WO2020095943A1 - Composition lubrifiante - Google Patents

Composition lubrifiante Download PDF

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Publication number
WO2020095943A1
WO2020095943A1 PCT/JP2019/043464 JP2019043464W WO2020095943A1 WO 2020095943 A1 WO2020095943 A1 WO 2020095943A1 JP 2019043464 W JP2019043464 W JP 2019043464W WO 2020095943 A1 WO2020095943 A1 WO 2020095943A1
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Prior art keywords
lubricating oil
oil composition
mass
less
composition according
Prior art date
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PCT/JP2019/043464
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English (en)
Japanese (ja)
Inventor
耕治 星野
慎太郎 楠原
明男 武藤
裕充 松田
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Ｊｘｔｇエネルギー株式会社
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Application filed by Ｊｘｔｇエネルギー株式会社 filed Critical Ｊｘｔｇエネルギー株式会社
Priority to EP19881130.9A priority Critical patent/EP3878931B1/fr
Priority to CN201980069747.3A priority patent/CN112888769B/zh
Publication of WO2020095943A1 publication Critical patent/WO2020095943A1/fr

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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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • 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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition for an internal combustion engine, and more particularly to a lubricating oil composition for a supercharged engine.
  • additives containing molybdenum and phosphorus tend to reduce the LSPI occurrence frequency, but friction modifiers containing molybdenum and antiwear agents containing phosphorus may decompose at high temperatures to form a deposit. There is. Therefore, when the amounts of the friction modifier containing molybdenum and the antiwear agent containing phosphorus are increased in order to reduce the LSPI generation frequency, there is a problem that the high temperature cleanability is deteriorated. That is, the technology for preventing LSPI and the technology for ensuring the performance required for the lubricating oil composition are sometimes contradictory, and a technology for achieving both of them is required.
  • an object of the present invention is to provide a lubricating oil composition for a supercharged engine, which is capable of providing coking resistance, LSPI suppression ability, and high temperature cleanability in a well-balanced manner.
  • the present inventors have used a specific polymer as a viscosity index improver in a lubricating oil composition in which a calcium-based detergent and a magnesium-based detergent are used in combination, and The inventors have found that the above problems can be solved by adjusting the amount of nitrogen within a specific range, and have completed the present invention.
  • the lubricating oil composition according to any one of [1] to [11] which does not contain poly (meth) acrylate as a viscosity index improver.
  • the lubricating oil composition according to the present invention can have a good balance of caulking resistance, LSPI suppression ability, and high temperature cleanability.
  • Such a lubricating oil composition can be suitably used for engine applications with a supercharger that requires a high degree of coking resistance.
  • the lubricating oil composition according to the present invention comprises at least (A) a lubricating base oil, (B) a calcium-based detergent, (C) a magnesium-based detergent, (D) a viscosity index improver, and (E). It comprises a nitrogen-containing dispersant, and may further comprise (F) an ashless friction modifier, (G) a molybdenum-containing compound, and (H) an antiwear agent.
  • the lubricating oil composition according to the present invention can be suitably used for an internal combustion engine, especially an engine with a supercharger. Further, the lubricating oil composition according to the present invention can be used for both gasoline and diesel engines, and can also be used for diesel engines.
  • each component constituting the lubricating oil composition according to the present invention will be described in detail.
  • the lubricating base oil is not particularly limited, and for example, a lubricating oil fraction obtained by distilling crude oil under atmospheric pressure and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrogenolysis, solvent removal.
  • the lubricating base oil include the base oils (1) to (8) shown below as raw materials, and the raw oil and / or the lubricating oil fraction recovered from the raw oil by a predetermined refining method.
  • a base oil obtained by refining and collecting a lubricating oil fraction can be mentioned.
  • Distillate oil of paraffinic crude oil and / or mixed crude oil by atmospheric distillation (2) Distillation oil of paraffinic crude oil and / or mixed crude oil under atmospheric pressure by vacuum distillation (WVGO) (3) Wax (slack wax, etc.) obtained by the dewaxing process of lubricating oil and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by gas-to-liquid (GTL) process, etc.
