WO2004013265A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

Info

Publication number
WO2004013265A1
WO2004013265A1 PCT/JP2003/009884 JP0309884W WO2004013265A1 WO 2004013265 A1 WO2004013265 A1 WO 2004013265A1 JP 0309884 W JP0309884 W JP 0309884W WO 2004013265 A1 WO2004013265 A1 WO 2004013265A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
group
lubricating oil
carbon atoms
general formula
Prior art date
Application number
PCT/JP2003/009884
Other languages
English (en)
Japanese (ja)
Inventor
Kazuhiro Yagishita
Original Assignee
Nippon Oil Corporation
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 Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to AU2003252378A priority Critical patent/AU2003252378A1/en
Priority to EP03766727A priority patent/EP1526170A4/fr
Publication of WO2004013265A1 publication Critical patent/WO2004013265A1/fr
Priority to US11/048,441 priority patent/US7563752B2/en

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
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, 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
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene 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
    • 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
    • C10M2215/08—Amides
    • 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
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • 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
    • C10M2223/042—Metal 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
    • 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
    • C10M2223/043—Ammonium or amine 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
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10M2223/049—Phosphite
    • 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
    • C10N2030/06—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/72—Extended drain
    • 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 a low-sulfur lubricating oil composition, and more particularly to a low-sulfur lubricating oil composition having excellent anti-wear properties and long drainage properties, and particularly suitable for use in internal combustion engines.
  • the disclosed low-phosphorus oils or non-phosphorus-free oils include, for example, JP-A-62-253691, JP-A-1-500912, and JP-A-6-415568.
  • examples of the low ash oil include JP-A-8-489. No. 89, JP-A-8-253782, JP-A-9-111275, JP-A-2000-256690, etc.
  • Japanese Patent Application 2002 Japanese Patent Application 2002
  • a salicylate-based detergent with a metal ratio of 5 or less particularly a salicylate-based detergent prepared with a metal ratio of 3 or less
  • low friction, high-temperature detergency, and oxidation stability are obtained.
  • anti-wear agents containing sulfur and phosphorus such as zinc dithiophosphate
  • the present invention has been made in view of the above circumstances, and provides a long drain type low sulfur lubricating oil composition containing a salicylate-based detergent, which is extremely excellent in anti-wear performance. is there.
  • the present invention relates to a lubricating base oil comprising, based on the total amount of the composition, (A) an alkali metal or alkaline earth metal salicylate containing at least one compound selected from the compounds represented by the following general formula (1): And 5 or 5 to 5% by mass in terms of a metal element, and (B) 0.05 to 0.2% by mass of a phosphorus-containing wear inhibitor in terms of a phosphorus element. And (C) an amide compound represented by the general formula (2) in an amount of 0.01 to 1% by mass, and the total sulfur content of the composition is 0.3% by mass or less.
  • a lubricating oil composition characterized in that
  • R 1 is a hydrocarbon group having 1 to 40 carbon atoms
  • R 2 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms
  • the hydrocarbon group is oxygen or nitrogen.
  • M may be an alkali metal or alkaline earth metal
  • n represents 1 or 2 depending on the valence of the metal.
  • R 3 represents 640 carbon atoms and R 4 and R 5 may be the same or different and each represents hydrogen or a hydrocarbon group having 1-40 carbon atoms.
  • ⁇ B An alkali metal or alkaline earth metal salicylate in which the component is (A-1) a monoalkyl salicylate having one secondary alkyl group having 10 to 40 carbon atoms and a constituent ratio of 85 mol% or more. , And Z or a (over) basic salt thereof, wherein R 1 in the above general formula (1) is a secondary alkyl group having 10 to 40 carbon atoms, and R 2 is hydrogen.
  • (A-2) a secondary alkyl group having 10 to 40 carbon atoms, wherein R 1 and R 2 in the general formula (1) are An alkali metal or alkaline earth metal salicylate, and Z or a (over) basic salt thereof, and (A-3) the general formula (1)
  • R 1 or R 2 is a hydrocarbon group having 1 to less than 10 carbon atoms, the other is a secondary alkyl group having 10 to 40 carbon atoms, and the difference in carbon number between R 1 and R 2 Is preferably at least one selected from an alkali metal or alkaline earth metal salicylate and / or a (over) basic salt thereof.
  • the secondary alkyl group having 10 to 40 carbon atoms in the component (A-1) has a carbon number of Preferably it is from 10 to less than 20 secondary alkyl groups.
  • the metal ratio of the component (A) is preferably -2.3 or less.
  • the metal ratio of the component (A) is preferably 3 or more.
  • the component (B) is at least one selected from the group consisting of a phosphorus compound represented by the following general formula (3), a phosphorus compound represented by the following general formula (4), and a metal salt or an amine salt thereof. Preferably, it is a single compound.
  • X 1 , X 2, and X 3 each independently represent an oxygen atom or a sulfur atom, and R 5 , 16, and 17 each independently represent a hydrogen atom or a carbon atom. Represents up to 30 hydrocarbon groups.
  • the component (B) is a metal salt of a phosphorus compound in which X 1 , X 2 and X 3 in the general formula (3) are all oxygen atoms. It is preferable that at least one compound selected from the group consisting of metal salts of phosphorus compounds in which X 4 , X 5 , X 6 and X 7 in the general formula (4) are all oxygen atoms.
  • X 4 , X 5 , X 6, and X 7 in the general formula (4) are all oxygen atoms, and R 8 , R 9, and R 1Q each independently have a carbon number of 1 to It is preferably a phosphorus compound having 30 hydrocarbon groups.
  • the component (B), two X 4, X 5, X 6 and X 7 in the general formula (4) is an oxygen atom, two of R 8, R 9 and R 1 Q is 1 to carbon atoms With 30 hydrocarbon groups
  • it is a zinc salt of a phosphorus compound in which one is hydrogen. It is preferable that the content of the component (B) is 0.08% by mass or less in terms of a phosphorus element based on the total amount of the composition.
  • the lubricating oil composition of the present invention preferably contains at least one selected from (D) an ashless dispersant and (E) an antioxidant.
  • the total sulfur content of the lubricating base oil is preferably 0.05% by mass or less.
  • the lubricating oil composition of the present invention is preferably used for an internal combustion engine.
  • the lubricating oil composition of the present invention preferably has a sulfated ash content of 1.0% by mass or less.
  • the lubricating oil composition of the present invention has a sulfated ash content of 0.5% by mass or less, a total sulfur content of 0.05% by mass or less, and a phosphorus content of 0.05% by mass or less. Preferably, one or more requirements are satisfied.
  • the present invention also provides a method for preventing wear of a valve train of an internal combustion engine, comprising using the lubricating oil composition.
  • the lubricating oil composition of the present invention will be described in detail.
  • the lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and a mineral base oil or a synthetic base oil used for ordinary lubricating oils can be used.
  • a mineral base oil specifically, lubricating oil fractions obtained by depressurizing distillation of atmospheric residual oil obtained by atmospheric distillation of crude oil are subjected to solvent removal, solvent extraction, and hydrocracking. , Refined by one or more treatments such as solvent dewaxing, hydrorefining, etc., or mineral oils with wax insensitivity, base oils produced by isomerizing GTL WAX (gas to liquid wax), etc. Can be exemplified.
  • the sulfur content in the mineral base oil is not particularly limited as long as the total sulfur content of the composition is 0.3% by mass or less, but is 0.05 mass. / 0 or less, more preferably 0.01% by mass or less, particularly preferably 0.05% by mass or less.
  • the sulfur content of the mineral base oil it has better long-drainability, and when used as a lubricating oil for internal combustion engines, it can be used in exhaust gas aftertreatment equipment. It is possible to obtain a low-sulfur lubricating oil composition capable of avoiding adverse effects as much as possible.
  • the total aromatic content of the mineral base oil is not particularly limited, but is preferably 10% by mass or less, more preferably 6% by mass or less, still more preferably 3% by mass or less, and particularly preferably 2% by mass or less. % By mass or less. By setting the total aromatic content of the base oil to 10% by mass or less, a composition having more excellent oxidation stability can be obtained.
  • the above-mentioned total aromatic content means a content of aromatic fraction (aromatiicfractione) measured according to ASTM D2549.
