PDF

Info

Publication number
EP1439217B1
EP1439217B1 EP02770233A EP02770233A EP1439217B1 EP 1439217 B1 EP1439217 B1 EP 1439217B1 EP 02770233 A EP02770233 A EP 02770233A EP 02770233 A EP02770233 A EP 02770233A EP 1439217 B1 EP1439217 B1 EP 1439217B1
Authority
EP
European Patent Office
Prior art keywords
mass
metal
alkaline earth
percent
earth metal
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.)
Expired - Fee Related
Application number
EP02770233A
Other languages
English (en)
French (fr)
Other versions
EP1439217A1 (de
EP1439217A4 (de
Inventor
Kazuhiro NIPPON OIL CORPORATION YAGISHITA
Jinichi NIPPON OIL CORPORATION IGARASHI
Takeo NIPPON OIL CORPORATION KOIZUMI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002086146A external-priority patent/JP3662228B2/ja
Priority claimed from JP2002086145A external-priority patent/JP3709379B2/ja
Priority claimed from JP2002086147A external-priority patent/JP3738228B2/ja
Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Publication of EP1439217A1 publication Critical patent/EP1439217A1/de
Publication of EP1439217A4 publication Critical patent/EP1439217A4/de
Application granted granted Critical
Publication of EP1439217B1 publication Critical patent/EP1439217B1/de
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2215/086—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
    • C10M2215/28—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
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
    • C10M2219/04—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
    • 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
    • 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
    • C10M2223/041—Triaryl phosphates
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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
    • C10N2010/02—Groups 1 or 11
    • 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
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—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