  • the predetermined purification methods include hydrocracking and hydrofinishing such as hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay.
  • Purification of clay Washing with chemicals (acid or alkali) such as washing with sulfuric acid and washing with caustic soda is preferable.
  • one of these purification methods may be used alone or two or more of them may be used in combination. When two or more purification methods are combined, the order is not particularly limited and can be appropriately selected.
  • the lubricating base oil the following base oil obtained by subjecting the base oil selected from the above base oils (1) to (8) or the lubricating oil fraction recovered from the base oil to a predetermined treatment ( 9) or (10) is particularly preferable.
  • the base oil selected from the above base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked, and the product or the product is recovered by distillation or the like.
  • a hydroisomerized base oil obtained by performing dewaxing treatment such as wax, or by performing distillation after performing the dewaxing treatment.
  • a base oil produced through a catalytic dewaxing step is preferable.
  • a solvent refining process and / or a hydrofinishing process may be further performed at an appropriate stage, if necessary.
  • the catalyst used for the hydrocracking / hydroisomerization is not particularly limited, but a complex oxide having a cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one type of the complex oxide.
  • Hydrogenolysis in which a metal having a hydrogenation ability (for example, one or more kinds of metals of Group VIa and Group VIII, etc.) is used as a carrier by combining the above and bound with a binder.
  • the hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.
  • the reaction conditions for hydrocracking / hydroisomerization are not particularly limited, but the hydrogen partial pressure is 0.1 to 20 MPa, the average reaction temperature is 150 to 450 ° C., the LHSV is 0.1 to 3.0 hr ⁇ 1 , and the hydrogen / oil ratio is It is preferably 50 to 20,000 scf / b.
  • the kinematic viscosity of the lubricating base oil at 100 ° C. is preferably 2.0 mm 2 / s or more, more preferably 2.5 mm 2 / s or more, further preferably 3.0 mm 2 / s or more, It is more preferably 3.5 mm 2 / s or more, preferably 8.0 mm 2 / s or less, more preferably 7.0 mm 2 / s or less, still more preferably 6.0 mm 2 / s. Or less, and more preferably 5.0 mm 2 / s or less.
  • the “kinematic viscosity at 100 ° C.” means the kinematic viscosity at 100 ° C. measured according to ASTM D-445.
  • the kinematic viscosity of the lubricating base oil at 40 ° C. is preferably 6.0 mm 2 / s or more, more preferably 8.0 mm 2 / s or more, still more preferably 10 mm 2 / s or more, and even more preferably at 15 mm 2 / s or more, and preferably not more than 40 mm 2 / s, more preferably not more than 30 mm 2 / s, more preferably 25 mm 2 / s or less, even more preferably 20 mm 2 / s It is below. If the kinematic viscosity of the lubricating base oil at 40 ° C.
  • kinematic viscosity at 40 ° C.” means the kinematic viscosity at 40 ° C. measured according to ASTM D-445.
  • the viscosity index of the lubricating base oil is preferably 100 or more, more preferably 110 or more, still more preferably 120 or more.
  • the viscosity index is within the above numerical range, the viscosity-temperature characteristics, heat / oxidation stability, and volatility-preventing property of the lubricating oil composition are improved, the friction coefficient is lowered, and the antiwear property is improved. it can.
  • the “viscosity index” means the viscosity index measured according to JIS K 2283-1993.
  • the density ( ⁇ 15 ) of the lubricating base oil at 15 ° C. is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less.
  • the density at 15 ° C. means the density at 15 ° C. measured in accordance with JIS K 2249-1995.
  • the pour point of the lubricating base oil is preferably -10 ° C or lower, more preferably -12.5 ° C or lower, and further preferably -15 ° C or lower. When the pour point is within the above numerical range, the low temperature fluidity of the entire lubricating oil composition can be improved.
  • pour point means a pour point measured according to JIS K 2269-1987.
  • the content of sulfur is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, and further preferably, from the viewpoint of improving heat / oxidation stability and reducing sulfur. It is 10 mass ppm or less.
