WO2004003117A1 - Composition d'huile de graissage - Google Patents

Composition d'huile de graissage Download PDF

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Publication number
WO2004003117A1
WO2004003117A1 PCT/JP2003/008338 JP0308338W WO2004003117A1 WO 2004003117 A1 WO2004003117 A1 WO 2004003117A1 JP 0308338 W JP0308338 W JP 0308338W WO 2004003117 A1 WO2004003117 A1 WO 2004003117A1
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WIPO (PCT)
Prior art keywords
mass
group
lubricating oil
component
content
Prior art date
Application number
PCT/JP2003/008338
Other languages
English (en)
Japanese (ja)
Inventor
Kazuhiro Yagishita
Akira Yaguchi
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
Priority claimed from JP2002191090A external-priority patent/JP4263878B2/ja
Priority claimed from JP2002191091A external-priority patent/JP4227764B2/ja
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to AU2003241824A priority Critical patent/AU2003241824A1/en
Priority to EP03736322A priority patent/EP1516910A4/fr
Publication of WO2004003117A1 publication Critical patent/WO2004003117A1/fr
Priority to US11/019,989 priority patent/US7790659B2/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
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    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms 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
    • 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
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    • 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
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    • 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
    • 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
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
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    • 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
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    • 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
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    • 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
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    • 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
    • C10N2030/74—Noack Volatility
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    • 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 lubricating oil composition, and more particularly, to a lubricating oil composition having excellent low-friction properties and improved long-drainability, particularly suitable for an internal combustion engine.
  • lubricating oil has been used in internal combustion engines, automatic transmissions, and the like in order to facilitate their operation.
  • lubricating oils for internal combustion engines (engine oils) are required to have high performance as internal combustion engines have higher performance, higher output, and severe operating conditions.
  • conventional engine oils contain various additives such as antiwear agents, metallic detergents, ashless dispersants, and antioxidants to meet these required performances.
  • organic molybdenum compounds containing sulfur such as molybdenum dicarbamate and molybdenum dithiophosphate are used. Has been used preferably because of its excellent friction reducing effect.
  • the present invention has been made in view of the above-mentioned demands, and provides a lubricating oil composition having both low friction properties and long drain properties (oxidation stability, base number maintenance properties, etc.) which is particularly suitable for an internal combustion engine. It is.
  • the present inventors have conducted intensive studies on the above-mentioned problems, and as a result, completed the present invention.
  • the present invention relates to a lubricant base oil comprising (A) a phosphorus compound represented by the general formula (1), a metal salt or an amine salt thereof, a phosphorus compound represented by the general formula (2), At least one phosphorus compound selected from the group consisting of a metal salt or an amine salt of (a) and (B) zinc dithiophosphate, in an amount of 0.005 to 0.5 mass in terms of phosphorus element, based on the total amount of the composition.
  • a lubricating oil composition comprising at least one additive selected from the group consisting of (C) a metal detergent, (D) an ashless dispersant, and (E) an antioxidant. Further, the present invention relates to a lubricating oil composition having any one of the following requirements (I) to (IV).
  • X 1 , 2 and 3 each independently represent an oxygen atom or a sulfur atom, and at least two of them are oxygen atoms, and RR 2 and R 3 are And each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • X 4 , X 5 , X 6 and X 7 each independently represent an oxygen atom or a sulfur atom, and at least three of these are oxygen atoms;
  • R 4 , R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms xxpnl
  • the component (A) is contained as the main component of R, and the sulfated ash content of the composition
  • the component (A) is contained as a main component, and (F) a sulfur-containing organic molybdenum complex is 0.001 in terms of molybdenum element based on the total amount of the composition.
  • the component (B) is contained as a main component, and (G) An ashless friction modifier is contained. And, based on the total amount of the composition, the content of the component (B) is expressed in terms of the elemental phosphorus. 0.05 mass% or less, and the sulfated ash content of the composition is 1.2 mass% or less.
  • the lubricating oil composition described above is brought into contact with a direct-acting type or a roller follower type valve operating mechanism.
  • the present invention also relates to a lubrication method for an internal combustion engine having the valve mechanism.
  • 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 mineral base oils and Z or synthetic base oils used for ordinary lubricating oils can be used.
  • a mineral base oil specifically, the atmospheric residual oil obtained by atmospheric distillation of crude oil is reduced.
  • a lubricating oil fraction obtained by pressure distillation is refined by one or more treatments such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, hydrorefining, or mineralized wax oil.
  • 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, further preferably 3% by mass or less, and particularly preferably 2% by mass or less. % Or less. If the total aromatic content of the base oil exceeds 15% by mass, the oxidation stability is poor, which is not preferable.
  • the above-mentioned total aromatic content means the content of an aromatic fraction (aromatic acid fracaction) measured according to ASTM D2549.
  • this aromatic fraction contains, 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, and naphthols And other compounds having heteroaromatics.
  • the sulfur content in the mineral base oil is not particularly limited, but is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and 0.005% by mass or less. It is particularly preferred that the content be 5% by mass or less.
  • the synthetic base oil examples include polybutene or its hydride; poly- a- olefin such as 1-octene oligomer and 1-decene oligomer or its hydride; ditridecyl glutarate, and di-ethylethylhexylazir.
  • Diesterols such as polyester, disodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl sepate; neopentinole glycol ester, trimethylol propyl caprylate, trimethylol propaneperargonate, pentaerythritol
  • Diesterols such as polyester, disodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl sepate
  • neopentinole glycol ester trimethylol propyl caprylate, trimethylol propaneperargonate, pentaerythritol
  • polyol esters such as 2-ethylhexanoate and pentaerythritol pelargonate
  • aromatic synthetic oils such as alkylnaphthalene, alkylbenzene, and aromatic ester, and mixtures thereof.
  • kinematic viscosity at its 1 00 ° C is preferably at most 20 m m 2 / s, more preferably not more than 1 0 mm 2 / s.
  • the kinematic viscosity is preferably at least 1 mm 2 / s, more preferably at least 2 mm 2 / s.