Definitions

  • the present invention relates to lubricating oil compositions for internal combustion, engines and particularly to those having excellent anti-wear properties, base number retaining properties, high-temperature detergency, and low friction characteristics.
  • Zinc dialkyldithiophosphates have excellent anti-wear properties and anti-oxidation properties as a peroxide decomposer and thus have been used as an essential additive in lubricating oils for internal combustion engines or in every sort of lubricating oils.
  • lubricating oil compositions blended with zinc dialkyldithiocarbamates and sulfur-based additives so as to retain the anti-wear properties are known as ZDTP-free lubricating oils as disclosed in Japanese Patent Laid-Open Publication Nos. 52-704 , 62-253691 , 63-304095 , and 6-41568 and Published Japanese Translation Nos. 62-501572 , 62-501917 , and 1-500912 .
  • the lubricating oils disclosed in these publications contain a large quantity of sulfur similarly to those containing ZDTP. Such lubricating oils are poor in oxidation stability and tend to be acceleratingly decreased in base number.
  • US 5,726,133 discloses a low ash natural gas engine oil which contains an additive package including a particular combination of detergents and also containing other standard additives such as dispersants, antioxidants, antiwear agents, metal deactivators, antifoamants and pour point depressants and viscosity index improvers.
  • additives such as dispersants, antioxidants, antiwear agents, metal deactivators, antifoamants and pour point depressants and viscosity index improvers.
  • metal dithiophosphates e.g. zinc diakyl dithiophosphate
  • EP 1 104 800 discloses a lubricating oil composition for internal combustion engines, particularly gas engines utilizing gaseous fuels, such as natural gas or liquid propane gas.
  • the lubricating oil composition comprises (a) a base oil, (b) a metal-containing detergent, (c) a carbon-containing alkenyl- or alkylsuccinimide, (d) a zinc dialkyldithiophosphate as antiwear agent, (e) an oxidation inhibitor and (f) an ashless dithiocarbamate.
  • the object of the present invention is to provide a lubricating oil composition for internal combustion engines, which composition retains or is improved in anti-wear properties and anti-oxidation properties as obtained by conventional ZDTP; is enhanced in long-drain properties by decreasing the sulfur content of the oil so as to suppress the exhaust of the base number caused by deterioration of the oil; and is also excellent in high-temperature detergency and low friction characteristics.
  • a lubricating oil which is excellent in anti-wear properties, high-temperature detergency, and low friction characteristics and improved in base number retaining properties leading to long drain properties can be obtained by blending a lubricating base oil with a specific phosphorus compound, a specific ashless dispersant, a specific metal detergent, and a specific anti-oxidant, in a specific amount, respectively.
  • A a triphosphate represented by formula (1) below in an amount of 0.01 to 0.2 percent by mass in terms
  • the alkali metal or alkaline earth metal detergent preferably contains an alkali metal or alkaline earth metal salicylate detergent.
  • the alkali metal or alkaline earth metal detergent is preferably an alkali metal or alkaline earth metal salicylate detergent whose metal ratio represented by "valence of metal element x metal element content (mol) / soap group content (mol)" is 3 or less.
  • the alkali metal or alkaline earth metal detergent is preferably a mixture of an alkali metal or alkaline earth metal salicylate detergent whose metal ratio represented by "valence of metal element x metal element content (mol) / soap group content (mol)" is 1.5 or less and an alkali metal or alkaline earth metal salicylate detergent whose metal ratio is more than 1.5.
  • the alkali metal or alkaline earth metal detergent is preferably a mixture of an alkali metal or alkaline earth metal salicylate detergent whose metal ratio represented by "valence of metal element x metal element content (mol) / soap group content (mol)" is 1.5 or less and an alkali metal or alkaline earth metal sulfonate detergent.
  • the lubricating oil composition of the present invention preferably contains a sulfur-containing anti-wear agent in an amount of 0.1 percent by mass or less in terms of sulfur.
  • the lubricating oil composition of the present invention preferably contains a lubricating base oil whose aromatic content is 3 percent by mass or less and sulfur content is 50 ppm by mass or less.
  • the lubricating oil composition of the present invention is preferably used in an internal combustion engine using a fuel whose sulfur content is 50 ppm by mass or less.
  • the lubricating oil composition of the present invention is preferably used in gas engines.
  • the lubricating base oil of the lubricating oil composition of the present invention may be any of conventional mineral oils, synthetic oils, or mixtures of two or more of these oils mixed at an arbitrary ratio.
  • the mixture may be those of one or more types of mineral lubricating oils, those of one or more types of synthetic lubricating oils, or those of one or more types of mineral lubricating oils and one or more types of synthetic lubricating oils.
  • mineral lubricating oils are paraffinic or naphthenic oils which can be obtained by subjecting a lubricating oil fraction produced by atmospheric- or vacuum-distilling a crude oil, to any one or more refining processes selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, washing with sulfuric acid, and clay treatment; and n-paraffines.
  • refining processes selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, washing with sulfuric acid, and clay treatment; and n-paraffines.
  • Particularly, preferred are those obtained by a high-degree hydrocracking process or those obtained by isomerizing GTL Wax (Gas To Liquid Wax), both of which methods are capable of further decreasing the aromatic content and sulfur content.
  • synthetic lubricating oils include poly- ⁇ -olefins such as 1-octene oligomer, 1-decene oligomer, and ethylene-propylene oligomer, and hydrides thereof; isobutene oligomer and hydrides thereof; isoparaffines; alkylbenzenes; alkylnaphthalenes: diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl cebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethyl hexanoate, and pentaerythritol pelargonate; polyoxyalky
  • the sulfur content of the lubricating base oil is preferably 500 ppm by mass or less, more preferably 50 ppm by mass or less, even more preferably 20 ppm by mass or less, and particularly preferably 10 ppm by mass or less.
  • a lubricating base oil containing too much sulfur would adversely affect the base number retaining properties of the resulting composition and the above-described exhaust gas purifying systems.
  • total aromatic content of the lubricating base oil is preferably 15 percent by mass or less, more preferably 10 percent by mass or less, and even more preferably 3 percent by mass or less, and particularly preferably 2 percent by mass of less.
  • total aromatic content used herein denotes an aromatic fraction content determined in accordance with ASTM D2549.
  • the aromatic fraction includes alkylbenzenes; alkylnaphthalens; anthracene, phenanthrene, and alkylated products thereof; compounds wherein four or more benzene rings are condensated to each other; and compounds having heteroaromatics such as pyridines, quinolines, phenols, and naphthols.
  • the kinematic viscosity at 100 °C of the lubricating base oil is preferably 1 to 20 mm 2 /s and particularly preferably 2 to 10 mm 2 /s in order to improve low-temperature viscosity characteristics and oil film formation capability at lubricated sites and reduce the evaporation loss of the lubricating base oil.
  • the viscosity index of the lubricating base oil is preferably 80 or higher, more preferably 100 or higher, and further more preferably 120 or higher.
  • R 1 is a hydrocarbon group having 1 to 30 carbon atoms. Three groups of R 1 may be the same or different from each other.
  • hydrocarbon group having 1 to 30 carbon atoms examples include alkyl, cycloalkyl, alkenyl, aryl, and arylalkyl groups.
  • alkyl group examples include straight-chain or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
  • the cycloalkyl group may have a substituent.
  • the cycloalkyl group include those having 5 to 7 carbon atoms, such as cyclopentyl, cyclohexyl, and cycloheptyl groups; and alkylcycloalkyl groups having 6 to 11 carbon groups, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl, and diethylcycloheptyl groups, of which the alkyl groups may bond to any position of the cycloalkyl groups.
  • alkenyl group examples include those having 2 to 30 carbon atoms, such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, noneyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl groups, all of which may be straight-chain or branched and the position of which the double bonds may vary.
  • the aryl group may be substituted by an alkyl group.
  • the aryl group include those having 6 to 18 carbon atoms, such as phenyl and naphtyl groups; and alkylaryl groups having 7 to 26 carbon atoms, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, diethylphenyl, dibutylphenyl, and dioctylphenyl groups, wherein the alkyl groups may be straight-chain or branched and the position thereof to the aryl group may vary.
  • arylalkyl groups include those having 7 to 12 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl groups, of which the alkyl groups may be straight-chain or branched.
  • the hydrocarbon group of R 1 is preferably a straight-chain or branched alkyl group having 3 to 18 carbon atoms, an aryl having 6 to 18 carbon atoms, or a straight-chain or branched alkylaryl group having 7 to 26 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms with the objective of excellent base number retaining properties, and is also preferably a straight-chain or branched alkyl group having 6 to 18 carbon atoms, an aryl having 6 to, 10 carbon atoms, or a straight-chain or branched alkylaryl group having 7 to 10 carbon atoms with the objective of high-temperature detergency.