  • sulfur content means a pour point measured according to JIS K 2541-2003.
  • The% C P of the lubricating base oil is preferably 70 or higher, more preferably 75 or higher, and even more preferably 80 or higher.
  • the viscosity-temperature characteristics, heat / oxidation stability and friction characteristics are good, and the additive solubility is good.
  • % C N of the lubricating base oil is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less.
  • The% C N of the lubricating base oil is preferably 1 or more, more preferably 4 or more. When the% C N of the lubricating base oil is within the above numerical range, the viscosity-temperature characteristic, the heat / oxidation stability and the friction characteristic are good, and the solubility of the additive is good.
  • % C A of the lubricating base oil is preferably 2 or less, more preferably 1 or less, further preferably 0.8 or less, and particularly preferably 0.5 or less.
  • the viscosity-temperature characteristics, heat / oxidation stability, and fuel economy will be good.
  • % C P ,% C N and% C A are the percentages of the number of paraffin carbon atoms to the total number of carbon atoms, which are determined by the method (ndM ring analysis) according to ASTM D 3238-85, respectively. , Naphthene carbon number to total carbon number, and aromatic carbon number to total carbon number. That is, the above-described% C P,% C preferred range of N and% C A are based on values determined by these methods, even lubricating base oil for example contains no naphthene, determined by the above The% C N given may show values above 0.
  • the content of the saturated component in the lubricating base oil is preferably 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more, based on the total amount of the lubricating base oil.
  • the ratio of the cyclic saturated component to the saturated component is preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less. , And more preferably 21% by mass or less.
  • the ratio of the cyclic saturated component in the saturated component is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the aromatic content in the lubricating base oil is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, still more preferably 3% by mass, based on the total amount of the lubricating base oil. % Or less, most preferably 2% by mass or less, and may be 0% by mass.
  • the content of the aromatic component is within the above numerical range, the viscosity-temperature characteristic, the heat / oxidation stability and the friction characteristic, and the volatility preventing property and the low temperature viscosity characteristic are improved.
  • aromatic content means a value measured according to ASTM D 2007-93.
  • Aromatic components usually include alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylated products thereof, and further compounds having four or more condensed benzene rings, pyridines, quinolines, phenols, naphthols and the like. An aromatic compound having a hetero atom is included.
  • the lubricating base oil Group II base oil, Group III base oil, Group IV base oil, Group V base oil, or a mixed base oil thereof of API base oil classification can be preferably used.
  • the API group II base oil is a mineral oil base oil having a sulfur content of 0.03 mass% or less, a saturated content of 90 mass% or more, and a viscosity index of 80 or more and less than 120.
  • the API group III base oil is a mineral oil base oil having a sulfur content of 0.03 mass% or less, a saturated content of 90 mass% or more, and a viscosity index of 120 or more.
  • API Group IV base oils are poly alpha-olefin base oils.
  • API Group V base oils are ester base oils.
  • a synthetic base oil may be used as the lubricating base oil.
  • synthetic base oils include poly- ⁇ -olefins and hydrides thereof, isobutene oligomers and hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate.
  • Di-2-ethylhexyl sebacate, etc. di-2-ethylhexyl sebacate, etc.
  • polyol ester trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.
  • polyoxyalkylene glycol dialkyldiphenyl ether
  • Examples thereof include polyphenyl ether, a mixture thereof, and the like, and among them, poly ⁇ -olefin is preferable.
  • the poly ⁇ -olefin is typically an oligomer or cooligomer of an ⁇ -olefin having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms (1-octene oligomer, decene oligomer, ethylene-propylene cooligomer, etc.) And their hydrogenation products.
  • the production method of the poly ⁇ -olefin is not particularly limited, but for example, polymerization such as a catalyst containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester.
  • polymerization such as a catalyst containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester.
  • a method of polymerizing an ⁇ -olefin in the presence of a catalyst can be mentioned.
  • the lubricating base oil may be composed of a single base oil component or may include a plurality of base oil components as the whole lubricating base oil.