  • the kinematic viscosity of the lubricating base oil at 100 ° C exceeds 20 mm 2 / s, the low-temperature viscosity characteristics deteriorate, while if the kinematic viscosity is less than lmm 2 Zs, the oil film at the lubricating point Insufficient formation results in poor lubricity, and large loss of evaporation of the lubricating base oil is undesirable.
  • 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.
  • NOACK evaporation amount of the lubricating base oil exceeds 20% by mass, not only the lubricating oil evaporation loss is large, but also when the lubricating oil is used as a lubricating oil for internal combustion engines, the sulfur compounds and phosphorus compounds in the composition, Alternatively, it is not preferable because the metal component may accumulate in the exhaust gas purification device together with the lubricating base oil, which may adversely affect the exhaust gas purification performance.
  • NO A CK evaporation amount referred to here which has been measured according to ASTM D 5800, lubricating oil sample 60 g of 250 ° C, under a reduced pressure of 20mm H 2 0 (1 96 P a) The amount of evaporation was measured after holding for one hour.
  • the viscosity index of the lubricating base oil is not particularly limited, but the value is preferably 80 or more, and more preferably 100 or more, so that excellent viscosity characteristics from low to high temperatures can be obtained. Preferably it is 120 or more. When the viscosity index is less than 80, the low-temperature viscosity characteristics deteriorate, which is not preferable.
  • the component (A) in the lubricating oil composition of the present invention includes a phosphorus compound represented by the general formula (1), a metal salt or an amine salt thereof, a phosphorus compound represented by the general formula (2), At least one phosphorus compound selected from the group consisting of metal salts or amine salts of (Phosphorus-containing wear inhibitor).
  • XIX 1, X 2 ⁇ Pi X 3 are each independently an oxygen atom or a sulfur atom, and two at least of these 2 X PI is an oxygen atom, I 1 ,
  • R 2 and R 3 each independently represent a 23-hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • XR 5 In the general formula (2), X 4 , X 5 , 6 and 7 each independently represent an oxygen atom or a sulfur atom, and at least three of these are oxygen atoms; 4, R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 3 0.
  • hydrocarbon group having 1 to 30 carbon atoms represented by 1 to! ⁇ 6 include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, and an alkyl-substituted aryl group. And arylalkyl groups.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a pendecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group.
  • alkyl groups such as a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group (the alkyl groups may be linear or branched).
  • Examples of the above cycloalkyl group include a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cyclohexyl group.
  • Examples of the above alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentinole group, a methinoleethynolecyclopentyl group, Clopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group, getylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, getylcycloheptyl group, etc.
  • An alkylcycloalkyl group having 6 to 11 carbon atoms (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary).
  • alkenyl group examples include a butenyl group, a pentyl group, a hexyl group, a hepturyl group, an otaturyl group, a nonenyl group, a decenyl group, a pentadecenyl group, a dodecyl group, a tridecyl group, a tetradecyl group, Alkenyl groups such as pentadecenyl group, hexadecenyl group, heptadecenyl group and octadecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is arbitrary) Can be mentioned.
  • Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group.
  • Examples of the alkylaryl group include, for example, a trinole group, a xylyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an otatinolphenylenol group, An alkylaryl group having 7 to 18 carbon atoms such as a ruphenyl group, a decylphenyl group, a didecylphenyl group, and a dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position of the aryl group) Is also optional).
  • arylalkyl group examples include arylalkyl having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutynole group, phenylolepentyl group, and phenylhexynole group.
  • Groups (these alkyl groups may be linear or branched).
  • the hydrocarbon group having 1 to 30 carbon atoms represented by the above scale 1 to! ⁇ 6 is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, and 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 (1) include the following phosphorus compounds.
  • X i X 3 in the general formula (1) are oxygen atoms.
  • Examples of the phosphorus compound represented by the general formula (2) include the following phosphorus compounds.
  • X 4 to X 7 in the general formula (2) are oxygen atoms.
  • a metal base such as a metal oxide, a metal hydroxide, a metal carbonate, a metal chloride, ammonia
  • a part or all of the remaining acidic hydrogen was neutralized by the action of a nitrogen compound such as an amine compound having only a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group containing a hydroxyl group in the molecule. Salts may be mentioned.
  • the metal in the above metal base include lithium metal, lithium, sodium, potassium, cesium and other alkaline metals, calcium, magnesium, barium and other alkaline earth metals, zinc, copper, iron, lead, nickel, and the like.
  • examples include heavy metals such as silver, manganese, and molybdenum.
  • alkaline earth metals such as lithium, calcium, and magnesium, and zinc are preferred.
  • the structure of the metal salt of the phosphorus compound varies depending on the valency of the metal and the number of OH groups or SH groups of the phosphorus compound, and thus the structure is not limited at all.
  • a compound having the structure represented by the following formula is considered to be obtained as a main component. It is thought that molecules also exist.
  • a compound having a structure represented by the following formula is considered to be obtained as a main component. It is considered that a polymerized molecule is also present.
  • the nitrogen compound include ammonia, monoamine, diamine, and polyamine.
  • alkyl group which may be linear or branched An alkyl group which may be linear or branched); ethyluamine, propenyla! Alkenylamine having an alkenyl group having 2 to 30 carbon atoms (these alkenyl groups may be straight-chain or branched), such as amine, ptenylamine, otaturamine and oleylamine; methanolamine , Ethanolamine, Propanolamine, Butanolamine, Pentanolamine, Hexanolamine, Heptanolamine, Octanolamine, Nonanolamine, Methanolethanolamine, Methanolpropanolamine, Methanolbutanolamine, Ethanol Pronoanolamine Alkanolamines having 1 to 30 carbon atoms such as ethanol butanolamine and propanol butanolamine (these alcohol groups may be straight-chain or branched); Methylenediamine Alkylenediamines having an anolex
  • nitrogen compounds those having an alkyl or alkenyl group having 10 to 20 carbon atoms such as decylamine, dodecylamine, dodecyldimethylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine, and stearylamine.