  • R 1 is desirously a straight-chain or branched alkyl group having 6 to 18, preferably 6 to 12 carbon groups because the resulting composition would be low in volatility and excellent in high temperature detergency and friction-reducing effect. All the groups of R 1 are preferably the same.
  • a triphosphate represented by formula (1) can decrease the metal content of the resulting composition compared with the use of a metal anti-wear agent such as ZDTP and can obtain a lubricating oil composition with more enhanced anti-wear properties, base number retaining properties, and high-temperature detergency, compared with the use of ZDTP, monophosphates, diesters, or phosphites.
  • the lower limit content of Component (A) is 0.01 percent by mass, preferably 0.02 percent by mass, and particularly preferably 0.05 percent by mass in terms of phosphorus, based on the total mass of the composition, while the upper limit content of Component (A) is 0.2 percent by mass, preferably 0.15 percent by mass, and particularly preferably 0.1 percent by mass in terms of phosphorus, based on the total mass of the composition.
  • Component (A) of less than 0.01 percent by mass would fail to obtain advantageous effects of the present invention sufficiently, while Component (A) of more than 0.2 percent by mass would adversely affect exhaust gas purifying catalysts or the like.
  • Component (B) of the lubricating oil composition of the present invention is a succinimide and/or derivative thereof.
  • succinimide examples include monosuccinimides represented by formula (2) below and bissuccinimides represented by formula (3) below:
  • R 10 , R 11 , and R 12 are each independently a polybutenyl group and n is an integer of from 2 to 7.
  • n is an integer of from 2 to 7.
  • preferred are bis-type succinimides represented by formula (3) because they can further enhance the advantageous effects achieved by the present invention.
  • the polybutenyl group of R 10 , R 11 , and R 12 has a number-average molecular weight of preferably 700 or greater, more preferably 900 or greater and preferably 3,500 or less, more preferably 2,500 or less, and particularly preferably 1,500 or less.
  • a polybutenyl group having a number-average molecular weight of 700 or greater makes it possible to produce a lubricating oil composition with excellent detergent and dispersion properties.
  • a polybutenyl group having a number-average molecular weight of 3,500 or less makes it possible to produce a lubricating oil composition with more excellent low-temperature flowability.
  • the lower limit of n is 2 and preferably 3, while the upper limit of n is 7 and preferably 6.
  • the polybutenyl group can be obtained from polybutene (polyisobutene) produced by polymerizing a mixture of 1-buten and isobutene or a highly purified isobutene using a catalyst such as aluminum chloride or boron fluoride.
  • the polybutene mixture contains polybutenes having a vinylidene structure at the terminal ends in an amount of generally 5 to 100 percent by mol.
  • the polybutene may be those of which a slight amount of the remaining fluorine and chlorine resulting from the catalyst used in the process has been removed with a suitable treatment. Therefore, the content of halogen atoms such as fluorine and chlorine is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, further more preferably 5 ppm by mass or less, and particularly preferably 1 ppm or less.
  • the succinimide may be produced by reacting a polybutenyl succinimide produced by reacting polybutene obtained by chlorinating the above polybutene, preferably one from which chorine and fluorine has been removed with maleic anhydride at a temperature of 100 to 200 °C, with polyamine such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or pentaethylene hexamine.
  • the polybutenyl succinimide in an amount (molar ratio) of twice as much as polyamine may be reacted therewith, while in the case of producing the monosuccinimide, the polybutenyl succinimide in the same amount (molar ratio) may be reacted therewith.
  • the succinimide derivative may be a compound obtained by neutralizing or amidizing the whole or part of the remaining amino groups and/or imide groups by allowing a compound of formula (2) or (3) to react with an oxygen-containing organic compound or a boron compound.
  • oxygen-containing organic compound examples include monocarboxylic acids having 1 to 30 carbon atoms, such as formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid, and eicosanoic acid; polycarboxylic acid having 2 to 30 carbon atoms, such as oxalic acid, phthalic acid, trimellitic acid; and pyromellitic acid, anhydrides thereof, and ester compounds thereof; alkyleneoxides having 2 to 6 carbon atoms, and hydroxy(poly)oxyalkylene carbonates.
  • R 13 is hydrogen, an alkyl, alkenyl or alkoxy group having 1 to 24 carbon atoms, or a hydroxy(poly)oxyalkylene group represented by -O-(R 14 O) m H wherein R 14 is an alkylene group having 1 to 4 carbon atoms, and m is an integer of from 1 to 5.
  • Examples of the boron compound include boric acid, borates, and boric acid esters.
  • Specific examples of boric acid include orthoboric acid, methaboric acid, and tetraboric acid.
  • Examples of borates include alkali metal salts, alkaline earth metal salts, or ammonium salts, of boric acid.
  • lithium borate such as lithium methaborate, lithium tetraborate, lithium pentaborate, and lithium perborate
  • sodium borate such as sodium methaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, and sodium octaborate
  • potassium borate such as potassium methaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate
  • calcium borate such as calcium methaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate, and calcium hexaborate
  • magnesium borate such as magnesium methaborate, magnesium diborate, trimagnesium tetraborate, pentamagnesium tetraborate, and magnesium hexaborate
  • ammonium borate such as ammonium methaborate, ammonium tetraborate, ammonium pentaborate, and ammonium
  • boric acid esters examples include esters of boric acid and an aliphatic alcohol having 1 to 6 carbon atoms and more specifically monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, dimethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, and tributyl borate.
  • the mass ratio of boron and nitrogen (B/N ratio) in the succinimide reacted with a boron compound is preferably from 0.1 to 1.2, more preferably from 0.2 to 1.0, and particularly preferably from 0.3 to 0.9 with the objective of enhancing the base number retaining properties and high-temperature detergency.
  • one or more selected from the above-described succinimides and derivatives thereof may be used as Component (B).
  • the lower limit content of Component (B) is 0.01 percent by mass, preferably 0.05 percent by mass, and particularly preferably 0.08 percent by mass in terms of nitrogen, based on the total mass of the composition.
  • the upper limit content of Component (B) is 0.3 percent by mass, preferably 0.2 percent by mass, and particularly preferably 0.15 percent by mass in terms of nitrogen, based on the total mass of the composition.
  • Component (B) of less than 0.01 percent by mass would fail to achieve the advantageous effect of the present invention, while Component (B) of more than 0.3 percent by mass would deteriorate the low-temperature viscosity characteristics and anti-emulsion properties of the resulting lubricating oil composition.
  • Component (C) of the lubricating oil composition of the present invention is an alkali metal or alkaline earth metal detergent.
  • Component (C) include alkali metal or alkaline earth metal sulfonates, alkali metal or alkaline earth metal phenates, and alkali metal or alkaline earth metal salicylates.
  • alkali metal or alkaline earth metal detergents selected from the above compounds may be used, and particularly alkaline earth metal detergents are preferably used in the present invention.
  • alkaline earth metal sulfonates are alkaline earth metal salts, such as magnesium and/or calcium salts, preferably calcium salts, of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 300 to 1,500 and preferably 400 to 700.
  • alkyl aromatic sulfonic acids include petroleum sulfonic acids and synthetic sulfonic acids.
  • Petroleum sulfonic acids may be those obtained by sulfonating alkyl aromatic compounds contained in the lubricant fraction of a mineral oil or mahogany acid by-produced upon production of white oil.
  • the synthetic sulfonic acid may be those obtained by sulfonating an alkyl benzene having a straight-chain or branched alkyl group, by-produced from a plant for producing an alkyl benzene used as materials of detergents or obtained by alkylating an oligomer of an olefin having 2 to 22 carbon atoms such as ethylene and propylene to benzene or those obtained by sulfonating an alkylnaphthalene such as dinonylnaphthalene.
  • sulfonating agents used for sulfonating these alkyl aromatic compounds may be generally fuming sulfuric acids and sulfuric acid anhydride.
  • alkaline earth metal phenates examples include alkaline earth metal salts, particularly magnesium salts and calcium salts of alkylphenols, alkylphenolsulfides or Mannich reaction products of alkylphenols. Specific examples are those represented by formulas (5) through (7):
  • R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 may be the same or different from each other and are each independently a straight-chain or branched alkyl group having 4 to 30, preferably 6 to 18 carbon atoms, M 1 , M 2 , and M 3 are each independently an alkaline earth metal, preferably calcium and magnesium, and x is an integer of 1 or 2.
  • alkyl group of R 2 , R 22 , R 23 , R 24 , R 25 , and R 26 include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups.
  • These alkyl groups may be straight-chain or branched and may be of primary, secondary, or tertiary.
  • alkaline earth metal salicylates examples include alkaline earth metal salts, preferably magnesium and calcium salts, of an alkyl salicylic acid. Specific examples include compounds represented by formula (8)
  • R 27 is a straight-chain or branched alkyl group having 4 to 30, preferably 6 to 18 carbon atoms and M 4 is an alkaline earth metal, preferably calcium or magnesium.
  • alkyl group of R 27 examples include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups.
  • These alkyl groups may be straight-chain or branched and may be of primary, binary or tertiary.