  • the content of the lubricating base oil in the lubricating oil composition is usually 70% by mass or more, preferably 75% by mass or more, based on the total amount of the lubricating oil composition. %, More preferably 80% by mass or more, and usually 90% by mass or less.
  • the lubricating oil composition is a single grade oil, it is usually 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, based on the total amount of the lubricating oil composition, and usually It is 95 mass% or less.
  • R 1 represents a linear or branched chain having 6 to 21 carbon atoms, a saturated or unsaturated alkyl group or alkenyl group
  • m represents a degree of polymerization and represents an integer of 1 to 10
  • a Re represents a sulfide (—S—) group or a methylene (—CH 2 —) group
  • x represents an integer of 1 to 3.
  • R 1 may be a combination of two or more different groups.
  • the carbon number of R 1 in formula (1) is preferably 9 to 18, and more preferably 9 to 15. When the carbon number of R 1 is within the above numerical range, the solubility and heat resistance are good.
  • the degree of polymerization m in the formula (1) is preferably 1 to 4. When the degree of polymerization m is within this range, heat resistance can be improved.
  • a calcium salt of an alkylaromatic sulfonic acid obtained by sulfonating an alkylaromatic compound or a basic salt or an overbased salt thereof can be preferably exemplified.
  • the weight average molecular weight of the alkyl aromatic compound is preferably 400 to 1500, more preferably 700 to 1300.
  • the thing which sulfonated the alkylbenzene which has a group can be mentioned.
  • an alkylnaphthalene such as dinonylnaphthalene may be sulfonated.
  • the sulfonating agent used for sulfonating these alkyl aromatic compounds is not particularly limited, and for example, fuming sulfuric acid or sulfuric anhydride can be used.
  • the method for producing calcium salicylate is not particularly limited, and a known method for producing monoalkyl salicylate or the like can be used.
  • phenol is used as a starting material, and alkylation is performed using an olefin, and then monoalkyl salicylic acid obtained by carboxylation with carbon dioxide gas or the like, or salicylic acid is used as a starting material, and is alkylated using an equivalent amount of the above olefin.
  • the obtained monoalkylsalicylic acid or the like is reacted with a calcium base such as calcium oxide or hydroxide, or these monoalkylsalicylic acid or the like is once converted into an alkali metal salt such as a sodium salt or potassium salt, and then calcium.
  • Calcium salicylate can be obtained by performing metal exchange with salt. ..
  • Calcium detergent may be overbased with carbonate (calcium carbonate) or borate (calcium borate).
  • the method for obtaining a calcium-based detergent overbased with a calcium carbonate is not particularly limited, but, for example, calcium-based detergents (calcium phenate, calcium sulfonate, calcium salicylate in the presence of carbon dioxide gas) can be used. Etc.) and a neutral salt thereof are reacted with a calcium base (calcium hydroxide, oxide, etc.).
  • the method for obtaining a calcium-based detergent overbased with calcium borate is not particularly limited, but in the presence of boric acid or boric anhydride or borate, a calcium-based detergent (calcium-based detergent) can be used. Salt, calcium sulfonate, calcium salicylate, etc.) can be obtained by reacting with a calcium base (calcium hydroxide, oxide, etc.).
  • the total base number of the calcium-based detergent is not particularly limited and is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 100 mgKOH / g or more, and preferably 500 mgKOH / g. g or less, more preferably 400 mgKOH / g or less, and further preferably 350 mgKOH / g or less.
  • the total base number of the calcium-based detergent is within the above numerical range, the acid neutralizing property required for the lubricating oil can be maintained, and the high temperature detergency can be further improved.
  • the base number obtained by mixing is preferably within the above range.
  • the total base number is a value measured by ASTM D2896.
  • the content of the calcium-based detergent in the lubricating oil composition is 1100 mass ppm or more and 1900 mass ppm or less, preferably 1150 mass ppm or more, and more preferably 1200 mass as a calcium amount based on the total amount of the lubricating oil composition. ppm or more, preferably 1850 mass ppm or less, more preferably 1800 mass ppm or less.