  • alkyl or alkenyl group having 10 to 20 carbon atoms such as decylamine, dodecylamine, dodecyldimethylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine, and stearylamine.
  • Aliphatic amines (which may be linear or branched) are preferred examples.
  • these components (A) can be arbitrarily compounded.
  • the content of the component (A) is not less than 0.05% by mass, preferably not less than 0.01% by mass, particularly preferably not less than 0.01% by mass in terms of phosphorus element based on the total amount of the composition. Is at least 0.2% by mass, while its content is at most 0.5% by mass, preferably at most 0.2% by mass, more preferably at most 0.1% by mass, still more preferably Is 0.08% by mass or less.
  • the content of the component (A) is less than 0.05% by mass as a phosphorus element, there is no effect on wear resistance, and the amount is 0.5% by mass.
  • the ratio exceeds / 0 , it is not preferable for use in an internal combustion engine because phosphorus may adversely affect the exhaust gas aftertreatment device.
  • the content of the component (A) is 0.08% by mass or less, particularly 0.05% by mass or less as a phosphorus element, the effect on the exhaust gas aftertreatment device can be significantly reduced. Particularly preferred.
  • the compound containing sulfur can also be contained within the range of the above-mentioned phosphorus element amount, but preferably, the content is 0 in terms of sulfur element. 1% by mass or less, more preferably 0.08% by mass or less, and most preferably contains no sulfur-containing compound.
  • an amine compound for example, the component (D), the nitrogen compound described above, or the amine compound of the component (E) It is particularly preferable to mix an antioxidant or a mixture thereof with the component (A), and dissolve or react the resulting product or reaction product, and to blend the resulting product as an oil-soluble additive in a lubricating oil composition.
  • oil-soluble additives include, for example,
  • the component (A) and the amine compound are preferably placed in an organic solvent such as hexane, toluene, or decalin at 15 to 150 ° C, preferably 30 to 120 ° C, and particularly preferably 40 to 100 ° C. 10 minutes to 5 hours, preferably 20 minutes to 3 hours, particularly preferably 3 to 90 ° C. It is obtained by mixing and dissolving or reacting for 0 minute to 1 hour and distilling off the solvent by distillation under reduced pressure or the like.
  • an organic solvent such as hexane, toluene, or decalin
  • the component (B) in the lubricating oil composition of the present invention is zinc dithiophosphate (ZDTP), and specifically, zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, Zinc hexyldithiophosphate, zinc diheptinoresitiophosphate, and zinc dioctyldithiophosphate, etc., having 3 to 18 carbon atoms, preferably 3 to 10 carbon atoms, are linear or branched Primary, secondary or tertiary, preferably primary or secondary) having 6 to 6 carbon atoms such as zinc dialkyldithiophosphate having an alkyl group; zinc diphenyldithiophosphate and zinc ditolyldithiophosphate; 18, preferably di ((alkyl) aryl) zinc dithiophosphate having an aryl group or an alkylaryl group having 6 to 10 carbon atoms, and a mixture thereof.
  • the lubricating oil composition of the present invention contains the above-mentioned component (A) as a main component as a phosphorus compound, even if it does not contain the component (B), long-drain performance such as oxidation stability and base number retention can be obtained.
  • a composition which is extremely excellent in high-temperature detergency and further excellent in a friction reducing effect can be obtained.
  • the content of the component (B) is 0.05% by mass or less in terms of a phosphorus element based on the total amount of the composition, and preferably 0.3% by mass. %, More preferably 0.01% by mass or less, and most preferably no component (B).
  • (B) zinc dithiophosphate is used as a main component or alone as a phosphorus compound, that is, when the lubricating oil composition of the present invention satisfies the above requirement (IV), its content Is less than 0.05 mass% in terms of phosphorus, based on the total amount of the composition, so that its effect is reduced as compared with the case where component (A) is contained as a main component as a phosphorus compound. A high friction reducing effect can be obtained.
  • the content of the component (B) is preferably from 0.01 to 0.05 mass%. When the content of the component (B) exceeds 0.08% by mass in terms of the phosphorus element based on the total amount of the composition, it is difficult to obtain a sufficient effect.
  • the lubricating oil composition of the present invention when it satisfies the above requirement (IV), it may contain the component (A).
  • the component (C) in the lubricating oil composition of the present invention is a metal-based detergent, for example, an alkali metal sulfonate or an alkaline earth metal sulfonate, an alkaline earth metal phenate or an alkaline earth metal phenate, or an alkaline earth metal phenate.
  • examples include lithium metal salicylate or alkaline earth metal salicylate, alkali metal phosphonate or alkaline earth metal phosphonate, or a mixture thereof.
  • alkali metal or alkaline earth metal sulfonate for example, an alkyl aromatic compound having a molecular weight of 100 to 150, preferably 200 to 700 is used.
  • Alkali metal salts or alkaline earth metal salts of alkyl aromatic sulfonic acids obtained by the conversion are preferably used, particularly magnesium salts and Z or calcium salts.
  • Specific examples of the alkyl aromatic sulfonic acids include: Examples include so-called petroleum sulfonic acids and synthetic sulfonic acids.
  • the petroleum sulfonic acid generally, a so-called mahoganic acid, which is obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of a mineral oil and is by-produced during the production of white oil.
  • the synthetic sulfonic acid include an alkylbenzene having a linear or branched alkyl group, which is obtained as a by-product from an alkylbenzene production plant used as a raw material for detergents or obtained by alkylating a polyolefin to benzene. Is used as a raw material, and a sulfonated product thereof, or a sulfonated product of dino-naphthalene is used.
  • the sulfonating agent used for sulfonating these alkyl aromatic compounds is not particularly limited, but fuming sulfuric acid or sulfuric acid is usually used.
  • alkali metal or alkaline earth metal phenate more specifically, an alkylphenol having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms
  • Alkali metal salts or alkyl earth metal salts of alkyl salicylic acids having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, particularly magnesium salts And / or calcium salts are preferably used.