  • the alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates may be (1) neutral (normal salt) alkaline earth metal sulfonates, neutral (normal salt) alkaline earth metal phenates, and neutral (normal salt) alkaline earth metal salicylates obtained by reacting alkyl aromatic sulfonic acids, alkylphenols, alkylphenolsuflides, Mannich reaction products of alkylphenol or alkyl salicylic acid as mentioned above directly with an alkaline earth metal base of the oxide or hydroxide of an alkaline earth metal such as magnesium and/or calcium or obtained by converting alkyl aromatic sulfonic acids, alkylphenols, alkylphenolsuflides, Mannich reaction products of alkylphenol or alkyl salicylic acid to an alkali metal salt such as sodium salt and potassium salt, followed by substitution with an alkaline earth metal salt; (2) basic alkaline earth metal sulfonates, basic al
  • the base number of these compounds is generally 500 mgKOH/g or less, preferably from 60 mgKOH/g to 400 mgKOH/g.
  • base number used herein denotes a base number measured by the perchloric acid potentiometric titration method in accordance with section 7 of JIS K2501 (1992) "Petroleum products and lubricants-Determination of neutralization number".
  • alkaline earth metal detergents are usually commercially available in the form of diluted with a light lubricating base oil, it is preferable to use metal detergents of which metal content is within the range of z1 to 20 percent by mass and preferably 2.0 to 16 percent by mass.
  • Component (C) No particular limitation is imposed on the metal ratio of Component (C). However, it is preferable to use Component (C) whose metal ratio is generally 1 to 20, preferably 1 to 15.
  • Component (C) preferably contains the alkali metal or alkaline earth metal salicylate detergent as an essential component.
  • the metal ratio of the detergent is preferably 3 or less, more preferably 2.6 or less, further more preferably 2 or less, and particularly preferably 1.5 or less.
  • the alkali metal or alkaline earth metal salicylate detergent may be used singlely or in the form of a mixture of those of different metal ratios.
  • an alkali metal or alkaline earth metal salicylate with a metal ratio of 2 or less, preferably 1.5 or less, and particularly preferably 1.2 or less may be used alone as an essential component.
  • an alkali metal or alkaline earth metal salicylate with a metal ratio of 1.5 or less, preferably 1.2 or less may be used in combination with one with a metal ratio in excess of 1.5, particularly 2.6, and the metal ratio of the mixture is adjusted to 1.3 or more and preferably 2.3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
  • Component (C) can enhance base number retaining properties, high-temperature detergency, and low friction characteristics by adjusting the metal ratio to be within the range of 1.3 to 2.3, even though the content of Component (C) is maintained the same.
  • Component (C) is preferably a combination of an alkali metal or alkaline earth metal salicylate with a metal ratio of 1.5 or less, preferably 1.2 or less and an alkali metal or alkaline earth metal sulfonate.
  • the metal ratio is generally from 1 to 20, preferably from 1 to 15, and particularly preferably from 5 to 12.
  • Component (C) thus prepared can further enhance advantageous effect to improve base number retaining properties, high-temperature detergency, and low friction characteristics.
  • metal ratio used herein is represented by "valence of metal element x metal element content (mol) / soap group (group such as alkylsalicylic acid group) content (mol)” and denotes the alkali metal or alkaline earth metal content against the content of the alkylsalicylic acid and alkylsulfonic acid groups in an alkali metal or alkaline earth metal detergent.
  • the lower limit content of Component (C) is 0.05 percent by mass, preferably 0.1 percent by mass, more preferably 0.15 percent by mass, and particularly preferably 0.2 percent by mass in terms of alkali metal or alkaline earth metal, based on the total mass of the lubricating oil composition of the present invention.
  • the upper limit content of Component (C) is 1 percent by mass, preferably 0.5 percent by mass, and more preferably 0.4 percent by mass in terms of alkali metal or alkaline earth metal, based on the total mass of the lubricating oil composition of the present invention.
  • Component (C) of less than 0.05 percent by mass would fail to exhibit excellent base number retaining properties and high-temperature detergency, while Component (C) of more than 1 percent by mass would fail to attain effects as expected.
  • Component (D) of the lubricating oil composition of the present invention is a phenol- and/or amine-based anti-oxidant.
  • phenol-based anti-oxidant examples include
  • amine-based anti-oxidant examples include phenyl- ⁇ -naphtylamine, alkylphenyl- ⁇ -naphtylamine, and dialkyldiphenylamine. Two or more of these amine-based anti-oxidants may be used in combination.
  • the above alkyl groups are those having 1 to 16 carbon atoms.
  • phenol-based and amine-based anti-oxidants may be used singlely but preferably used in combination because the advantageous effects can be further enhanced.
  • the lower limit content of Component (D) is 0.01 percent by mass, preferably 0.1 percent by mass, more preferably 0.5 percent by mass, and particularly preferably 1.0 percent by mass, based on the total mass of the lubricating oil composition of the present invention with the objective of further enhancing the base number retaining properties and high-temperature detergency.
  • the upper limit content of Component (D) is 3.0 percent by mass and preferably 2.5 percent by mass, based on the total mass of the lubricating oil composition of the present invention. Component (D) of more than 3.0 percent by mass would fail to attain sufficient anti-oxidant properties as balanced with the content.
  • the lubricating oil composition of the present invention may contain an anti-wear agent other than Component (A).
  • Examples of an anti-wear agent other than Component (A) include phosphorus-and/or sulfur-containing anti-wear agents such as thiophosphates and metal salts of phosphates, represented by formula (9) and thiophosphates, phosphates, and metal salts and amine salts thereof, represented by formula (10) and further include those such as phosphates, thiophosphites, and metal salts and amine salts thereof, thiotriphosphtes, zinc dialkyldithiophosphates, zinc dialkyldithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dialkyldithiocarbamates, disulfides, olefinsulfides, and sulfurized fats and oils:
  • phosphorus-and/or sulfur-containing anti-wear agents such as thiophosphates and metal salts of phosphates, represented by formula (9) and thiophosphates, phosphates, and metal salts and
  • R 30 , R 31 , R 32 , R 33 , R 34 , and R 35 are each independently hydrogen or a hydrocarbon group having 1 to 30 carbon atoms.
  • Examples and preferred examples of the hydrocarbon group having 1 to 30 carbon atoms include the same as those exemplified with respect to R 2 in formula (1) representing Compound (A) described above.
  • X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 are each independently oxygen or sulfur, at least one of them is oxygen, and preferably two or more of them are oxygen, and particularly preferably all 1 of them are oxygen. Due to the presence of at least one oxygen, the resulting composition can be decreased in sulfur content and in the amount of sulfuric acid produced when being oxidized or thermally decomposed and thus can be significantly suppressed in the exhaust of the base number.
  • Y is a metal atom and specifically zinc, copper, iron, lead, nickel, silver, and manganese. With the objective of enhanced anti-wear properties, Y is preferably zinc.
  • U is hydrogen (proton), a monovalent metal ion, or an ammonium ion.
  • k indicates the number of ion of U and is an integer of from 1 to 20, preferably from 1 to 10, and more preferably from 1 to 8.
  • the monovalent metal ion of U is a metal atom which can form a salt and thus may be an alkali metal, such as lithium, sodium, potassium and cesium.
  • the ammonium ion may be those providing ammonium ion such as nitrogen-containing compounds which can form an amine salt.
  • nitrogen-containing compounds include ammonia, monoamines, diamines, and polyamines. More specific examples include alkylamines having a straight-chain or branched alkyl group having 1 to 30 carbon atoms, such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecyl
  • an anti-wear agent containing sulfur selected from the above anti-wear agents other than Component (A) no particular limitation is imposed on the content of the anti-wear agents.
  • the content is preferably 0.1 percent by mass or less and more preferably 0.09 percent by mass or less in terms of sulfur, based on the total mass of the lubricating oil composition of the present invention.
  • a lubricating oil composition with significantly excellent base number retaining properties and high-temperature detergency can be obtained by decreasing the amount of the sulfur-containing anti-wear agent to 0.1 percent by mass or less.
  • the content is from 0.01 to 0.2 percent by mass in terms of phosphorus, based on the total mass of the lubricating oil composition of the present invention. Even in such a case, the total content of the anti-wear agent and Component (A) does not exceed preferably 0.2 percent by mass and particularly preferably 0.15 percent by mass in terms of phosphorus, based on the total mass of the composition because there is a risk that exhaust gas purifying catalysts are adversely affected.
  • the lubricating oil composition for internal combustion engines of the present invention is excellent in anti-wear properties, base number retaining properties, and high-temperature detergency
  • various additives may be optionally added in order to further improve these properties.
  • additives include viscosity index improvers, ashless dispersants other than Component (B), metal detergents other than Component (C), anti-oxidants other than Component (D), friction modifiers, corrosion inhibitors, rust preventives, anti-emulsifiers, metal deactivators, anti-foamers, and dyes.