  • the content of the calcium-based detergent is within the above numerical range, the high temperature detergency can be improved while maintaining the coking resistance and the LSPI suppressing ability.
  • an overbased salt of a magnesium salt of a compound having a structure represented by the following formula (3) can be preferably exemplified.
  • R 3 represents a linear or branched chain having 6 to 21 carbon atoms, a saturated or unsaturated alkyl group or alkenyl group, m represents a degree of polymerization and represents an integer of 1 to 10, and A Represents a sulfide (—S—) group or a methylene (—CH 2 —) group, and x represents an integer of 1 to 3.
  • R 3 may be a combination of two or more different groups.
  • the carbon number of R 3 in the formula (3) is preferably 9 to 18, and more preferably 9 to 15. When the carbon number of R 3 is within the above numerical range, the solubility and heat resistance are good.
  • the degree of polymerization m in the formula (3) is preferably 1 to 4. When the degree of polymerization m is within this range, heat resistance can be improved.
  • a magnesium salt of an alkylaromatic sulfonic acid obtained by sulfonating an alkylaromatic compound or a basic salt or an overbased salt thereof can be preferably exemplified.
  • the weight average molecular weight of the alkyl aromatic compound is preferably 400 to 1500, more preferably 700 to 1300.
  • alkyl aromatic sulfonic acid examples include so-called petroleum sulfonic acid and synthetic sulfonic acid.
  • Examples of the petroleum sulfonic acid include those obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil, and so-called mahogany acid, which is a by-product during the production of white oil.
  • the synthetic sulfonic acid a linear or branched alkyl obtained by recovering a by-product in an alkylbenzene production plant which is a raw material of a detergent or by alkylating benzene with a polyolefin.
  • magnesium salicylate or its basic salt or overbased salt can be preferably exemplified.
  • magnesium salicylate a compound represented by the following formula (4) can be preferably exemplified.
  • R 4's each independently represent an alkyl group or an alkenyl group having 14 to 30 carbon atoms, and M's represent magnesium.
  • R 4 may be a combination of different groups.
  • the method for producing magnesium salicylate is not particularly limited, and a known method for producing monoalkyl salicylate or the like can be used.
  • phenol is used as a starting material, and alkylation is performed using an olefin, and then monoalkyl salicylic acid obtained by carboxylation with carbon dioxide gas or the like, or salicylic acid is used as a starting material, and is alkylated using an equivalent amount of the above olefin.
  • the obtained monoalkylsalicylic acid or the like is reacted with a magnesium base such as magnesium oxide or hydroxide, or these monoalkylsalicylic acid or the like is once converted into an alkali metal salt such as sodium salt or potassium salt, and then magnesium.
  • Magnesium salicylate can be obtained by performing metal exchange with salt. ..
  • the magnesium-based detergent may be overbased with a carbonate (magnesium carbonate) or borate (magnesium borate).
  • the method for obtaining the magnesium-based detergent overbased with magnesium carbonate is not particularly limited, but, for example, in the presence of carbon dioxide gas, magnesium-based detergents (magnesium phenate, magnesium sulfonate, magnesium salicylate) can be used. Etc.) and a neutral salt thereof are reacted with a magnesium base (magnesium hydroxide, oxide, etc.).
  • the method for obtaining the magnesium-based detergent overbased with magnesium borate is not particularly limited, but the magnesium-based detergent (magnesium phosphate Salt, magnesium sulfonate, magnesium salicylate, etc.) can be obtained by reacting with a base of magnesium (hydroxide, oxide, etc.) of magnesium.
  • magnesium-based detergent magnesium phosphate Salt, magnesium sulfonate, magnesium salicylate, etc.
  • magnesium-based detergent magnesium phenate, magnesium sulfonate, magnesium salicylate, or a combination thereof can be used, and magnesium salicylate is preferably used.
  • the total base number of the magnesium-based detergent is not particularly limited and is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 100 mgKOH / g or more, and preferably 500 mgKOH / g. g or less, more preferably 400 mg KOH / g or less.
  • the base number obtained by mixing is preferably within the above range.