  • Alkali metal or alkaline earth metal sulphonate, alkali metal or alkaline earth metal phenate and alkali metal or alkaline earth metal salicylate include alkyl aromatic sulfonic acid, aryl phenol, alkyl phenol sulfa Mannich reaction products of alkyls and alkylphenols, alkylsalicylic acid, etc., directly react with metal bases such as oxides and hydroxides of alkali metals or alkaline earth metals, or once sodium salt or potassium Not only neutral salts (normal salts) obtained by substituting alkaline earth metal salts with alkaline earth metal salts such as lime salts, but also these neutral salts (normal salts) and excess alkali metal or alkali Earth metal salt or alkaline metal or alkaline earth metal base (water of alkaline metal or alkaline earth metal Or neutral salts in the presence of carbon dioxide or boric acid or borate are converted to alkali metals or alkaline earth metals. And perbasic salt
  • Metal-based detergents are usually commercially available diluted with a light lubricating base oil or the like, and are available, but generally have a metal content of 1.0 to 20. wt%, preferably 2.0 to 1 6 mass 0/0 is preferable to use those.
  • the total base number of the component (C) is from 0 to 500 mg KO HZ g, preferably from 20 to 450 mg KOH / g.
  • One or more of sulfonate, phenate, salicylate and the like can be used in combination.
  • the term “total base number” as used herein means the total base number by the perchloric acid method measured in accordance with 7 of JISK 2501 “Testing methods for petroleum products and lubricating oils in Japan”. I do.
  • the component (C) of the present invention is not particularly limited in its metal ratio, and a metal ratio of usually 20 or less can be used.
  • the metal ratio is 2.3 or less, more preferably 1.5.
  • the metal-based cleaning agent be made of a metal-based detergent having a metal ratio of 2.3 or less, more preferably 1.3 or less.
  • a series of detergents can be used alone or in combination of two or more.
  • the metal ratio is expressed by the valence of the metal element in the metal-based detergent X the content of the metal element (mo 1%) / the content of the soap group (mo 1%).
  • Potassium, magnesium, and the like, and the soap group means a sulfonic acid group, a salicylic acid group, and the like.
  • an alkali metal salicylate or an alkaline earth metal salicylate is particularly preferable because it has a large friction reducing effect due to low ash and has excellent long drain properties.
  • the upper limit of the compounding amount when the component (C) is contained is not particularly limited as long as the sulfated ash content of the composition is 0.8% by mass or less. Although it can be adjusted by the content of the additive, it is preferably 0.15% by mass, more preferably 0.11% by mass, particularly preferably 0.1% by mass in terms of the metal element based on the total amount of the composition. 0% by mass.
  • the lower limit is usually 0.01% by mass, preferably 0.02% by mass, particularly preferably 0.05% by mass.
  • any ashless dispersant used in lubricating oils can be used, and for example, a straight chain or a branched chain having 40 to 400 carbon atoms.
  • examples include a nitrogen-containing compound having at least one branched alkyl group or alkenyl group in a molecule or a derivative thereof, and a modified product of alkenyl succinic acid imide. One or two or more arbitrarily selected from these can be blended.
  • the carbon number of this alkyl group or alkenyl group is 40 to 400, preferably 60 to 350.
  • the solubility of the compound in the lubricating base oil decreases, while when the number of carbon atoms in the alkyl group or alkenyl group exceeds 400, the lubricating oil composition
  • the low-temperature fluidity of the material Each is not preferred.
  • This alkyl group or alkenyl group may be linear or branched, but is preferably, for example, an oligomer of an olefin such as propylene, 1-butene or isobutylene, or a copolymer of ethylene and propylene. Derived branched alkyl groups and branched alkenyl groups are exemplified.
  • component (D) include, for example, the following compounds, and 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 alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • (D-3) a polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof.
  • (D-1) succinic acid imide more specifically, Examples include compounds represented by the following general formulas (3) and (4).
  • R 2 Represents an alkyl group or an alkyl group having 40 to 400, preferably 60 to 350 carbon atoms, and h represents an integer of 1 to 5, preferably 2 to 4.
  • R 21 and R 22 are each independently 40 to 4 carbon atoms. And preferably represents 60 to 350 alkyl groups or alkyl groups, and is preferably a polypter group. i represents an integer of 0 to 4, preferably 1 to 3.
  • succinic acid imid includes a so-called monotype succinic acid imid represented by formula (3) in which succinic anhydride is added to one end of a polyamine, and a formula (in which succinic anhydride is added to both ends of polyamine). And the so-called bis-type succinic acid imid represented by 4).
  • the composition of the present invention may contain any of them or a mixture thereof.
  • the method for producing these succinic imides is not particularly limited.
  • a compound having an alkyl group or an alkenyl group having 40 to 400 carbon atoms is reacted with maleic anhydride at 100 to 200 ° C. It can be obtained by reacting the resulting alkyl or arcel succinic acid with a polyamine.
  • the polyamine include, for example, ethylene triamine, triethylene tetramine, tetraethylene pentamine, and ethylene hexamine.
  • examples of the above (D-2) benzylamine include compounds represented by the following general formula (5).
  • R 2 3 the number 4 0-4 0 0 atoms, preferably an alkyl or alkenyl group having 6 0 to 3 5 0, j is 1 to 5, preferably 2 to 4 Indicates an integer.
  • a polyolefin such as propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer is reacted with phenol to form an alkylphenol, and It can be obtained by reacting formaldehyde with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by a Mannich reaction.
  • a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by a Mannich reaction.
  • R 24 represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and k represents an integer of 1 to 5, preferably 2 to 4.
  • the method for producing this polyamine is not limited at all.
  • polyolefin such as propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer
  • ammonia ethylenediamine, diethylenetol, etc. It can be obtained by reacting a polyamine such as liamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • the derivatives of the nitrogen-containing compound mentioned as an example of the component (D) specifically, for example, a monocarboxylic acid having 1 to 30 carbon atoms (fatty acid, etc.)