  • this aromatic fraction includes, in addition to alkylbenzene and alkylnaphthalene, anthracene, phenanthrene, their alkylated compounds, compounds in which four or more benzene rings are condensed, or pyridines, quinolines, phenols, naphthols And compounds having a heteroaromatic group such as a class.
  • the synthetic base oil include polyptene or a hydride thereof; 1-octene oligomer, poly- ⁇ -olefin such as 1-decene oligomer or a hydride thereof; ditridecinoregolelate, G 2 —Diestenoles such as ethinolehexynoleate, disodecyl adipate, ditridecyl adipate, and di-ethylhexyl sebacate; neopentylglyconoleestenole, trimethylolpropanecapritolate, trimethylolonepropaneperano Polyol esters such as legonate, pentaerythritol and pentaerythritol hexanoate, and pentaerythritol peralgonate; aromatic synthetic oils such as alkyl naphthalene, alkyl benzene, and aromatic ester; And the like can be
  • the above-mentioned mineral base oil, the above-mentioned synthetic base oil, or an arbitrary mixture of two or more kinds selected from these can be used.
  • examples thereof include one or more mineral base oils, one or more synthetic base oils, and a mixed oil of one or more mineral base oils and one or more synthetic base oils.
  • the kinematic viscosity of the lubricating base oil used in the present invention is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 20 mm 2 / s or less, more preferably 10 mm 2 / s or less. It is. On the other hand, the kinematic viscosity is preferably 1 mm 2 Zs or more, and more preferably 2 mm 2 / s or more. If the kinematic viscosity at 100 ° C of the lubricating base oil exceeds 20 mm 2 Zs, the low-temperature viscosity characteristics will deteriorate, while the kinematic viscosity will decrease.
  • the evaporation loss of the lubricating base oil is preferably 20% by mass or less, more preferably 16% by mass or less, particularly preferably 10% by mass or less, in terms of NOACK evaporation amount. preferable.
  • the NOACK evaporation amount of the lubricating base oil exceeds 20% by mass, not only is the lubricating oil evaporation loss large, but also when it is used as a lubricating oil for internal combustion engines, the sulfur compound or phosphorus compound in the composition, or metal This is not desirable because there is a risk that the oil will accumulate in the exhaust gas purification device together with the lubricating base oil, which may have a negative effect on exhaust gas purification performance.
  • NOACK evaporation loss is, AS TM D 5800 which has been measured according to, under a reduced pressure of the lubricating oil sample 60 g 250 ° C, 2 Omm H 2 0 (1 9 6 P a) The amount of evaporation after holding for 1 hour at was measured.
  • the viscosity index of the lubricating base oil is not particularly limited, but the value is preferably 80 or more, more preferably 100 or more, so as to obtain excellent viscosity properties from low to high temperatures. Preferably it is at least 120. When the viscosity index is less than 80, the low-temperature viscosity characteristics are unfavorably deteriorated.
  • the component (A) in the lubricating oil composition of the present invention is an alkali metal or alkaline earth metal salicylate containing at least one compound selected from the compounds represented by the following general formula (1), and Z or (Z) It is a basic salt.
  • R 1 is a hydrocarbon group having 1 to 40 carbon atoms
  • R 2 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms
  • the hydrocarbon group contains oxygen or nitrogen.
  • M represents an alkali metal such as sodium, potassium, magnesium, norium, or calcium or an alkaline earth metal, particularly magnesium and / or magnesium. Alternatively, calcium is preferably used.
  • N represents 1 or 2 depending on the valence of the metal M.
  • hydrocarbon group having 1 to 40 carbon atoms examples include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group.
  • cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methyl cyclopentyl group, dimethyl Cyclopentyl group, Methylethylcyclopentyl group, Getylcyclopentyl group, Methylcyclohexyl group, Dimethyl / Recyclohexyl group, Methynorethynolecyclohexynole group, Getinolecyclohexyl group, Methy / lecycloheptyl group, To Dimethylcyclo mouth
  • An alkylcycloalkyl group having 6 to 10 carbon atoms such as a butyl group and a methylethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary), a butyr group, a pentenyl
  • alkyl-aryl groups having 7 to 10 carbon atoms
  • alkyl The group may be linear or branched, and the position of substitution on the aryl group is arbitrary.
  • a reel alkyl group (these alkyl groups may be linear or branched).
  • the hydrocarbon group is oxygen or nitrogen. Element may be contained.
  • the hydrocarbon group having 10 to 40 carbon atoms is a secondary alkyl group having 10 to 40 carbon atoms derived from a polymer or copolymer such as ethylene, propylene, or 1-butene. It is particularly preferably a secondary alkyl group having 14 to 19 carbon atoms or 20 to 26 carbon atoms.
  • the component (A) in the present invention is one or a mixture of two or more salicylates of alkali metal or alkaline earth metal of the following (A-1) to (A-3). Is preferred.
  • a monoalkyl salicylate having one secondary alkyl group having 10 to 40 carbon atoms has a constitutional ratio of 85 moles 0 /.
  • An alkali metal or alkaline earth metal salicylate having a composition ratio of the compound in which R 2 is hydrogen is 40 mol% or more
  • R 1 or R 2 in the general formula (1) is a secondary alkyl group having 10 to 40 carbon atoms, and is a salicylate or an alkaline earth metal salicylate; (Over) basic salts,
  • R 1 and R 2 in the general formula (1) is a hydrocarbon group having 1 to 10 carbon atoms, the other is a secondary alkyl group having 10 to 40 carbon atoms, and R 1 And an alkali metal or alkaline earth metal salicylate having a difference of 10 or more carbon atoms between R 2 and R 2 , and R or a (over) basic salt thereof.
  • the (A- 1) Composition ratio of monoalkyl salicylate in component although 85 mol% or more, preferably 8 8 mole 0/0 or more, 1 00 mole 0/0 also good in terms of production cost as
  • the composition may be comprised of 3-alkyl salicylate, 4-alkyl salicylate and 5-alkyl salicylate.
  • the component (A-1) In the salicylate structure to be constituted, the composition ratio of 3-alkyl salicylate (the compound in the above general formula (1) wherein R 1 is a secondary alkyl group having 10 to 40 carbon atoms and R 2 is hydrogen) is 40 moles. %, Preferably 50 mol% or more, more preferably 60 mol% or more, and may be 100 mol%, but may be 95 mol% or less from the viewpoint of production cost.
  • composition ratio of 3-alkyl salicylate is 80 mol% or less, further 60 mol% or less, particularly 55 mol% or less, particularly when the secondary alkyl group having less than 20 carbon atoms of R 1 is described below ( If the component (C) is not used together, depending on the selection of the component (B) or the reduction of the content of the component (B), the anti-wear performance such as the rocker arm anti-scuffing performance and the anti-cam wear performance in the internal combustion engine is sufficiently exhibited. There is a possibility that the wear prevention performance is extremely improved by using the component (C) in combination, so that the constitution of the present invention is useful.
  • the anti-wear performance is improved without using the component (C) in combination.
  • the combined use of the component (C) makes it possible to further reduce the content of the component (B) (for example, 0.05% by mass or less in terms of phosphorus element).
  • the composition ratio of 3-alkyl salicylate is less than 40 mol%, the composition ratio of 5-salicylate is relatively high, and the oil solubility is poor.
  • R 1 and R 2 are a secondary alkyl group having 10 to 40 carbon atoms, and R 1 and R 2 may be different or the same, In terms of production, it is preferably a secondary alkyl group derived from the same olefin.
  • the component (A-1) is used alone, a composition having excellent anti-wear performance can be obtained without using the component (C).
  • the component (B) can be obtained. Is preferred because it can be further reduced (for example, 0.05 mass% or less in terms of phosphorus element).
  • the component ratio of the component (A-2) is 10 moles 0 /.
  • the difference between the carbon number of R 1 and R 2 in the general formula (1) is 10 or more, and one of R 1 and R 2 has a carbon number of 1 to less than 10 A hydrocarbon group, preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, It is more preferably an alkyl group such as a tert-butyl group, particularly preferably a methyl group, and the other is a secondary alkyl group having 10 to 40 carbon atoms, preferably 10 to 30 carbon atoms.
  • R 1 is a secondary alkyl group having 10 to 40 carbon atoms and R 2 is a hydrocarbon group having 1 to less than 1 ° C.
  • the hydrocarbon group having 1 to 10 carbon atoms may contain oxygen or nitrogen, for example, a carboxyl group derived from a carboxylic acid having 1 to less than 10 carbon atoms such as a COOH group. And the like.
  • a composition having excellent anti-wear performance can be obtained without using the component (C). It is preferable to use the component (B) because the component (B) can be further reduced (for example, 0.05% by mass or less in terms of a phosphorus element).
  • composition ratio of the components is 1 0 mol% or more, preferably rather 2 0 mol% or more, particularly 3 0 mole 0/0 or more It is preferable to prepare it in such a way that the anti-wear performance can be further improved.