  • the total base number is a value measured by ASTM D2896.
  • the content of the magnesium-based detergent in the lubricating oil composition is, based on the total amount of the lubricating oil composition, preferably 100 mass ppm or more, more preferably 200 mass ppm or more, and further preferably 300 mass ppm as the amount of magnesium. It is above, and preferably 1000 mass ppm or less, more preferably 900 mass ppm or less, and further preferably 800 mass ppm or less.
  • the content of the magnesium-based detergent is within the above numerical range, the high temperature detergency can be further improved while maintaining the coking resistance and the LSPI suppressing ability.
  • Viscosity index improver examples include a styrene-diene copolymer and an ethylene- ⁇ -olefin copolymer, and a styrene-diene copolymer is preferably used. These viscosity index improvers can be used alone or in combination of two or more. By using these viscosity index improvers, the caulking resistance can be improved while maintaining the LSPI suppressing ability and the high temperature cleanability.
  • the content of styrene-based monomer units in the styrene-diene copolymer may be, for example, 1 to 30 mol% or 5 to 20 mol% based on the total amount of monomer units.
  • the content of the diene monomer unit in the styrene-diene copolymer may be, for example, 70 to 99 mol% or 80 to 95 mol% based on the total amount of monomer units.
  • the ethylene- ⁇ -olefin copolymer contains ethylene and an ⁇ -olefin having 3 or more carbon atoms as a monomer unit.
  • the ⁇ -olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1-pentene.
  • 1-octene and 1-decene are preferable, and propylene is preferable.
  • the content of ethylene units in the ethylene- ⁇ -olefin copolymer may be, for example, 30 to 80 mol%, 35 to 75 mol%, or 40 to 70 mol% based on the total amount of monomer units. May be
  • the content of ⁇ -olefin units in the ethylene- ⁇ -olefin copolymer may be, for example, 20 to 70 mol%, 25 to 65 mol%, or 30 based on the total amount of the monomer units. It may be up to 60 mol%.
  • the lubricating oil composition preferably does not contain poly (meth) acrylate as a viscosity index improver.
  • the coking resistance can be further improved.
  • the PSSI (Permanent Shear Stability Index) of the viscosity index improver in the diesel injector method is preferably 40 or less, more preferably 35 or less, still more preferably 30 or less, and usually more than 0.
  • PSSI Permanent Shear Stability Index
  • "PSSI" is based on ASTM D 6022-01 (Standard Practical for Calculating of Permanent Shearing Stability Indexing), and is based on ASTM D 6278-02 (Testeed beforeMath. Permanent Shear Stability Index of the polymer, calculated based on the data measured by the European Diesel Injector Apparatus.
  • the weight average molecular weight (Mw) of the viscosity index improver is, for example, preferably 10,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, and still more preferably 200, 000 or more, preferably 1,000,000 or less, more preferably 700,000 or less, and further preferably 500,000 or less.
  • Mw weight average molecular weight
  • the weight average molecular weight of the viscosity index improver is within the above numerical range, a sufficient viscosity index improving effect can be obtained, fuel economy is excellent, and a moderate viscosity increasing effect, shear stability and lubricating base oil are obtained. It has excellent solubility in water and storage stability.
  • the content of the viscosity index improver is, based on the total amount of the lubricating oil composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. In addition, it is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and further preferably 10.0% by mass or less.
  • the content of the viscosity index improver is within the above numerical range, the viscosity-temperature characteristic is excellent, and the coking resistance can be further improved.
  • the nitrogen-containing dispersant (hereinafter sometimes referred to as “component (E)”) is not particularly limited, and may be, for example, one or more compounds selected from the following (E-1) to (E-3). Can be used.
  • (E-1) Succinimide having at least one alkyl group or alkenyl group in the molecule or a derivative thereof (hereinafter sometimes referred to as “component (E-1)”), (E-2) Benzylamine having at least one alkyl group or alkenyl group in the molecule or a derivative thereof (hereinafter sometimes referred to as “component (E-2)”), (E-3) A polyamine having at least one alkyl group or alkenyl group in the molecule or a derivative thereof (hereinafter sometimes referred to as “component (E-3)”).