  • a polycarboxylic acid having 2 to 30 carbon atoms such as an acid, trimellitic acid, and pyromellitic acid
  • a so-called acid-modified compound By reacting a polycarboxylic acid having 2 to 30 carbon atoms such as an acid, trimellitic acid, and pyromellitic acid to neutralize or amidate a part or all of the remaining amino and / or imino groups, A so-called acid-modified compound; a so-called boron-modified compound in which boric acid acts on the above-mentioned nitrogen-containing compound to neutralize or amidate a part or all of the remaining amino and / or imino groups; A sulfur-modified compound obtained by reacting a sulfur-containing compound with a nitrogen-containing compound; and a modified compound obtained by combining the above
  • the boric acid-modified compound of alkenyl succinic acid imid has excellent heat resistance and antioxidant properties, and is effective in the lubricating oil composition of the present invention to further enhance the base number retention and high-temperature detergency. .
  • the component (D) When the component (D) is contained in the lubricating oil composition of the present invention, its content is usually from 0.01 to 20% by mass, preferably from 0.1 to 10% by mass, based on the total amount of the lubricating oil composition. It is expressed in mass%. 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.
  • (ii) a phenolic acid Antioxidants Pamine-based antioxidants, metal-based antioxidants, etc. can be used as long as they are generally used in lubricating oils. By adding the antioxidant, the antioxidant property of the lubricating oil composition can be further enhanced, so that the base number maintenance property and high-temperature detergency can be further enhanced.
  • phenolic antioxidants examples include 4,4, -methylenebis (2,6-di-tert-butynolephenore) and 4,4,1-bis (2,6-di-tert-butinolephenol).
  • amine-based antioxidants examples include, for example, ebony, phenol- ⁇ -naphthylamine, thiol-fueryl-a-naphthylamine, and dianole-kyldiphenylamine. 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 thereof is 5% by mass or less, preferably 3% by mass or less, more preferably 2.0% by mass based on the total amount of the lubricating oil composition. 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 compounding amount.
  • the content thereof is preferably 0.1% by mass or more based on the total amount of the lubricating oil composition in order to further enhance the base number maintaining property and the high-temperature detergency during the lubricating oil deterioration process. 1% by mass or more.
  • the lubricating oil composition of the present invention comprises a lubricating base oil containing at least one phosphorus compound selected from the group consisting of the component (A) and the component (B), and the components (C) to (E).
  • a lubricating oil composition comprising at least one additive selected from the group consisting of: and having any one of the following requirements (I) to (IV): .
  • the component (A) is contained as a main component as a phosphorus compound, and the sulfated ash content of the composition is 0.8% by mass or less.
  • the component (A) is contained as a main component, and (F) a sulfur-containing organic molybdenum complex is contained in an amount of 0.0001 to 0.2% by mass in terms of molybdenum element, based on the total amount of the composition. And the sulfated ash content of the composition is not more than 1.2% by mass.
  • the component (A) is contained as a main component
  • (G) The ashless friction modifier is contained, and the sulfated ash content of the composition is 1.2% by mass or less.
  • (IV) As a phosphorus compound, the component (B) is contained as a main component, and (G) The ashless friction modifier is contained, and the content of the component (B) is converted to elemental phosphorus based on the total amount of the composition. Not more than 0.05% by mass and the amount of sulfated ash in the composition not more than 1.2% by mass.
  • the requirement (I) is when the component (A) is contained as a main component as a phosphorus compound.
  • the amount of sulfated ash in the yarn composition is 0.8% by mass or less.
  • the sulfated ash content of the composition is preferably 0.6% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less.
  • Specific examples of the (F) sulfur-containing organic molybdenum complex in the requirement (ii) include organic molybdenum complexes containing sulfur in the molecule, such as molybdenum dithiophosphate and molybdenum dithiocarbamate.
  • molybdenum dithiophosphate specifically, for example, a compound represented by the following general formula (6) can be used.
  • I 11 , R 12 , R 13 and R 14 may be the same or different and each have 1 to 30 carbon atoms, preferably 5 to 18 carbon atoms, more preferably An alkyl group of 5 to 12 or 6 to 18 carbon atoms, preferably 10 to 15 carbon atoms
  • Alkyl represents a hydrocarbon group such as an aryl group.
  • ⁇ 2 , ⁇ 3 and ⁇ 4 each independently represent a sulfur atom or an oxygen atom.
  • alkyl group examples include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.
  • Preferred examples of the (alkyl) aryl group include a phenyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, an octylphenyl group, a noerphenyl group, A decylphenyl group, a pendecylphenyl group, a dodecylphenyl group, and the like.
  • the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, or may be a linear or branched alkyl group. May be.
  • these (alkyl) aryl groups include all substituted isomers in which the substitution position of the alkyl group on the aryl group is different.
  • molybdenum dithiophosphate examples include molybdenum diethyl dithiophosphate, molybdenum dipropyl dithiophosphate, molybdenum disulfide dibutyl dithiophosphate, molybdenum dipentyl dithiophosphate and molybdenum disulfide.
  • molybdenum dithiophosphates compounds having a different number of carbon atoms and different or different hydrocarbon groups in one molecule can also be preferably used.
  • molybdenum dicarbamate for example, a compound represented by the following general formula (7) can be used.
  • R 15 , R 16 , R 17 and R 18 may be the same or different, and each have 2 to 24 carbon atoms, preferably alkyl having 4 to 13 carbon atoms.
  • a hydrocarbon group such as a (alkyl) aryl group having 6 to 24 carbon atoms, preferably 10 to 15 carbon atoms.
  • the ⁇ 5, ⁇ 6, ⁇ 7 and Upsilon 8 are each independently represents a sulfur atom or an oxygen atom.
  • alkyl group examples include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.
  • Preferred examples of the (alkyl) aryl group include a phenyl group, a tolyl group, an ethyl phenol group, a propynolepheninole group, a butyl phenyl group, a pentyl phenyl group, a hexyl phenyl group, an octyl phenyl group, a nonyl phenyl group and a decynole phenyl group.