  • the total ratio of salicylates having a substituent at least at the 3-position is 55 mol% or more. It is more preferably at least 5 mol%, particularly preferably at least 70 mol%.
  • the component (A) of the present invention can be produced by a known method or the like, and there is no particular limitation.
  • the component (A-1) is a compound having 10 to 4 carbon atoms per mole of phenol. Alkylation using a olefin such as an ethylene polymer and carboxylation with carbon dioxide gas, or alkylation using 1 mol of the olefin per 1 mol of salicylic acid.
  • Alkyl salicylic acid containing chilic acid as a main component is reacted with metal base such as oxide or hydroxide of alkali metal or alkaline earth metal, or alkali metal such as sodium salt or potassium salt. It can be obtained by preparing a metal salt or by replacing an alkali metal salt with an alkaline earth metal salt.
  • component (A-2) and the component (A-3) are known compounds disclosed in, for example, Japanese Patent Publication No. 48-33532, Japanese Patent Publication No. 50-3802, and the like. Using methods, etc. Obtainable.
  • the component (A-2) is used in an amount of 1.1 to 4 mol, preferably 2 to 3 mol, and particularly preferably, instead of using 1 mol of the olefin in the method for producing the component (A-1). Can be obtained by a method using 2 to 2.5 mol.
  • the component (A-3) is, specifically, ortho-taresol or para-cresol, or ortho-t-butylphenol or para-t-butylphenol as a starting material, preferably having 10 to 40 carbon atoms.
  • An alkylsalicylic acid obtained by a method of carboxylating 3-t-butyl-5-alkylphenol or 3-anthalkyl-5-t-butylphenol with carbon dioxide gas or the like is used to convert an alkali metal or alkaline earth metal to an alkylsalicylic acid.
  • Reaction with metal bases such as oxides and hydroxides, or alkali metal salts such as sodium salts and potassium salts Further, it can be obtained by, for example, replacing an alkali metal salt with an alkaline earth
  • the component (A) of the present invention is obtained by adding an alkali metal or alkaline earth metal salicylate (neutral salt) obtained as described above to a further excess alkali metal or alkaline earth metal salt, alkali metal or aluminum salt.
  • Basic salts obtained by heating lithium earth metal bases (hydroxide metals or hydroxides or oxides of alkaline earth metal) in the presence of water, carbon dioxide, boric acid or boric acid.
  • Overbased salts obtained by reacting the above neutral salt with a base such as an alkali metal or alkaline earth metal hydroxide in the presence of an acid salt are also included.
  • reaction are usually carried out in a solvent (aliphatic hydrocarbon solvent such as hexane, aromatic hydrocarbon solvent such as xylene, light lubricating oil base oil, etc.), and the metal content is 1. It is desirable to use 0 to 20% by mass, preferably 2.0 to 16% by mass.
  • solvent aliphatic hydrocarbon solvent such as hexane, aromatic hydrocarbon solvent such as xylene, light lubricating oil base oil, etc.
  • the total base number of the component (A) is usually 0 to 500 mg KO HZ g, preferably 20 to 45 O mg KOH / g, and one or more selected from these. Can be used in combination of two or more.
  • the total base number mentioned here is JISK 2501 Means the total base number by the perchloric acid method measured in accordance with 7 of “Testing Methods for Neutralization Number of Petroleum Products and Lubricating Oils”.
  • the component (A) of the present invention has no particular limitation on its metal ratio. Generally, one or more components having a metal ratio of 20 or less can be used.
  • the salicylate prepared in the following, more preferably 2.3 or less, particularly 1.5 or less is particularly preferable because it is excellent in oxidation stability, high-temperature detergency, low friction, and the like.
  • the metal ratio is 5 or less, particularly the metal ratio is 3 or less, and the component (A-1) having one secondary alkyl group having less than 20 carbon atoms is used, the component (C) If the metal is not used, the anti-wear property may not be sufficiently exhibited as described above.
  • the lubricating oil composition of the present invention using the component (A-1) having a metal ratio adjusted to 5 or less is extremely useful. It is. According to the present invention, when the above-mentioned component (A-1) having a metal ratio of 2.3 or less or 3 or more, particularly a salicylate having a secondary alkyl group having a carbon number of less than 20 is used, the metal ratio is reduced. However, it is interesting that the anti-wear performance can be more excellent than when the above-mentioned (A-1) component of 2.4 to 2.9 is used.
  • the metal ratio here is represented by the valence of the metal element in the salicylate-based detergent X the content of the metal element (mol%) Z The content of the soap group (mol%), and the metal element is calcium, magnesium And the like.
  • the soap group means a salicylic acid group and the like.
  • the upper limit of the content of the component (A) is 0.4% by mass or less in terms of a metal element, and in order to reduce the sulfated ash content of the composition to 1.0% by mass or less,
  • the content of the component (A) is not more than 0.3% by mass.
  • the content of the component (A) should be 0.2% by mass or less, preferably 0.15% by mass or less, in order to minimize adverse effects on the exhaust gas aftertreatment device. More preferably, the content is most preferably 0.10% by mass or less, and a lubricating oil composition having a sulfated ash content of 0.5% by mass or less can be obtained.
  • the lower limit of the content of the component (A) is 0.05% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly It is preferably at least 0.05 mass%.
  • the composition has a high sulfated ash content, and when used as a lubricating oil for an internal combustion engine, it is not preferable because it may adversely affect an exhaust gas aftertreatment device. Further, the content of the component (A) is less than the lower limit. In this case, the basic performance as a metal-based detergent is not exhibited, and it becomes difficult to obtain long drain performance such as high-temperature detergency, oxidative stability, and base number retention.
  • the term "sulfated ash” used herein refers to the value measured by the method specified in JIS K2272, 5. “Test Methods for Sulfated Ash”, and is mainly attributed to metal-containing additives.
  • the component (B) in the present invention is a phosphorus-containing wear inhibitor, and there is no particular limitation as long as it is a wear inhibitor containing phosphorus in a molecule.
  • the phosphorus-containing antiwear agent of the present invention includes a phosphorus compound represented by the general formula (3), a phosphorus compound represented by the general formula (4), and a metal salt or an amine salt thereof. It is preferably at least one compound selected from the group consisting of: (
  • X 1 , X 2 and X 3 each independently represent an oxygen atom or a sulfur atom
  • R 5 , R 6 and R 7 each independently represent a hydrogen atom or a carbon atom Represents up to 30 hydrocarbon groups.
  • X 4 , X 5 , 6 and 7 each independently represent an oxygen atom or a sulfur atom
  • R 8 , 19 and 11 ° each independently represent a hydrogen atom or a carbon atom.
  • Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 5 to R 1 C) include an alkyl group, a cycloalkyl group, and an alkenyl group. And alkyl-substituted cycloalkyl groups, aryl groups, alkyl-substituted aryl groups, and arylalkyl groups.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, Alkyl groups such as pentyl, hexyl, heptyl, octyl, noel, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. (These alkyl groups may be linear or branched).
  • Examples of the cycloalkyl group include a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a acetylcyclopentinole group, a methylcyclohexylole group, a dimethylcyclohexyl group, a methynoleethylcyclohexyl group, and a methylethylcyclohexyl group.
  • Alkylcycloalkyl groups having 6 to 11 carbon atoms such as hexyl group, methylcycloheptyl group, dimethylcyclyl heptyl group, methynoleethynolecycloheptinol group, and ethynolecycloheptyl group.
  • the substitution position is also arbitrary.).
  • alkenyl group examples include a butenyl group, a pentenyl group, a hexenyl group, a heptyl group, an octenyl group, a nonenyl group, a decenyl group, a pentadecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and a hexadecenyl group.
  • alkenyl groups such as a heptadecenyl group and an octadecyl group (the alkenyl groups may be linear or branched, and the position of the double bond is also arbitrary).
  • Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group.
  • Examples of the alkylaryl group include a tolyl group, a xylinole group, an ethylphenyl group, a propynolephenyl group, a butynolepheno-nole group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, and a nonylphenyl group.
  • a C7-C18 alkylaryl group such as an alkyl group, a decylphenyl group, an decylphenyl group, a dodecylphenyl group, etc.
  • the alkyl group may be linear or branched; The substitution position is also arbitrary.).
  • arylalkyl group examples include a benzyl group, a phenylethyl group, a phenolepropyl group, a phenolebutynole group, a phenylpentinole group, and a phenylequinolene group.
  • an arylalkyl group having 7 to 12 carbon atoms such as a group (the alkyl group may be linear or branched).