  • viscosity index improvers examples include non-dispersion type viscosity index improvers such as copolymers of one or more monomers selected from various methacrylates or hydrides thereof; dispersion type viscosity index improvers such as copolymers of various methacrylates further containing nitrogen compounds; non-dispersion- or dispersion-type ethylene- ⁇ -olefin copolymers of which the ⁇ -olefin may be propylene, 1-butene, or 1-pentene, or the hydrides thereof; polyisobutylenes or the hydrides thereof; styrene-diene hydrogenated copolymers; styrene-maleic anhydride ester copolymers; and polyalkylstyrenes.
  • non-dispersion type viscosity index improvers such as copolymers of one or more monomers selected from various methacrylates or hydrides thereof
  • dispersion type viscosity index improvers such as
  • the number-average molecular weight of non-dispersion or dispersion type polymethacrylates is from 5,000 to 1,000,000 and preferably from 10,000 to 350,000.
  • the number-average molecular weight of polyisobutylenes or hydrides thereof is from 800 to 5, 000 and preferably from 1,000 to 4,000.
  • the number-average molecular weight of ethylene- ⁇ -olefin copolymers and hydrides thereof is from 800 to 500,000 and preferably from 3,000 to 200,000.
  • viscosity index improvers the use of ethylene- ⁇ -olefin copolymers or hydrides thereof is contributive to production of a lubricating oil composition which is excellent particularly in shear stability.
  • One or more compounds selected from the above-described viscosity index improvers may be blended in an arbitrary amount.
  • the content of the viscosity index improvers is generally within the range of 0.1 to 20.0 percent by mass, based on the total mass of the lubricating oil composition.
  • Examples of ashless dispersants other than Component (B) include benzylamines having in the molecules at least one alkyl or alkenyl group having 40 to 400 carbon atoms and derivatives thereof; and polyamines having in the molecules at least one alkyl or alkenyl group having 40 to 400 carbon atoms and derivatives thereof.
  • friction modifiers include aliphatic amines, fatty acids, fatty acid esters, and aliphatic alcohols, having an alkyl or alkenyl group having 6 to 30 carbon atoms.
  • corrosion inhibitors examples include benzotriazole-, tolyltriazole-, thiazole-, thiadiazole-, and imidazole-based compounds.
  • rust-preventives include petroleum sulfonates, alkylbenzene sulfonates, dinonylnaphthalenesulfonates, alkenyl succinic acid esters, and polyhydric alcohol esters.
  • anti-emulsifiers include polyalkylene glycol-based non-ionic surfactants such as polyoxyethylenealkyl ether, polyoxyethylenealkylphenyl ether, and polyoxyethylenealkylnaphthyl ether.
  • metal deactivators include imidazolines, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles and derivatives thereof, 1,3,4-thiadiazolepolysulfide, 1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamte, 2-(alkyldithio)benzoimidazole, and ⁇ -(o-carboxybenzylthio)propionitrile.
  • anti-foamers examples include silicone, fluorosilicone, and fluoroalkyl ether.
  • the content of each of the ashless dispersant other than Component (B), metal detergent other than Component (C), anti-oxidant other than Component (D), friction modifier, corrosion inhibitor, rust inhibitor, and anti-emulsifier is 0.01 to 5 percent by mass based on the total mass of the composition.
  • the content of the metal deactivator is 0.005 to 1 percent by mass, while the content of the anti-foamer is 0.0005 to 1 percent by mass.
  • the lubricating oil composition of the present invention is preferably limited in the content of additive containing sulfur as well as the content of the above-described sulfur-containing anti-wear agent.
  • the content of the sulfur-containing additive including the sulfur-containing anti-wear agent is preferably 0.1 percent by mass or less and more preferably 0.09 percent by mass or less based on the total mass of the composition.
  • the lubricating oil composition contains no sulfur-containing additives including the sulfur-containing anti-wear agent.
  • sulfur-containing additives used herein does not refer to sulfur compounds derived from such a solvent or diluting oil.
  • the composition of the present invention contains sulfur originating from the solvent or diluting oil
  • the total sulfur content of the composition is 0.2 percent by mass or less, preferably 0.15 percent by mass or less, and particularly preferably 0.1 percent by mass or less.
  • a composition containing sulfur in an amount of 10 ppm by mass or less or containing substantially no sulfur can be obtained using a high-degree hydrocracked base oil whose content of sulfur originating from a solvent or diluting oil is 10 ppm by mass or less or a base oil produced by isomerizig GTL Wax (Gas To Liquid Wax) or a synthetic oil, containing substantially no sulfur.
  • the lubricating oil composition for internal combustion engines, of the present invention is decreased in the amount of a sulfur-containing agent such as ZDTP having both anti.-wear and anti-oxidation properties or contains no such an agent at all, the composition is extremely improved in anti-oxidation properties and in base number retaining properties, i.e., long-drain properties, and also excellent in high-temperature detergency and low friction characteristics, but free from the decrease of anti-wear properties.
  • a sulfur-containing agent such as ZDTP having both anti.-wear and anti-oxidation properties or contains no such an agent at all
  • the total sulfur content of the lubricating oil composition of the present invention can be held down and prevented from raising more than 0.2 percent by mass, the composition can suppress exhaust gas purifying catalysts from poisoning by sulfur and be used suitably for engines equipped with an exhaust-gas after-treatment device such as an exhaust gas purifying catalyst.
  • the lubricating oil composition of the present invention can also be used suitably as lubricating oils required to have anti-wear properties, base number retaining properties, and high-temperature detergency, such as lubricating oils for driving means such as automatic or manual transmissions; those for wet brakes; hydraulic oils; turbine oils; gear oils; and bearing oils.
  • Lubricating oil compositions for internal combustion engines each having the formulation and properties shown in Table 1 were prepared.
  • the compositions containing C.05 percent by mass of sulfur are those containing sulfur originating from the diluting oils contained in the additives.
  • compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated by the following performance characteristics evaluating tests.
  • the compositions of the present invention were significantly higher in base number retaining properties than the compositions (Comparative Examples 1 and 2) containing ZDTP (sulfur-containing anti-wear agent) in such a general amount that they are used as lubricating oils for internal combustion engines, i.e., 0.16 percent by mass in terms of sulfur and 0.08 percent by mass in terms of phosphorus.
  • the triphenylphosphate-containing compositions (Example 4) and particularly the tributylphosphate-containing composition (Example 3) were significantly higher in base number retaining properties that the trioctylphosphate-containing composition (Example 1).
  • compositions of the present invention (Examples 1 to 4) were found to exhibit excellent base number retaining properties and long drain properties under such an atmosphere that lubricating oils for internal combustion engines are exposed to NOx, similarly to the results in the above-described ISOT.
  • the seizuring load of each of sample pieces was measured by FALEX test in accordance with ASTM D3233 (A method, 290 rpm, room temperature). The results are shown in Table 1. The larger the securing load, the composition exhibits more excellent anti-wear properties.
  • the anti-wear properties of the compositions of the present invention were equal to or higher than those of Comparative Examples 1 and 2.
  • a hot tube test was conducted in accordance with JPI-5S-5599. The evaluation was made by grading the compositions as 1C points when they were colorless and transparent (no fouling) and those as 0 point when they were black and opaque. Between 10 and 0 point, evaluation was done using reference tubes which were made per grade beforehand. At 290 °C, 6 points or higher indicate that the oil composition has an excellent detergency for an ordinary gasoline or diesel engine. However, a lubricating oil composition for a gas engine preferably exhibits excellent detergency also at 300 °C or higher in this test.
  • compositions of the present invention exhibited extremely excellent high-temperature detergency even at a temperature of 300 °C or higher.
  • composition containing trioctylphosphate which is conceivably lower in evaporation than tributylphosphate exhibited extremely excellent high-temperature detergency.
  • Lubricating oil compositions (Examples 5 to 9 and Comparative Example 3) with the formulations and properties shown in Table 2 were prepared and evaluated by the following test. The results are shown in Table 2.
  • the composition of Example 9 is the same as the one of Example 1 in Table 1,
  • composition of Example 9 is also excellent in low friction characteristics, compared with the compositions of Comparative Example 3.
  • the compositions containing a low metal ratio alkaline earth metal salicylate essentially as Component (C) were found to exhibit extremely superior low friction characteristics. These compositions exhibited base number retaining properties, anti-wear properties, and high temperature detergency equally to or better than the composition of Example 9.
  • Component (C) of the composition of Example 6 was a mixture of calcium salicylate whose metal ratio is 1.0 and calcium salicylate whose metal ratio is 2.7, and the total metal ratio of Component (C) is 1.46.
  • Example 6 contained less amount of Component (C) of Example 5 but was recognized to be decreased in friction coefficient particularly in the high velocity region synergistically, compared with the average between Examples 5 and 9.
  • the composition containing tributylphosphate or triphenylphosphate was superior in low friction characteristics to Comparative Example 3 but the composition containing trioctylphosphate exhibited the most excellent low friction characteristics.