  • Groups such as a phenyl group, a pendecyl phenyl group, and a dodecyl phenyl group
  • the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, or may be a linear or branched alkyl group. May be.
  • these (alkyl) aryl groups include all substituted isomers in which the substitution position of the alkyl group on the aryl group is different.
  • molybdenum dithiocarbamate other than the above-mentioned structure dithio or polytrimononuclear molybdenum as disclosed in WO98 / 26030 or WO99 / 3113 may be used. And those having a structure in which a carbamate group is coordinated.
  • molybdenum dithiocarbamate examples include molybdenum diethyl dithiocarbamate, molybdenum dipropyl dithiocarbamate, molybdenum dibutyl dithiocarbamate, molybdenum dipentyl dithiocarbamate, and molybdenum dihexyl sulfide.
  • Dithiocarbamate molybdenum dioctyl sulfide Dithiocarbamate, molybdenum didecyldithiocarbamate, molybdenum sulfide Dendidodecyldithiocarbamate, molybdenum sulfide (butylphenyl) dithiocarbamate, molybdenum sulfide (nonylphenyl) dithiocarbamate, oxymolybdenum decyldithiocarbamate, oxymolybdenum dipropyldithiocarbamate Palmate, oxymolybdenum diptyl dithiocarbamate, oxymolybdenum dipentyl dithiocarbamate, oxymolybdenum disulfide hexyl dithiocarbamate, oxymolybdene dioctyl sulfide Dithiocarbamate, Oxymolybdenum
  • molybdenum dithiocarbamates compounds having a hydrocarbon group having a different number of carbon atoms and / or structure in one molecule can also be preferably used.
  • Other organic molybdenum complexes containing sulfur include molybdenum compounds (for example, molybdenum oxides such as molybdenum dioxide and molybdenum trioxide, orthomolybdic acid, paramolybdic acid, and molybdenum acid such as (poly) molybdenum sulfide.
  • Metal salts of these molybdic acids, molybdates such as ammonium salts, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum polysulfide, etc., molybdenum sulfide, molybdenum sulfide, metal salts of molybdenum sulfide or amine salts , Molybdenum halides such as molybdenum chloride) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mecaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di Chi O) Hydro Cal bilge Chio phosphonate) disulfide, organic (poly) sulfates eyed include complexes like the sulfurized esters) or other organic compounds.
  • molybdates such
  • (F) content of the component the total amount of the composition, of molybdenum terms of element amount, 0. 0 0 1-0. 2 mass 0/0, preferably 0. 0 1-0. It is preferably 15% by mass, particularly preferably from 0.02 to 0.1% by mass.
  • content of the component (F) exceeds 0.2% by mass, it is difficult to obtain a friction reduction effect commensurate with the content, increase ash and sulfur content, and may deteriorate storage stability. is there.
  • the sulfated ash content of the composition is 1.2% by mass or less, preferably 1.0% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less, and particularly preferably 0% by mass or less. Less than 5% by mass.
  • any compound usually used as a friction modifier for lubricating oils can be used.
  • examples thereof include a hydrocarbon group having 6 to 30 carbon atoms, preferably an alkyl group or an alkenyl group, especially a linear alkyl group or a linear alkenyl group having 6 to 30 carbon atoms in the molecule.
  • Fatty acid esters, amine compounds, etc. which also have one.
  • straight-chain alkyl group or straight-chain alkenyl group having 6 to 30 carbon atoms specifically, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a pentadecyl group, a dodecyl group, a tridecyl group, Tetradecyl, pentadecyl, hexadecinole, heptadecyl, octadecyl, nonadecyl, icosyl, henycosinole, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl Alkyl groups such as nonacosyl group and triacontyl group (these alkyl groups may be straight-chain or branched); hexyl group, heptenyl group,
  • the fatty acid ester may be a straight-chain or branched, preferably straight-chain, having 7 to 31 carbon atoms.
  • Esters of a chain fatty acid with an aliphatic monohydric alcohol or an aliphatic polyhydric alcohol can be exemplified.
  • the amine compound a linear or branched, preferably linear aliphatic monoamine having 6 to 30 carbon atoms, a linear or branched, preferably linear aliphatic polyamine, or a fatty acid thereof. Examples thereof include an alkylene oxide adduct of an aromatic amine.
  • fatty acid esters of a fatty acid having 12 to 20 carbon atoms and glycerin / sorbitan among which glycerin monoester and sorbitan monoester, are preferred, and glycerin monoester of oleic acid is particularly preferred.
  • the content of the (G) ashless friction modifier is not particularly limited, but is usually preferably 0.1% by mass or more, more preferably, based on the lubricating oil composition. 0.2% by mass or more. Further, the content is preferably 1% by mass or less, more preferably 0.8% by mass or less. If the content of the component (G) exceeds 1% by mass, the storage stability may be poor.
  • the sulfated ash content of the composition in the requirements (II) and (IV) is 1.2 mass% or less, preferably 1.0 mass% or less, more preferably 0.8 mass% or less, and It is preferably 0.6% by mass or less, more preferably 0.5% by mass, and particularly preferably 0.4% by mass.
  • the component (B) is contained as a main component or alone as a phosphorus compound, and the component (G) is contained.
  • the content of the component (B) is determined based on the lubricating oil composition based on phosphorus element.
  • the equivalent amount is 0.05% by mass or less, preferably 0.01% to 0.05% by mass, particularly preferably 0.04% to 0.05% by mass.
  • any additive generally used in lubricating oils can be added according to the purpose.
  • additives include, for example, anti-wear agents other than component (A) and component (B), friction modifiers other than component (G), viscosity index improvers, corrosion inhibitors, and anti-oxidants.
  • additives such as a demulsifier, a metal deactivator, a defoamer, and a colorant.