  • the hydrocarbon group having 1 to 30 carbon atoms represented by R 5 to R 1 is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably It is preferably an alkyl group having 3 to 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.
  • Examples of the phosphorus compound represented by the general formula (3) include the following phosphorus compounds.
  • two or more X i X 3 of the general formula (3) are oxygen atoms. It is particularly preferable that all of them are oxygen atoms.
  • the phosphorus compound represented by the general formula (4) include the following phosphorus compounds.
  • Phosphoric acid monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, tetrathiophosphoric acid; phosphoric acid monoester, monothiophosphoric acid monoester, dithiophosphoric acid monoester, trithiophosphoric acid monoester having one of the above hydrocarbon groups having 1 to 30 carbon atoms Ester, tetrathiophosphoric acid monoester; the above phosphoric diester, monothiophosphoric acid diester, dithiophosphoric acid diester, trithiophosphoric acid diester, and tetrathiophosphoric acid diester having two hydrocarbon groups each having 1 to 30 carbon atoms; Phosphoric acid triesters having three 0 hydrocarbon groups, monothiophosphoric acid triester, dithiophosphoric acid triester, trithiophosphoric acid triester, tetrathiophosphoric acid triester; and mixtures thereof.
  • two or more of X 4 to X 7 in the general formula (4) are oxygen atoms in order to further enhance long drain performance such as high-temperature detergency, oxidation stability, and base number retention. It is more preferable that three or more are oxygen atoms, and it is particularly preferable that all of them are oxygen atoms.
  • Examples of the salt of the phosphorus compound represented by the general formula (3) or (4) include a metal base such as a metal oxide, a metal hydroxide, a metal carbonate, and a metal chloride, ammonia, and a compound having 1 carbon atom.
  • the metal in the metal base include alkali metals such as lithium, sodium, potassium, and cesium; alkaline earth metals such as calcium, magnesium, and barium; zinc, copper, iron, lead, nickel, silver, and the like.
  • alkaline earth metals such as calcium and magnesium and zinc are preferred.
  • the structure of the metal salt of the phosphorus compound varies depending on the valence of the metal, the number of the ⁇ groups or SH groups of the phosphorus compound, and thus the structure is not limited at all.
  • 1 mol of zinc oxide and phosphoric acid When two moles of a diester (one ⁇ group) are reacted, a compound having a structure represented by the following formula is considered to be obtained as a main component, but it is considered that a polymerized molecule also exists.
  • nitrogen compound examples include ammonia, monoamine, diamine, And polyamines. More specifically, methylamine, ethylamine, propylamine, propylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pendecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, pentadecylamine, pentadecylamine, pentadecylamine, pentadecylamine , Heptadecylamine, octadecylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didindecylamine, didodecyl
  • alkanolamine having a linear or branched structure such as propanolanolamine, methanolbutanolamine, ethanolpropanolenoamine, ethanolanolbutanolamine, and propanolbutanolamine (these alcohols)
  • An alkanolamine having a linear or branched structure an alkylene diamine having an alkylene group having 1 to 30 carbon atoms such as methylenediamine, ethylenediamine, propylenediamine, and butylenediamine; diethylenetriamine; Polyamines such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; pentadecyl getylamine, pentadecyl cetanolamine, dodecyldipropanolamine, oleyl cetanolamine, oleyl Propylene diamine, Compounds having an alkyl group or alkyl group having 8 to 20 carbon atoms in the above mono
  • aliphatic amines having an alkyl group having 10 to 20 carbon atoms or alkaryl groups such as decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine (these are Linear or branched) may be mentioned as a preferable example.
  • the component (B) includes a metal salt of a phosphorus compound wherein X 1 , X 2 and X 3 in the general formula (3) are all oxygen atoms, and X 4 , X 5 , X 6 and the like in the general formula (4).
  • X 7 is at least one compound selected from the group consisting of metal salts of phosphorus compounds in which all are oxygen atoms, because it has excellent oxidation stability, high drainability such as high-temperature detergency, and low friction. preferable.
  • (B) component, two of X 4, X 5, X 6 and X 7 in the general formula (4) is an oxygen atom, two of R 8, R 9 and R 1 Q is C1-30 It is preferable to use a zinc salt of a phosphorus compound, one of which is hydrogen, from the viewpoint of more excellent abrasion prevention properties and enabling further reduction in phosphorus.
  • salts of zinc or calcium with a phosphite diester having two alkyl groups or aryl groups having 3 to 18 carbon atoms, alkyl groups or aryl groups having 3 to 18 carbon atoms Preferably, a phosphite triester having three alkyl groups having 6 to 12 carbon atoms, a monoester of phosphoric acid having one alkyl group having 3 to 18 carbon atoms or one aryl group, and zinc or calcium
  • it is a phosphoric acid triester having three alkyl groups having 6 to 12 carbon atoms.
  • One or more of these components (B) can be arbitrarily compounded.
  • the content of the component (B) is 0.005% by mass or more, preferably 0.01% by mass or more, particularly preferably 0.1% by mass or more in terms of a phosphorus element based on the total amount of the composition. It is at least 02% by mass, while its content is at most 0.2% by mass, preferably at most 0.1% by mass, more preferably at most 0.08% by mass.
  • the content of the component (B) is less than 0.005% by mass as a phosphorus element, it is not preferable because it has no effect on the anti-wear property.
  • the component (C) in the present invention is an amide compound represented by the following general formula (2).
  • R 3 has 6 to 40 carbon atoms
  • R 4 and R 5 may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms.
  • fatty acid in the component (C) for example, a linear fatty acid or a branched fatty acid, a saturated fatty acid or an unsaturated fatty acid may be used, and the alkyl group or the alkyl group has 6 carbon atoms. -40, preferably 9-24, and more preferably 12-20. If the fatty acid has less than 6 carbon atoms in the alkyl or alkenyl group, the solubility will be poor, and if it exceeds 40, the anti-wear properties will be reduced. Not preferred.
  • fatty acid examples include heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecane Saturated fatty acids such as acid, icosanoic acid, henycosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, and triacontyl group.
  • Saturated fatty acids such as acid, icosanoic acid, henycosa
  • heptenoic acid otatenic acid, nonenoic acid, decenoic acid, pendecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenenoic acid, heptadecenoic acid, octadedecenoic acid, nonadecenenoic acid, Icosenoic acid, f Unsaturated fatty acids such as icosenoic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic acid, heptacosenoic acid, octacosenoic acid, nonacosenic acid, and triaconthenic acid (these unsaturated fatty acids may be linear or branched. And the position of the double bond is also arbitrary).
  • the fatty acid amide of the component (C) specifically, for example, the above-mentioned fatty acid or its oxychloride contains only ammonia or a hydrocarbon group having 1 to 40 carbon atoms or a hydroxyl group-containing hydrocarbon group in a molecule. And amides obtained by reacting a nitrogen compound such as an amine compound.
  • nitrogen compound examples include ammonia; monomethylamine, monoethynoleamine, monopropynoleamine, monobutynoleamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, and dimethylamido.
  • Methinoleethynoleamine getinoleamine, methinolepropynoleamine, ethynolepropyramine, dipropylamine, methylbutylamine, ethylbutyramine, propylpyrubutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, etc.
  • Alkylamines (alkyl groups may be linear or branched); monomethanolamine, monoethanolamine, monopropanolenoamine, monoptanolenoamine, monopeamine Tano one ⁇ / amine, Monoeki Sanoruamin, Putanoruamin to mono, mono O click pentanol ⁇ Min, Mononona Noruamin, dimethano one Ruamin, methanol ethanol ⁇ Min, Jietano Noreamine, methanolepropanoleamine, ethanolepropanoleamine, dipropanolenoamine, methanolebutanoreamine, ethanolebutanoleamine, propanolebutanolamine, dibutanoolenoamine, dipentanooleamine, dipentanooleamine, Alkanolamines such as dihexanolamine, diheptanoamine and dioctanolamine (the alkanol groups may be linear or branched); and
  • component (C) in the present invention examples include lauric acid amide, diethanolamide laurate, monopropanol amide lauric acid, amide myristic acid, diethanolamide myristic acid, and monopropanol myristic acid.
  • the lower limit of the content of the component (C) in the lubricating oil composition of the present invention is 0.01% by mass, preferably 0.05% by mass, based on the total amount of the composition.
  • the upper limit of the content is 1% by mass, preferably 0.6% by mass, particularly preferably 0.4% by mass, based on the total amount of the composition.
  • the content of the component (C) is less than 0.01% by mass, the anti-wear property cannot be improved.
  • the content of the component (C) exceeds 1% by mass, the storage stability is improved. It is not preferable because the properties deteriorate.