  • the component (E) can be particularly preferably used.
  • examples of the succinimide having at least one alkyl group or alkenyl group in the molecule include compounds represented by the following formula (5) or formula (6).
  • R 6 and R 7 each independently represent an alkyl group or an alkenyl group having 40 to 400 carbon atoms, and may be a combination of different groups.
  • R 6 and R 7 are particularly preferably polybutenyl groups.
  • i represents an integer of 0 to 4, preferably 1 to 3.
  • the carbon number of R 6 and R 7 is preferably 60 or more, and preferably 350 or less.
  • the alkyl group or alkenyl group (R 5 to R 7 ) in formulas (5) and (6) may be linear or branched, and is preferably an oligomer of an olefin such as propylene, 1-butene or isobutene. And a branched alkyl group or a branched alkenyl group derived from a cooligomer of ethylene and propylene. Among them, a branched alkyl group or alkenyl group derived from an oligomer of isobutene which is conventionally called polyisobutylene, and a polybutenyl group are most preferable.
  • the number average molecular weight of the alkyl group or alkenyl group (R 5 to R 7 ) in formulas (5) and (6) is preferably 800 to 3500.
  • Succinimide having at least one alkyl group or alkenyl group in the molecule is a so-called monotype succinimide represented by formula (5) in which succinic anhydride is added to only one end of a polyamine chain.
  • a so-called bis-type succinimide represented by the formula (6) in which succinic anhydride is added to both ends of a polyamine chain.
  • the lubricating oil composition of the present invention may contain either a monotype succinimide or a bis type succinimide, or both of them may be contained as a mixture.
  • the method for producing the succinimide having at least one alkyl group or alkenyl group in the molecule is not particularly limited, and for example, a compound having an alkyl group or alkenyl group having 40 to 400 carbon atoms may be combined with maleic anhydride and 100 It can be obtained by reacting an alkylsuccinic acid or an alkenylsuccinic acid obtained by reacting at ⁇ 200 ° C. with a polyamine.
  • the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • examples of the benzylamine having at least one alkyl group or alkenyl group in the molecule include compounds represented by the following formula (7).
  • R 8 represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms
  • j represents an integer of 1 to 5, preferably 2 to 4.
  • the carbon number of R 8 is preferably 60 or more, and preferably 350 or less.
  • the manufacturing method of the component (E-2) is not particularly limited.
  • propylene oligomer, polybutene, or polyolefin such as ethylene- ⁇ -olefin copolymer is reacted with phenol to form an alkylphenol, and then formaldehyde, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine are added thereto.
  • a polyamine such as the above by a Mannich reaction.
  • examples of the polyamine having at least one alkyl group or alkenyl group in the molecule include compounds represented by the following formula (8).
  • R 9 represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms
  • k represents an integer of 1 to 5, preferably 2 to 4.
  • the carbon number of R 9 is preferably 60 or more, and preferably 350 or less.
  • the manufacturing method of the component (E-3) is not particularly limited.
  • a polyolefin such as propylene oligomer, polybutene or ethylene- ⁇ -olefin copolymer
  • ammonia or a polyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine.
  • Examples of the derivatives in the components (E-1) to (E-3) include (i) succinimide, benzylamine or polyamine having at least one alkyl group or alkenyl group described above in the molecule (hereinafter, referred to as “above-mentioned”).
  • Nonrogen-containing compound a monocarboxylic acid having 1 to 30 carbon atoms such as a fatty acid, and a polycarboxylic acid having 2 to 30 carbon atoms (eg, oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.)
  • a monocarboxylic acid having 1 to 30 carbon atoms such as a fatty acid
  • a polycarboxylic acid having 2 to 30 carbon atoms eg, oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.
  • the molecular weight of the component (E) is not particularly limited, but the weight average molecular weight of the component (E-1) is preferably 1,000 to 20,000, more preferably 2,000 to 10,000.