  • Examples of the antiwear agent other than the components (A) and (B) include disulfides, olefin sulfides, sulfide oils, dithiophosphoric zinc zinc, and dithiophosphoric acid. And yellow-containing compounds such as dithiocarbamate. Since these sulfur-containing wear inhibitors tend to inhibit the friction reducing effect of the present invention, the content is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, based on the total amount of the composition. More preferably,
  • Examples of the friction modifier other than the component (G) and the component (E) include a molybdenum amine complex, a molybdenum-succinic imid complex, molybdenum disulfide, a long-chain fatty acid, a long-chain aliphatic alcohol, and a long-chain aliphatic ether. And fatty acid amides.
  • 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 methacrylate esters containing a nitrogen compound; a non-dispersion type or dispersion type ethylene monoolefin copolymer (propylene as ⁇ -olefin, 1-butene; 1-pentene, etc.) or hydrides thereof, polyisobutylene or hydrogenated products thereof, hydrides of styrene-one-gen copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes.
  • ethylene monoolefin copolymer propylene as ⁇ -olefin, 1-butene; 1-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 the dispersion type and the ⁇ dispersion type polymethalate.
  • 0,000 to 900,000 is polyisobutylene or a hydride thereof, it is usually 800 to 5,000, preferably 1,000 to 4,000.
  • 0 is ethylene- ⁇ -olefin copolymer or a hydride thereof, it is usually 800 to 500,000, preferably 3,000 to 200,000. ⁇ is 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.
  • Corrosion inhibitors include, for example, benzotriazoles, Compounds, thiadiazole compounds, and imidazole compounds.
  • the protective agent include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.
  • demulsifier examples include a polyalkylene glycol-based nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
  • metal deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolylol 2 , 5_bisdialkyldithiocarbamate, 2— (alkyldithio) benzimidazole, and jS— (o-potoxybenzylthio) propionnitryl.
  • 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 has a sulfur content of 0.5% by mass or less, preferably 0.3% by mass or less, depending on the selection of the lubricating base oil, each component and various additives. It is possible to provide a low sulfur lubricating oil composition having excellent low friction properties, more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less. In particular, it is also possible to obtain a lubricating oil composition substantially containing no sulfur at 0.01% by mass or less, or even 0.05% by mass or less.
  • the lubricating oil composition of the present invention is not only excellent in friction reducing effect, but also excellent in wear prevention effect, long drain property (oxidation stability, base number maintenance property, etc.) and high-temperature detergency, It can be preferably used as a lubricating oil for internal combustion engines such as gasoline engines, motorcycle engines, diesel engines, gas engines, etc. for motorcycles, automobiles, power generation, ships, etc., and has a low ash content, low sulfur, and low phosphorus. Therefore, it is particularly suitable for an internal combustion engine equipped with an exhaust gas aftertreatment device.
  • the valve operating mechanism is a direct drive type or a roller follower type, particularly a roller follower type, the effect of reducing friction is particularly exhibited.
  • low-sulfur fuels for example, gasoline, gas oil or kerosene having a sulfur content of 50 mass ppm or less, more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less, or a sulfur content of 1 mass ppm
  • a lubricating oil for internal combustion engines particularly a lubricating oil for gas engines, using the following fuels (LPG, natural gas, hydrogen substantially free of sulfur, dimethyl ether, alcohol, GTL (gas to liquid) fuel, etc.)
  • LPG natural gas, hydrogen substantially free of sulfur, dimethyl ether, alcohol, GTL (gas to liquid) fuel, etc.
  • lubricating oils that require any of the above-described performances of the present invention, for example, lubricating oils for drive systems of automatic or manual transmissions, grease, wet brake oils, hydraulic oils, turbine oils It can also be suitably used as a lubricating oil such as compressor oil, bearing oil, refrigerating machine oil and the like.
  • a lubricating oil composition of the present invention (Examples 1-2) and a comparative lubricating oil composition (Reference Example 1 and Comparative Example 1) were prepared.
  • Alkyl group secbutyl / sec hexyl group, phosphorus content: 7.2 mass, sulfur content: 15.2 mass%, zinc content: 7.80 / 0 , sulfated ash content: 11.7 mass%
  • Example 1 using the metal-based detergent-1 having a metal ratio of 2.3 or less was obtained by mixing the metal-based detergent-2 (metal ratio: 2.7) in the composition of Reference Example 1.
  • the friction reduction effect is superior to that when the amount is reduced, and it has been confirmed that there is no problem with the wear prevention performance of the valve train.
  • the composition in which the sulfated ash content of the composition exceeds 0.8% by mass deteriorates the friction reducing effect and reduces the wear resistance. Inferior results.
  • the lubricating oil composition of the present invention can exert a friction reducing effect even when the valve operating mechanism is an engine other than a direct-acting type or a roller follower type, but the valve operating mechanism is a direct-acting type or a roller follower type. Since the effect of reducing friction is particularly exhibited in the case of an engine, application to such an engine is most preferable.
  • Lubricating oil compositions of the present invention (Examples 3 to 7) and comparative lubricating oil compositions (Comparative Examples 2 to 4) having the compositions shown in Tables 2 and 3 were respectively prepared. The following performance evaluation tests were performed on each of the obtained compositions.
  • Oil temperature 80 ° C, 95 ° C
  • Viscosity index 125, NOACK evaporation: 8% by mass
  • Alkyl group sec butyl / sec hexyl group, phosphorus content: 7.2% by mass, sulfur content: 15.2% by mass, zinc content: 7.8 ⁇ 1 ⁇ 2, sulfated ash content: 11.7% by mass
  • the lubricating oil thread and component (Examples 3 and 4) of the present invention containing the components (A) and (G)
  • the component (B) is used in place of the component (A) in the same amount in terms of the amount of phosphorus element, and shows a very excellent friction reduction effect as compared with the case of the composition not containing the component (G) (Comparative Example 2).