  • the lubricating oil composition of the present invention has excellent anti-wear properties by adopting the above constitution, and also has long drain properties such as low friction property, high-temperature detergency, base number maintenance property, and oxidation stability.
  • any ashless dispersant used in lubricating oils can be used.
  • a linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms may be used in the molecule.
  • at least one nitrogen-containing compound or a derivative thereof, or a modified product of alkenyl succinic acid imide may be blended.
  • the alkyl or alkenyl group has 40 to 400, preferably 60 to 350, carbon atoms.
  • the solubility of the compound in the lubricating base oil decreases, while when the alkyl group or alkenyl group has more than 400 carbon atoms, the lubricating oil composition has a low temperature.
  • This alkyl group or alkyl group may be straight-chain or branched, but is preferably, specifically, an oligomer of an olefin such as propylene, 1-butene, or isobutylene, or a copolymer of ethylene and propylene. Examples include a branched alkyl group and a branched alkenyl group derived from one.
  • component (D) include, for example, the following compounds. One or more compounds selected from these can be used.
  • (D-1) Succinic imid having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • (D-2) Benzylamine having at least one alkyl or alkyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • (D-3) Polyamine having at least one alkyl group or alkyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof.
  • examples of the above (D-1) succinic acid imide include compounds represented by the following general formulas (5) and (6).
  • R 2 ° is 40 to 400 carbon atoms, preferably 60 to 35 carbon atoms.
  • 0 represents an alkyl group or an alkyl group; and h represents an integer of 1 to 5, preferably 24.
  • R 21 and R 22 each independently represent an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and is preferably a polyptenyl group.
  • i represents an integer of 0 to 4, preferably 1 to 3.
  • succinic acid imid is a so-called monotype succinic acid imid represented by general formula (5) in which succinic anhydride is added to one end of polyamine, and succinic anhydride is added to both ends of polyamine.
  • a so-called bis-type succinic acid imid represented by the general formula (6) is included, and the composition of the present invention may contain any of them or a mixture thereof. good.
  • the method for producing these succinic imides is not particularly limited.For example, they are obtained by reacting a compound having an alkyl group or an alkyl group having 40 to 400 carbon atoms with maleic anhydride at 1.00 to 20 ° C. It can be obtained by reacting an alkyl or alkenyl succinic acid with a polyamine. Specific examples of the polyamine include dimethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • examples of the above (D-2) benzylamine include compounds represented by the following general formula (7).
  • R 23 represents an alkyl group or an alkenyl group having 40 to 400, preferably 60 to 350 carbon atoms, and j represents an integer of 1 to 5, preferably 2 to 4. .
  • the method for producing this benzylamine is not limited at all.
  • a polyolefin such as a propylene oligomer, a polybutene, or an ethylene-a-olefin copolymer is reacted with a phenol to form an alkylphenol. It can be obtained by reacting formaldehyde with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by a Mannich reaction.
  • examples of the polyamine (D-3) include compounds represented by the following general formula (8).
  • R 24 - NH- (CH 2 CH 2 NH) k - H 8
  • R 24 is 40 to 400 carbon atoms, preferably represents a 6 0-3 50 alkyl or alkenyl group
  • K represents an integer of 1 to 5, preferably 2 to 4.
  • the method for producing the polyamine is not limited at all.
  • polyolefin such as propylene oligomer, polybutene, and ethylene-co-olefin copolymer
  • ammonia ethylenediamine, and diethylenetriamine are added thereto.
  • polyethylene such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • the aforementioned nitrogen-containing compound may be a monocarboxylic acid having 1 to 30 carbon atoms (such as a fatty acid), oxalic acid, or phthalic acid.
  • oxygen-containing compounds such as polycarboxylic acids having 2 to 30 carbon atoms, such as acids, trimellitic acid, and pyromellitic acid, and hydroxy (poly) alkylene carbonates.
  • oxygen-containing compounds such as polycarboxylic acids having 2 to 30 carbon atoms, such as acids, trimellitic acid, and pyromellitic acid, and hydroxy (poly) alkylene carbonates.
  • so-called boron-modified compound the above-mentioned nitrogen-containing compound is treated with phosphoric acid to neutralize the remaining amino group and part or all of Z or imino group, ,
  • phosphoric acid-modified compounds aforementioned sulfur-modified compounds obtained by a work of sulfur compounds in the nitrogen-containing compound; and modified with an organic acid such as nitrogen-containing compounds described above, boric A modified compound obtained by combining two or more types of modifications selected from elementary modification, phosphoric acid modification, and sulfur modification.
  • boric acid-modified compounds of alkenyl succinic acid imid have excellent heat resistance, antioxidant properties and antiwear properties, and maintain the base number, high temperature cleanliness and antiwear properties in the lubricating oil composition of the present invention. It is effective to enhance the sex.
  • the component (D) When the component (D) is contained in the lubricating oil composition of the present invention, its content is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total amount of the lubricating oil composition. %. If the content of the component (D) is less than 0.01% by mass, the effect on high-temperature detergency is small, while if it exceeds 20% by mass, the low-temperature fluidity of the lubricating oil composition is significantly deteriorated. Therefore, each is not preferred.
  • antioxidant any phenolic antioxidant, a amine-based antioxidant, a metal-based antioxidant and the like generally used in lubricating oils can be used. Since the antioxidant of the lubricating oil composition can be further enhanced by the addition of the antioxidant, the base number retention and high-temperature detergency of the composition of the present invention can be further enhanced.
  • phenolic antioxidants examples include 4,4,1-methylenebis (2,6-DG tert-butyl phenol), 4,4,1-bis (2,6-G tert-butyl phenol), 4,4,1 Bis (2-methinole 6-tert-butynolephenol), 2,2, -methylenebis (4-ethynole 6-tert-butylphenol), 2,2'-methylenebis (4-methynole 6-tert-butylinophenol), 4,4'-butylidenebis (3-methynole-6-tert-butynolephenol), 4,4,1-isopropylidenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methylenolenate) 6-noninolephenole, 2, 2'-isobutylidenebis (4,6-dimethylphenol), 2,2, -methylenebis (4-methinole 6-hexylhexylphenol 2,6-di-tert
  • amine-based antioxidant may be, for example, phenylene Lou monument one Nafuchiruamin, Al Kirufue two routes a one Nafuchinoreamin, the ⁇ Pi di ⁇ Honoré Kino registration phenylalanine ⁇ Min. These may be used as a mixture of two or more.
  • the above phenolic antioxidant and amine antioxidant may be combined and compounded.
  • the content is usually 5% by mass or less, preferably 3% by mass or less, more preferably 3% by mass or less, based on the total amount of the lubricating oil composition. 2.5 mass% or less. If the content exceeds 5% by mass, it is not preferable because sufficient antioxidant properties cannot be obtained in proportion to the content.
  • its content is preferably 0.00 based on the total amount of the lubricating oil composition in order to further enhance long drain performance such as high-temperature detergency, oxidative stability, and base number retention during lubricating oil deterioration. It is at least 1 mass%, preferably at least 1 mass%, particularly preferably at least 1.5 mass%.
  • an amine compound such as the component (D), the amine antioxidant of the component (E) or a mixture thereof (B)
  • an organic solvent such as hexane, toluene and decalin at a temperature of 15 to 150 ° C, preferably 30 to 120 ° C (: particularly preferably 40 to 90 ° C).
  • the lubricating oil composition of the present invention has a Any additive commonly used in lubricating oils can be added according to the purpose.
  • metal-based detergents other than the component (A) wear inhibitors other than the component (B), friction modifiers, viscosity index improvers, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators And additives such as an antifoaming agent and a coloring agent.
  • an alkali metal or alkaline earth metal sulfonate, phenate, or the like may be used as the metal detergent other than the component (A).
  • Examples of the antiwear agent other than the component (B) include sulfur-containing compounds such as disulfides, sulfurized oils, sulfurized oils and fats, and zinc dithiol zinc rubinate. These can be contained in the composition of the present invention in the range of 0.05 to 5% by mass as long as the total sulfur content of the composition is not more than the specified amount of the present invention. It is preferred that a composition having extremely excellent abrasion resistance can be obtained without using it, and that it is not blended from the viewpoints of low sulfur content and mouth water drainage.
  • any compound usually used as a friction modifier for lubricating oils can be used.
  • molybdenum dithiolbamate, molybdenum dithiophosphate, molybdenumamine complex, molybdenum-succinic acid A molybdenum-based friction modifier such as a meido complex or molybdenum disulfide; an alkyl group or an alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl or alkenyl group having 6 to 30 carbon atoms.