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 (9)

  1. Schmierölzusammensetzung für einen Verbrennungsmotor, die folgendes umfasst: ein Basisschmieröl;
    (A) ein Triphosphat nach Formel (1), dessen Menge einem Phosphormassenanteil von 0,01 bis 0,2 Prozent entspricht;
    (B) ein Succinimid und/oder ein Succinimid-Derivat, dessen Menge einem Stickstoffmassenanteil von 0,01 bis 0,3 Prozent entspricht;
    (C) ein Alkalimetall- oder ein Erdalkalimetall-Detergens, das ein Alkalimetall- oder Erdalkalimetall-Salicylat enthält und dessen Menge einem Metallmassenanteil von 0,05 bis 1 Prozent entspricht; und
    (D) ein Antioxidans auf Phenolbasis und/oder auf Aminbasis, dessen Menge einem Massenanteil von 0,01 bis 3 Prozent entspricht:

            O = P(OR1)3     (1)

    wobei die R1-Gruppen unabhängig voneinander aus einer Alkylgruppe mit 1 bis 30 Kohlenstoffatomen bestehen und jeweils identisch oder unterschiedlich sind, wobei der Gesamtmassenanteil an Schwefel in der Zusammensetzung ≦ 0,2 Prozent beträgt.
  2. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, wobei der Gesamtmassenanteil an Schwefel in der Zusammensetzung ≤ 0,1 Prozent beträgt.
  3. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, wobei das Alkalimetall- oder Erdalkalimetall-Salicylat-Detergens ein Metallverhältnis hat, das nach "Metallelementvalenz x Metallelementanteil (mol) / Seifengruppenanteil (mol)" einen Wert von ≤ 3 hat.
  4. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, wobei das Alkalimetall- oder Erdalkalimetall-Detergens eine Mischung aus Folgendem ist:
    einem Alkalimetall- oder einem Erdalkalimetall-Salicylat-Detergens, dessen Metallverhältnis nach "Metallelementvalenz x Metallelementanteil (mol) / Seifengruppenanteil (mol)" einen Wert von ≤ 1,5 hat, und
    einem Alkalimetall- oder Erdalkalimetall-Salicylat-Detergens, dessen Metallverhältnis einen Wert von > 1,5 hat.
  5. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, wobei das Alkalimetall- oder Erdalkalimetall-Detergens eine Mischung aus Folgendem ist:
    einem Alkalimetall- oder Erdalkalimetall-Salicylat-Detergens, dessen Metallverhältnis nach "Metallelementvalenz x Metallelementanteil (mol) / Seifengruppenanteil (mol)" einen Wert von ≤ 1,5 hat, und
    einem Alkalimetall- oder Erdalkalimetall-Sulfonat-Detergens.
  6. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, die ein schwefelhaltiges, verschleißhemmendes Mittel enthält, dessen Menge einem Schwefelmassenanteil von ≤ 0,1 Prozent entspricht.
  7. Schmierölzusammensetzung für einen Verbrennungsmotor nach Anspruch 1, die ein Basisschmieröl enthält, dessen aromatischer Massenanteil ≤ 3 Prozent und dessen Schwefelmassenanteil ≤ 50 ppm ist.
  8. Verwendung der Schmierölzusammensetzung nach Anspruch 1 in einem Verbrennungsmotor, der mit einem Treibstoff betrieben wird, dessen Schwefelmassenanteil ≤ 50 ppm ist.
  9. Verwendung der Schmierölzusammensetzung nach einem der Ansprüche 1 bis 7 in Gasmotoren.
EP02770233A 2001-10-12 2002-10-15 Schmierölzusammensetzung für verbrennungsmotor Expired - Fee Related EP1439217B1 (de)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2001315941 2001-10-12
JP2001315941 2001-10-12
JP2002086145 2002-03-26
JP2002086146A JP3662228B2 (ja) 2002-03-26 2002-03-26 潤滑油組成物
JP2002086145A JP3709379B2 (ja) 2002-03-26 2002-03-26 潤滑油組成物
JP2002086146 2002-03-26
JP2002086147A JP3738228B2 (ja) 2002-03-26 2002-03-26 潤滑油組成物
JP2002086147 2002-03-26
PCT/JP2002/010679 WO2003033629A1 (fr) 2001-10-12 2002-10-15 Composition d'huile de lubrification pour moteur thermique