  • the composition of Comparative Example 3 in which the component (B) and the component (G) are used in combination, the composition of Comparative Example 2 hardly exhibits a friction reducing effect. Therefore, as shown in Example 3,
  • the lubricating oil composition of the present invention containing the components (A) and (G) was used in a roller follower type engine with a valve train (Examples 5 and 6). ⁇ 6) Even if component (B) and component (G) are used together, if the content of component (B) is 0.05% by mass or less in terms of phosphorus (Example 7), Compared to the case of using the same amount of component (B) as in Example 7 but not using component (G) (Comparative Example 4), it shows extremely excellent friction reducing effect. In particular, when the phosphoric acid triester was used (Examples 4 and 6), it was found that the friction reducing effect was excellent.
  • the lubricating oil composition of the present invention can exert a friction reducing effect even in the case of an engine other than a direct drive type or a roller follower type with a valve operating mechanism, but the valve operating mechanism is a direct hit type or a roller follower type. Since the effect of reducing friction is particularly exhibited in the case of an engine, it is most preferable to apply to such an engine.
  • Lubricating oil compositions of the present invention having compositions shown in Table 4 (Examples 8 to 11) and comparative lubricating oil compositions (Comparative Examples 5 to 9) were prepared.
  • the lubricating oil compositions of the present invention show excellent low friction performance. Especially when a metal-based detergent with a metal ratio of 2.3 or less is used
  • Example 10 It can be seen that a more excellent friction reducing effect is exhibited as compared with the case where a metal-based detergent having a metal ratio of more than 2.3 is used (Example 10). Further, instead of the component (A) in the composition of Example 9, zinc di (2-ethylhexyl) monothiophosphate was added in an amount of 0.05 mass in terms of phosphorus element. /. With respect to the lubricating oil composition contained therein, the result of the frictional property test was 0.048, confirming that the lubricating oil composition was also excellent in friction reducing effect.
  • the lubricating oil composition of the present invention is particularly excellent in the friction reducing effect when the valve operating mechanism of the engine is a direct hit type or a roller follower type. Further, the lubricating oil composition of the present invention can suppress the deterioration of the organic molybdenum compound itself because there is no sulfuric acid generation due to the decomposition of zinc dithiophosphate as compared with the case where zinc dithiophosphate is used. In addition to the effect of reducing friction, it also has excellent maintainability, anti-oxidation properties, long drainability such as base number maintenance, and high-temperature cleanliness.
  • the lubricating oil composition of the present invention not only exhibits excellent performance in reducing friction but also achieves low sulfur, low ash, and low phosphorus, and also has excellent long drain properties. It is. Therefore, in addition to lubricating oils for internal combustion engines, lubricating oils that require such performance, for example, lubricating oils for drive systems such as automatic or manual transmissions, grease, wet brake oils, hydraulic oils, turbine oils, It can be suitably used as a lubricating oil such as a compressor oil, a bearing oil, and a refrigerator oil.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Cette invention concerne une composition d'huile de graissage qui est remarquable en termes de réduction des frottements et d'espacement des vidanges, et qui convient tout particulièrement bien pour les moteurs thermiques. Cette composition comprend une huile de graissage de base, un composé phosphoré spécifique à raison de 0,005-0,5 % de phosphore en pourcentage de masse de la composition totale, et au moins un additif pris dans le groupe comprenant (C) des détergents métalliques, (D) des dispersants sans cendre et (E) des antioxydants, ainsi que (F) un complexe d'organomolybdène contenant du soufre et (G) un modificateur de coefficient de frottement sans cendres. Cette composition satisfait aux exigences spécifiées et à une teneur en cendres sulfatées ne dépassant pas un niveau déterminé.
PCT/JP2003/008338 2002-06-28 2003-06-30 Composition d'huile de graissage WO2004003117A1 (fr)

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US11/019,989 US7790659B2 (en) 2002-06-28 2004-12-22 Lubricating oil compositions

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JP4613265B2 (ja) * 2004-03-03 2011-01-12 Ｊｘ日鉱日石エネルギー株式会社 ローラーフォロワ型動弁系エンジン用潤滑油組成物
WO2005118758A1 (fr) * 2004-06-01 2005-12-15 Nippon Oil Corporation Composition d’une huile de lubrification pour transmission mécanique
US7704928B2 (en) 2004-06-01 2010-04-27 Nippon Oil Corporation Lubricating oil composition for manual transmission
US7531487B2 (en) 2004-08-18 2009-05-12 Walid Al-Akhdar Lubricating oil compositions with improved performance
US8133290B2 (en) 2004-10-12 2012-03-13 The Lubrizol Corporation Tartaric acid derivatives in fuel compositions
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US7651987B2 (en) 2004-10-12 2010-01-26 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
US8198222B2 (en) 2004-10-12 2012-06-12 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparations thereof
CN101040035B (zh) * 2004-10-12 2012-03-28 卢布里佐尔公司 在曲轴箱油中作为燃料经济性改进剂和抗磨剂的酒石酸衍生物及其制备
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US7807611B2 (en) 2004-10-12 2010-10-05 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
EP1835013A4 (fr) * 2004-10-19 2010-08-04 Nippon Oil Corp Formule d'huile lubrifiante
US20080020952A1 (en) * 2004-10-19 2008-01-24 Kazuhiro Yagishita Lubricant Composition
US8148307B2 (en) 2006-02-06 2012-04-03 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparations thereof
WO2007119299A1 (fr) * 2006-03-22 2007-10-25 Nippon Oil Corporation 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
EP1997871A4 (fr) * 2006-03-22 2010-04-28 Nippon Oil Corp Formule d'huile moteur à faible teneur en cendres
JP2010174221A (ja) * 2009-02-02 2010-08-12 Kyodo Yushi Co Ltd 潤滑油組成物及びグリース
US11345872B2 (en) 2020-01-30 2022-05-31 ExxonMobil Technology and Engineering Company Sulfur-free, ashless, low phosphorus lubricant compositions with improved oxidation stability

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CN100497560C (zh) 2009-06-10
CN1671827A (zh) 2005-09-21
EP1516910A4 (fr) 2010-01-27
EP1516910A1 (fr) 2005-03-23
AU2003241824A1 (en) 2004-01-19

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