  • Ashless friction modifiers such as amine compounds, fatty acid esters, fatty acids, aliphatic alcohols and aliphatic ethers, etc., which are present in at least one, and are usually 0.1 to 5% by mass. In the case of a sulfur-containing molybdenum complex, it can be contained within a range where the total sulfur content of the composition is not more than the prescribed amount of the present invention.
  • the ashless friction modifiers such as the above-mentioned amine compounds and fatty acid esters are inferior to the component (C) in terms of anti-wear properties and cannot be used in place of the component (C).
  • the molybdenum-based friction modifier can be particularly preferably used.
  • a so-called non-dispersion type viscosity index improver such as a polymer or copolymer of one or more monomers selected from various methacrylates or a hydrogenated product thereof is used.
  • a so-called dispersion type viscosity index improver obtained by copolymerizing various methacrylates containing a nitrogen compound, a non-dispersion type or dispersion type ethylene- ⁇ -olefin copolymer ( ⁇ -olefin is propylene, 1-butene , 11-pentene, etc.) or hydrides thereof, polyisobutylene or its hydrogenated products, hydrides of styrene-one-gen copolymers, styrene-mono-maleic anhydride copolymers, and polyalkylstyrenes.
  • ⁇ -olefin is propylene, 1-butene , 11-pentene, etc.
  • the molecular weight of these viscosity index improvers must be selected in consideration of shear stability.
  • the number average molecular weight of the viscosity index improver is, for example, usually 5,000 to 1, 0000, 0000, preferably 100, in the case of dispersible and non-dispersible polymethacrylates.
  • the thing of 0,000 to 900,000 is polyisobutylene or a hydride thereof, it is usually 800 to 5,000, preferably 1,000 to 4,0,000.
  • Is ethylene- ⁇ -olefin copolymer or a hydride thereof usually 800 to 500,000, preferably 3,000 to 200,000. Used.
  • a lubricating oil composition having particularly excellent shear stability can be obtained.
  • One or more compounds arbitrarily selected from the above viscosity index improvers can be contained in an arbitrary amount.
  • the content of the viscosity index improver is usually 0.1 to 20% by mass based on the lubricating oil composition.
  • the corrosion inhibitor include 'benzotriazole-based, tolyltriazole-based, thiadiazole-based, and imidazole-based compounds.
  • fire retardant examples include petroleum sulfonate, alkylbenzene sulfonate, di-nornaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.
  • demulsifier examples include polyalkylene glycol-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenylene ether, and polyoxyethylene alkynolenaphthyl ether.
  • metal deactivator examples include imidazoline, pyrimidine derivatives, alkinorethiadiazole, mercaptobenzothiazonole, benzotriazonole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4- Thiadiazolyl-1,2,5-bisdialkyldithiocarbamate, 21 (alkyldithio) benzoimidazole, and [3- (o-carboxybenzylthio) propionnitrile.
  • antifoaming agent examples include silicone, fluorosilicole, and fluoroalkyl ether.
  • the content is 0.005 to 5 for the corrosion inhibitor, the antioxidant, and the demulsifier, based on the total amount of the lubricating oil composition.
  • % By mass, 0.001 to 1% by mass for a metal deactivator, and 0.005 to 1% by mass for an antifoaming agent.
  • the lubricating oil composition of the present invention can provide a lubricating oil composition having excellent anti-wear properties in which the total sulfur content of the composition is 0.3% by mass or less. by the selection of components ⁇ Pi various additives, the total sulfur content of 0.2% by weight of the composition or less, more preferably 0.1 mass 0/0 or less, more preferably 0.0 to 5% by weight of anti-wear It is also possible to obtain a low sulfur lubricating oil composition having excellent properties. Particularly, it is possible to obtain a lubricating oil composition having a sulfur content of not more than 0.01% by mass or not more than 0.05% by mass.
  • the lubricating oil composition of the present invention comprises the component (A), the component (B) or other metals.
  • the content of additives contained it is possible to reduce the sulfated ash content of the composition to 1.0% by mass or less, 0.8% by mass, more preferably 0.6% by mass or less, In particular, it can be set to 0.5% by mass or less.
  • the lubricating oil composition of the present invention has low sulfur and is excellent not only in anti-wear properties, but also in low friction properties, long drain properties (oxidation stability, base number maintenance properties, etc.) and high-temperature detergency. It can be preferably used as a lubricating oil for internal combustion engines such as gasoline engines for automobiles, automobiles, power generation, and marine engines, diesel engines, gas engines, etc., and is lubricating oil with low sulfur, low phosphorus and low ash. This is particularly suitable for an internal combustion engine equipped with an exhaust gas aftertreatment device.
  • low-sulfur fuels such as gasoline, gas oil, kerosene, LPG, natural gas, or sulfur having a sulfur content of 50 mass ppm or less, more preferably 30 mass ppm or less, and particularly preferably 10 mass ppm or less are preferably used. It can be particularly preferably used as a lubricating oil for an internal combustion engine using a fuel (eg, hydrogen, dimethyl ether, alcohol, GTL (gas to liquid) fuel) which is not substantially contained, and particularly for a gasoline engine or a gas engine.
  • a fuel eg, hydrogen, dimethyl ether, alcohol, GTL (gas to liquid) fuel
  • lubricating oil that requires any of the above-described performances of the present invention, lubricating oil for drive systems such as automatic or manual transmissions, grease, wet brake oil, hydraulic oil, turbine oil, compressor oil It can also be suitably used as a lubricating oil such as a bearing oil and a refrigerator oil.
  • the lubricating oil composition of the present invention can exhibit extremely excellent performance in terms of anti-wear properties, and can achieve low sulfur, low phosphorus and low ash, low friction, long drainage It is also excellent. Therefore, in addition to lubricating oils for internal combustion engines, lubricating oils that require any of these performances, such as lubricating oils for drive systems of automatic or manual transmissions, greases, wet brake oils, hydraulic oils, It can also be suitably used as a lubricating oil such as turbine oil, compressor oil, bearing oil, and refrigerating oil.
  • lubricating oil compositions of the present invention (Examples 1 to 3) and comparative lubricating oil compositions (Comparative Examples 1 and 2) were prepared.
  • the lubricating oil composition of the present invention is a low-sulfur lubricating oil composition having a total sulfur content of 0.3% by mass or less, and a total sulfur content of 0.01% by mass or less. Even when the phosphorus content is reduced to 0.08% by mass or less, the use of the component (C) results in extremely excellent wear resistance (the anti-scruffing of the rocker arm pad, the rocker arm).
  • the component (A-1) having a metal ratio of 1 was used, and the sulfated ash content of the composition was reduced to 0.5% by mass or less.
  • the (Al) component having a metal ratio of 5.8 when the (Al) component having a metal ratio of 5.8 is used (Example 3), when the (A-1) component having a metal ratio of 2.7 is used (actually, It can be seen that the abrasion prevention performance was superior to that of Example 2).
  • the component (A-1) in addition to the component (A-1) having a secondary alkyl group having 10 to less than 20 carbon atoms shown in the examples, the component (A-1) can be used without using the component (C).
  • a sulfur- and phosphorus-containing antiwear agent such as zinc dithiophosphate
  • the anti-wear performance is maintained as compared with a phosphorus-containing antiwear agent containing no sulfur.
  • Abrasion-preventing properties that are even better than the above compositions can be exerted. For example, phosphorus content is reduced to 0.05% by mass or less, total sulfur content is reduced to 0.1% by mass or less, or sulfated ash content is 0%. It is considered that a composition with low ashing of 5% by mass or less and excellent in antiwear properties can be obtained.
  • the use of the component (C) also significantly improves the anti-wear property. It is possible to further reduce ash.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hydrorefined mineral oil *% by mass Remaining Remaining Remaining Remaining Remaining Remaining
  • CO demulsifier 9 mass% 0.01 0.01 0.01 0.01 0.01 0.01 0.01
  • Salicylic acid composition ratio 3A salicylic acid 51 mol%, 4A salicylic acid 6mol%, 5A salicylic acid 35mol%, 3,5-dialkyl salicylic acid 7mol%,
  • 5A Female droxyisophthalic acid 1 mol%, A (alkyl group): secondary C14, C16, C18, metal ratio 1, Ga content: 2.0 mass%, sulfated ash content: 6.8 mass% * 3) Salicylic acid composition ratio: 3A salicylic acid 51 mol%, 4A salicylic acid 6 mol ° /. , 5A salicylic acid 35 mol%, 3,5-dialkyl salicylic acid 7 mol%,
  • 5A Female droxyisophthalic acid 1 mol%, A (alkyl group): secondary G14, C16, G18, metal ratio 2.7, Ca content: 6.2 mass%, sulfated ash: 21.1 mass% * Salicylic acid composition ratio: 3A salicylic acid 51 mol%, 4A salicylic acid 6 mol%, 5A salicylic acid 35 mol%, 3,5-dialkyl salicylic acid 7 mol%,