Publications (3)

Publication Number Publication Date
EP1439217A1 EP1439217A1 (de) 2004-07-21
EP1439217A4 EP1439217A4 (de) 2009-09-02
EP1439217B1 true EP1439217B1 (de) 2012-06-20

Family

ID=27482619

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02770233A Expired - Fee Related EP1439217B1 (de) 2001-10-12 2002-10-15 Schmierölzusammensetzung für verbrennungsmotor

Country Status (3)

Country Link
US (1) US20040242434A1 (de)
EP (1) EP1439217B1 (de)
WO (1) WO2003033629A1 (de)

Families Citing this family (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004083746A (ja) * 2002-08-27 2004-03-18 Nippon Oil Corp 内燃機関用潤滑油組成物
US20040176256A1 (en) * 2002-11-07 2004-09-09 Nippon Oil Corporation Lubricating oil composition for transmissions
JP4824406B2 (ja) * 2003-08-06 2011-11-30 Ｊｘ日鉱日石エネルギー株式会社 Ｄｌｃ接触面を有するシステム、該システムの潤滑方法及び該システム用潤滑油
WO2005014760A1 (ja) * 2003-08-06 2005-02-17 Nippon Oil Corporation Dlc接触面を有するシステム、該システムの潤滑方法及び該システム用潤滑油
US20050070447A1 (en) * 2003-09-25 2005-03-31 The Lubrizol Corporation Ashless stationary gas engine lubricant
JP4486338B2 (ja) * 2003-10-16 2010-06-23 新日本石油株式会社 潤滑油組成物
JP4541681B2 (ja) * 2003-10-16 2010-09-08 Ｊｘ日鉱日石エネルギー株式会社 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
EP2343354A1 (de) * 2003-10-16 2011-07-13 Nippon Oil Corporation Schmieröladditiv und Schmierölzusammensetzung
JP4541680B2 (ja) * 2003-10-16 2010-09-08 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
JP4578115B2 (ja) * 2004-02-04 2010-11-10 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
WO2006018403A1 (en) * 2004-08-18 2006-02-23 Ciba Specialty Chemicals Holding Inc. Lubricating oil compositions with improved performance
JP4885442B2 (ja) * 2004-11-26 2012-02-29 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物及びそれを用いた駆動伝達装置
US8709988B2 (en) 2004-11-30 2014-04-29 Infineum International Limited Lubricating oil compositions
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
US7485603B2 (en) * 2005-02-18 2009-02-03 Infineum International Limited Soot dispersants and lubricating oil compositions containing same
JP4955998B2 (ja) * 2005-12-27 2012-06-20 シェブロンジャパン株式会社 潤滑油組成物
US20090048129A1 (en) * 2006-01-31 2009-02-19 Nissan Motor Co., Ltd. Nanoparticle-containing lubricating oil compositions
CN101336286B (zh) * 2006-01-31 2013-01-02 日产自动车株式会社 含有纳米颗粒的润滑油组合物
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
WO2008013752A2 (en) * 2006-07-28 2008-01-31 Exxonmobil Research And Engineering Company Improving lubricant air release rates
WO2008013754A2 (en) * 2006-07-28 2008-01-31 Exxonmobil Research And Engineering Company Lubricant compositions, their preparation and use
CA2658289A1 (en) * 2006-07-28 2008-01-31 Exxonmobil Research And Engineering Company Lubricant compositions having improved rates of air release
SG176430A1 (en) * 2006-07-28 2011-12-29 Exxonmobil Res & Eng Co Novel application of thickeners to achieve favorable air release in lubricants
US20080103072A1 (en) * 2006-11-01 2008-05-01 The Lubrizol Corporation Antiwear Containing Lubricating Composition
US20080119377A1 (en) * 2006-11-22 2008-05-22 Devlin Mark T Lubricant compositions
US20080128184A1 (en) * 2006-11-30 2008-06-05 Loper John T Lubricating oil compositions having improved corrosion and seal protection properties
US20080146473A1 (en) * 2006-12-19 2008-06-19 Chevron Oronite Company Llc Lubricating oil with enhanced piston cleanliness control
JP5180466B2 (ja) * 2006-12-19 2013-04-10 昭和シェル石油株式会社 潤滑油組成物
KR101435701B1 (ko) 2007-03-28 2014-09-01 이데미쓰 고산 가부시키가이샤 윤활유 조성물
US7910530B2 (en) * 2007-03-30 2011-03-22 Exxonmobil Research And Engineering Company Method for improving the air release rate of GTL base stock lubricants using synthetic ester, and composition
JP5806802B2 (ja) * 2007-03-30 2015-11-10 出光興産株式会社 潤滑油組成物
US7989408B2 (en) 2007-04-10 2011-08-02 Exxonmobil Research And Engineering Company Fuel economy lubricant compositions
US7770914B2 (en) * 2007-07-31 2010-08-10 Autoliv Asp, Inc. Passenger airbag mounting apparatus
EP2128232A1 (de) * 2008-05-20 2009-12-02 Castrol Limited Schmiermittelzusammensetzung für mit Ethanol betriebene Motoren
JP5432537B2 (ja) 2009-01-28 2014-03-05 昭和シェル石油株式会社 耐摩耗剤およびそれを含む耐摩耗性に優れた潤滑油組成物
CA2758301A1 (en) * 2009-04-10 2010-10-14 Ls9, Inc. Production of fatty acid derivatives
US8288326B2 (en) * 2009-09-02 2012-10-16 Chevron Oronite Company Llc Natural gas engine lubricating oil compositions
US8841243B2 (en) * 2010-03-31 2014-09-23 Chevron Oronite Company Llc Natural gas engine lubricating oil compositions
CA2827438A1 (en) 2011-02-17 2012-08-23 The Lubrizol Corporation Lubricants with good tbn retention
US9909083B2 (en) 2012-12-27 2018-03-06 Jx Nippon Oil & Energy Corporation System lubricating oil composition for crosshead diesel engine
US20140187455A1 (en) * 2012-12-28 2014-07-03 Chevron Oronite LLC Ultra-low saps lubricants for internal combustion engines
US9777021B2 (en) 2016-02-02 2017-10-03 Qatar Foundation Lubricant additives
EP3950904A4 (de) * 2019-03-29 2022-12-07 Idemitsu Kosan Co., Ltd. Schmierölzusammensetzung
CN113512452B (zh) * 2020-04-09 2023-10-10 中国石油化工股份有限公司 一种柴油发动机润滑油组合物及其制备方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2584884A (en) * 1983-09-16 1985-03-21 Bankamerica Corp. Lubricant for use with alcoholic fuels
JP2614149B2 (ja) * 1991-03-11 1997-05-28 富士写真フイルム株式会社 新規アルキルホスフェート
US5629272A (en) * 1991-08-09 1997-05-13 Oronite Japan Limited Low phosphorous engine oil compositions and additive compositions
JP3086727B2 (ja) * 1991-08-09 2000-09-11 オロナイトジャパン株式会社 低リンエンジン油製造用の添加剤組成物
US5672572A (en) * 1993-05-27 1997-09-30 Arai; Katsuya Lubricating oil composition
JP3500445B2 (ja) * 1994-06-06 2004-02-23 新日本石油株式会社 内燃機関用潤滑油組成物
JP3615267B2 (ja) * 1995-04-28 2005-02-02 新日本石油株式会社 エンジン油組成物
US5726133A (en) * 1996-02-27 1998-03-10 Exxon Research And Engineering Company Low ash natural gas engine oil and additive system
JP4334623B2 (ja) * 1996-06-12 2009-09-30 出光興産株式会社 自動変速機用潤滑油組成物
WO1998017747A1 (fr) * 1996-10-22 1998-04-30 Tonen Corporation Composition d'huile lubrifiante pour transmissions automatiques
US5792733A (en) * 1997-08-14 1998-08-11 The Lubrizol Corporation Antiwear compositions containing phosphorus compounds and olefins
WO1999038939A1 (fr) * 1998-01-29 1999-08-05 Idemitsu Kosan Co., Ltd. Nouvelles compositions d'addition
JP2000001685A (ja) * 1998-06-18 2000-01-07 Cosmo Sogo Kenkyusho:Kk エンジン油組成物
US6001780A (en) * 1998-06-30 1999-12-14 Chevron Chemical Company Llc Ashless lubricating oil formulation for natural gas engines
JP2000319682A (ja) * 1999-05-10 2000-11-21 Tonen Corp 内燃機関用潤滑油組成物
JP2001158896A (ja) 1999-12-02 2001-06-12 Chevron Oronite Ltd ガスエンジンの潤滑に特に有効な内燃機関用潤滑油組成物
JP2001164283A (ja) * 1999-12-10 2001-06-19 Tonengeneral Sekiyu Kk 内燃機関用潤滑油組成物
JP4416261B2 (ja) * 2000-03-29 2010-02-17 新日本石油株式会社 エンジン油組成物
US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
JP4856305B2 (ja) * 2000-10-30 2012-01-18 Ｊｘ日鉱日石エネルギー株式会社 エンジン油組成物
JP3841687B2 (ja) * 2001-01-24 2006-11-01 新日本石油株式会社 潤滑油組成物
CA2434332A1 (en) * 2001-02-07 2002-08-15 The Lubrizol Corporation Lubricating oil composition
US6784143B2 (en) * 2001-05-11 2004-08-31 Infineum International Ltd. Lubricating oil composition