Landscapes

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

Abstract

L'invention concerne la composition d'une huile lubrifiante comprenant une huile de base, un dérivé salicylé de métal alcalin spécifique, un dérivé salicylé métal terreux alcalin et/ou leur sel (per)basique dans une quantité de 0,005 à 5 % en masse en termes de la quantité de l'élément métal, (B) un inhibiteur d'usure phosphoré dans une quantité de 0,005 à 0,2 % en masse en termes de la quantité de phosphore et (C) 0,01 à 1 % en masse d'un composé d'amide et ayant une teneur totale en soufre de maximum 0,3 % en masse, tous ces pourcentages étant exprimés par rapport à la quantité totale de la composition. La composition d'huile lubrifiante est une huile lubrifiante à basse teneur en soufre qui a d'excellentes propriétés d'inhibition d'usure et aussi d'écoulement et équivalent, et est ainsi particulièrement adaptée à un moteur à combustion interne.
PCT/JP2003/009884 2002-08-05 2003-08-04 Composition d'huile lubrifiante WO2004013265A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003252378A AU2003252378A1 (en) 2002-08-05 2003-08-04 Lubricating oil composition
EP03766727A EP1526170A4 (fr) 2002-08-05 2003-08-04 Composition d'huile lubrifiante
US11/048,441 US7563752B2 (en) 2002-08-05 2005-02-01 Lubricating oil compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002227484A JP4373650B2 (ja) 2002-08-05 2002-08-05 潤滑油組成物
JP2002-227484 2002-08-05

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/048,441 Continuation US7563752B2 (en) 2002-08-05 2005-02-01 Lubricating oil compositions

Publications (1)

Publication Number Publication Date
WO2004013265A1 true WO2004013265A1 (fr) 2004-02-12

Family

ID=31492211

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/009884 WO2004013265A1 (fr) 2002-08-05 2003-08-04 Composition d'huile lubrifiante

Country Status (5)

Country Link
EP (1) EP1526170A4 (fr)
JP (1) JP4373650B2 (fr)
CN (1) CN100500818C (fr)
AU (1) AU2003252378A1 (fr)
WO (1) WO2004013265A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006047486A1 (fr) * 2004-10-25 2006-05-04 The Lubrizol Corporation Inhibition de la corrosion
WO2007119299A1 (fr) * 2006-03-22 2007-10-25 Nippon Oil Corporation Formule d'huile moteur à faible teneur en cendres
US20080146474A1 (en) * 2004-11-26 2008-06-19 Masato Takahashi Lubricant Composition and Driving Force Transmitting System Using Same