Also Published As

Publication number Publication date
EP1439217A1 (de) 2004-07-21
US20040242434A1 (en) 2004-12-02
WO2003033629A1 (fr) 2003-04-24
EP1439217A4 (de) 2009-09-02

Similar Documents

Publication Publication Date Title
EP1439217B1 (de) Schmierölzusammensetzung für verbrennungsmotor
US7790659B2 (en) Lubricating oil compositions
US7612025B2 (en) Lubricating oil composition
US7696137B2 (en) Lubricating oil compositions
JP3841687B2 (ja) 潤滑油組成物
EP1227145B1 (de) Schmierölzusammensetzungen
US7625847B2 (en) Lubricating oil compositions
EP1516910A1 (de) Schmierölzusammensetzung
US7563752B2 (en) Lubricating oil compositions
JP3662228B2 (ja) 潤滑油組成物
JP2004083891A (ja) 潤滑油組成物
JP3738228B2 (ja) 潤滑油組成物
JP4309635B2 (ja) 内燃機関用潤滑油組成物
JP4227764B2 (ja) 潤滑油組成物
JP3709379B2 (ja) 潤滑油組成物
JP4373650B2 (ja) 潤滑油組成物
JP4528286B2 (ja) 潤滑油組成物
EP1526169B1 (de) Schmierölzusammensetzung
JP4286500B2 (ja) 潤滑油組成物
JP4257082B2 (ja) 潤滑油組成物
JP4286501B2 (ja) 潤滑油組成物
JP4257081B2 (ja) 潤滑油組成物

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: 20040413

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 IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

A4 Supplementary search report drawn up and despatched

Effective date: 20090731

RIC1 Information provided on ipc code assigned before grant

Ipc: C10M 133/56 20060101ALI20090727BHEP

Ipc: C10N 40/12 20060101ALI20090727BHEP

Ipc: C10M 133/16 20060101ALI20090727BHEP

Ipc: C10M 135/00 20060101ALI20090727BHEP

Ipc: C10M 133/12 20060101ALI20090727BHEP

Ipc: C10M 137/04 20060101ALI20090727BHEP

Ipc: C10M 159/20 20060101ALI20090727BHEP

Ipc: C10N 10/02 20060101ALI20090727BHEP

Ipc: C10N 30/08 20060101ALI20090727BHEP

Ipc: C10N 40/25 20060101ALI20090727BHEP

Ipc: C10N 10/04 20060101ALI20090727BHEP

Ipc: C10N 30/04 20060101ALI20090727BHEP

Ipc: C10N 30/06 20060101ALI20090727BHEP

Ipc: C10M 163/00 20060101AFI20030508BHEP

Ipc: C10M 129/10 20060101ALI20090727BHEP

17Q First examination report despatched

Effective date: 20091015

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60243187

Country of ref document: DE

Effective date: 20120823

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: 20130321

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60243187

Country of ref document: DE

Effective date: 20130321

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

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

Ref country code: DE

Payment date: 20181002

Year of fee payment: 17

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

Ref country code: GB

Payment date: 20181010

Year of fee payment: 17

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

Ref country code: FR

Payment date: 20190913

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60243187

Country of ref document: DE

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: 20200501

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

Effective date: 20191015

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: 20191015

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: 20201031