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4430538B2 (ja) 2002-08-05 2010-03-10 新日本石油株式会社 潤滑油組成物
EP1580257A4 (fr) * 2002-12-17 2006-03-29 Nippon Oil Corp Additif pour huile lubrifiante et composition d'huile lubrifiante
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
JP2006124536A (ja) * 2004-10-29 2006-05-18 Nippon Oil Corp 鉛含有金属材料に好適な潤滑油組成物
TR201909324T4 (tr) * 2005-03-21 2019-07-22 Basf Se Yanmalı motorlarda kullanıma yönelik aşınma karşıtı yağlayıcı bileşimler.
JP5030402B2 (ja) * 2005-08-15 2012-09-19 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
JP5213215B2 (ja) * 2007-03-28 2013-06-19 Ｊｘ日鉱日石エネルギー株式会社 潤滑剤組成物およびこれを用いた潤滑システム
CA2737773A1 (fr) * 2008-10-02 2010-04-08 The Lubrizol Corporation Apport d'additifs pratiquement insolubles a des fluides fonctionnels
JP2013216872A (ja) 2012-03-16 2013-10-24 Idemitsu Kosan Co Ltd 潤滑油組成物、該潤滑油組成物を用いた摺動機構
DE112015001419B4 (de) * 2014-03-24 2023-09-28 Autonetworks Technologies, Ltd. Elektrische Verbindungsstruktur mit Oberflächenschutzmittelzusammensetzung, Verfahren zur Herstellung derselben, Verfahren zum Unterdrücken einer Korrosion einer elektrischen Verbindungsstruktur und Kabelbaum für ein Kraftfahrzeug, der die elektrische Verbindungsstruktur umfasst.
JP6753608B2 (ja) 2016-10-19 2020-09-09 出光興産株式会社 潤滑油組成物、潤滑方法、及び変速機
JP7045878B2 (ja) * 2018-02-08 2022-04-01 Ｅｎｅｏｓ株式会社 油圧作動油組成物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1146925A (en) * 1967-06-28 1969-03-26 Shell Int Research Lubricant compositions
GB1184020A (en) * 1968-12-19 1970-03-11 Shell Int Research Salts of Polyvalent Metals and Alkylsalicylic Acids
WO1994028094A1 (fr) * 1993-05-27 1994-12-08 Exxon Research And Engineering Company Composition d'huile lubrifiante
JPH07150169A (ja) * 1993-11-30 1995-06-13 Tonen Corp 潤滑油組成物
JPH11302679A (ja) * 1998-04-24 1999-11-02 Japan Energy Corp 潤滑油組成物
EP0953629A1 (fr) * 1998-05-01 1999-11-03 Shell Internationale Researchmaatschappij B.V. Compositions lubrifiantes pour moteurs à combustion interne
EP1018539A2 (fr) * 1999-01-04 2000-07-12 Infineum International Limited Détergents surbasiques contenant des métaux
JP2002212579A (ja) * 2001-01-12 2002-07-31 Showa Shell Sekiyu Kk 環境負荷低減型の潤滑油組成物
EP1227145A1 (fr) * 2001-01-24 2002-07-31 Nippon Mitsubishi Oil Corporation Compositions d'huile lubrifiante

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07316577A (ja) * 1994-05-20 1995-12-05 Tonen Corp 潤滑油組成物
CN1115397C (zh) * 2000-09-27 2003-07-23 中国石油天然气股份有限公司兰州炼化分公司 一种发动机润滑油组合物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1146925A (en) * 1967-06-28 1969-03-26 Shell Int Research Lubricant compositions
GB1184020A (en) * 1968-12-19 1970-03-11 Shell Int Research Salts of Polyvalent Metals and Alkylsalicylic Acids
WO1994028094A1 (fr) * 1993-05-27 1994-12-08 Exxon Research And Engineering Company Composition d'huile lubrifiante
JPH07150169A (ja) * 1993-11-30 1995-06-13 Tonen Corp 潤滑油組成物
JPH11302679A (ja) * 1998-04-24 1999-11-02 Japan Energy Corp 潤滑油組成物
EP0953629A1 (fr) * 1998-05-01 1999-11-03 Shell Internationale Researchmaatschappij B.V. Compositions lubrifiantes pour moteurs à combustion interne
EP1018539A2 (fr) * 1999-01-04 2000-07-12 Infineum International Limited Détergents surbasiques contenant des métaux
JP2002212579A (ja) * 2001-01-12 2002-07-31 Showa Shell Sekiyu Kk 環境負荷低減型の潤滑油組成物
EP1227145A1 (fr) * 2001-01-24 2002-07-31 Nippon Mitsubishi Oil Corporation Compositions d'huile lubrifiante

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1526170A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006047486A1 (fr) * 2004-10-25 2006-05-04 The Lubrizol Corporation Inhibition de la corrosion
CN101084295B (zh) * 2004-10-25 2011-08-10 卢布里佐尔公司 包含腐蚀抑制剂的润滑组合物
US20080146474A1 (en) * 2004-11-26 2008-06-19 Masato Takahashi Lubricant Composition and Driving Force Transmitting System Using Same
WO2007119299A1 (fr) * 2006-03-22 2007-10-25 Nippon Oil Corporation Formule d'huile moteur à faible teneur en cendres
EP1997871A4 (fr) * 2006-03-22 2010-04-28 Nippon Oil Corp Formule d'huile moteur à faible teneur en cendres
US8071518B2 (en) 2006-03-22 2011-12-06 Nippon Oil Corporation Low ash engine oil composition

Also Published As

Publication number Publication date
JP2004067812A (ja) 2004-03-04
CN100500818C (zh) 2009-06-17
EP1526170A4 (fr) 2006-04-05
AU2003252378A1 (en) 2004-02-23
JP4373650B2 (ja) 2009-11-25
EP1526170A1 (fr) 2005-04-27
CN1681910A (zh) 2005-10-12

Similar Documents

Publication Publication Date Title
JP4578115B2 (ja) 潤滑油組成物
JP3841687B2 (ja) 潤滑油組成物
JP4327519B2 (ja) 潤滑油組成物
WO2005037967A1 (fr) Additif pour huile lubrifiante et composition d'huile lubrifiante
WO2006043527A1 (fr) Formule d’huile lubrifiante
US7563752B2 (en) Lubricating oil compositions
WO2004003117A1 (fr) Composition d'huile de graissage
JP4263878B2 (ja) 潤滑油組成物
WO2004013265A1 (fr) Composition d'huile lubrifiante
JP4663288B2 (ja) 鉛含有金属材料と接触する潤滑油組成物
JP4227764B2 (ja) 潤滑油組成物
JP3709379B2 (ja) 潤滑油組成物
JP4889179B2 (ja) 潤滑油組成物
JP5097350B2 (ja) 潤滑油組成物、酸化防止剤組成物及び潤滑油の粘度増加抑制方法
JP2005220197A (ja) 鉛含有金属材料と接触する潤滑油組成物
WO2004111162A1 (fr) Composition lubrifiante pour moteur a combustion interne
JP4670072B2 (ja) 鉛含有金属材料と接触する潤滑油組成物
JP4806524B2 (ja) 潤滑油組成物
JP2005002214A (ja) 潤滑油組成物
JP4528286B2 (ja) 潤滑油組成物
JP4286500B2 (ja) 潤滑油組成物
WO2004013264A1 (fr) Composition d'huile lubrifiante
JP4257082B2 (ja) 潤滑油組成物
JP4286501B2 (ja) 潤滑油組成物
JP4612393B2 (ja) 鉛含有金属材料に好適な潤滑油組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 11048441

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2003766727

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 20038219816

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2003766727

Country of ref document: EP