  • the content of the component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, based on the total amount of the lubricating oil composition. In addition, it is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less.
  • the content of the component (E) is at least the above lower limit value, the caulking resistance of the lubricating oil composition can be sufficiently improved. Further, when the content of the component (E) is not more than the above upper limit value, fuel economy can be improved.
  • the content of the ashless friction modifier is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, based on the total amount of the lubricating oil composition. , Preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.8% by mass or less.
  • the content of the ashless friction modifier is within the above numerical range, the friction reducing effect is improved, the effects of the antiwear agent are not impaired, and the solubility of the additive can be maintained.
  • R 10 to R 13 may be the same or different, and are an alkyl group having 2 to 24 carbon atoms or an (alkyl) aryl group having 6 to 24 carbon atoms, preferably 4 carbon atoms.
  • the alkyl group may be any of a primary alkyl group, a secondary alkyl group and a tertiary alkyl group, and may be linear or branched.
  • the “(alkyl) aryl group” means an “aryl group or an alkylaryl group”. In the alkylaryl group, the substitution position of the alkyl group on the aromatic ring is arbitrary.
  • Y 1 to Y 4 are each independently a sulfur atom or an oxygen atom, and at least one of Y 1 to Y 4 is a sulfur atom.
  • molybdenum-containing compound other than the component (G1) examples include molybdenum dithiophosphate; molybdenum compounds (for example, molybdenum dioxide, molybdenum oxide such as molybdenum trioxide, ortho-molybdic acid, para-molybdic acid, (poly) sulfurized molybdic acid, etc.) Molybdenum acid, metal salts of these molybdic acids, molybdates such as ammonium salts, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polymolybdenum sulfide, molybdenum sulfide, molybdenum sulfide metal salts or amines Salts, molybdenum halides such as molybdenum chloride, etc.
  • molybdenum compounds for example, molybdenum dioxide, molyb
  • sulfur-containing organic compounds eg, alkyl (thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfi).
  • sulfur-containing molybdenum such as molybdenum sulfide, molybdenum sulfide, etc. Mention may be made of molybdenum-containing compounds containing sulfur, such as complexes of compounds with alkenyl succinimides.
  • the molybdenum-containing compound may be a mononuclear molybdenum compound or a polynuclear molybdenum compound such as a binuclear molybdenum compound or a trinuclear molybdenum compound.
  • a molybdenum-containing compound containing no sulfur as a constituent element can be used as the molybdenum-containing compound other than the component (G1).
  • the molybdenum-containing compound containing no sulfur as a constituent element include molybdenum-amine complex, molybdenum-succinimide complex, molybdenum salt of organic acid, molybdenum salt of alcohol, and the like. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.
  • the content of the component (G) is, as the amount of molybdenum based on the total amount of the lubricating oil composition, preferably 10 mass ppm or more, preferably 100 mass ppm or more, and preferably 2000 mass ppm or less. It is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less. When the content of the component (G) is within the above numerical range, the friction reducing effect can be improved and the LSPI suppressing ability can be further improved.
  • the antiwear agent is not particularly limited, and compounds commonly used as antiwear agents for lubricating oils can be used.
  • As the antiwear agent for example, a sulfur-based, phosphorus-based, sulfur-phosphorus-based antiwear agent, or the like can be used.
  • phosphite esters As the antiwear agent, phosphite esters, thiophosphite esters, dithiophosphite esters, trithiophosphite esters, phosphoric acid esters, thiophosphoric acid esters, dithiophosphoric acid Examples thereof include esters, trithiophosphoric acid esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamates, zinc dithiocarbamates, disulfides, polysulfides, sulfurized olefins, sulfurized oils and fats.
  • ZnDTP zinc dialkyldithiophosphate
  • R 14 to R 17 each independently represent a linear or branched alkyl group having 1 to 24 carbon atoms, and may be a combination of different groups.
  • the carbon number of R 14 to R 17 is preferably 3 or more, preferably 12 or less, more preferably 8 or less.
  • R 14 to R 17 may be any of a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group, but a primary alkyl group or a secondary alkyl group or their The combination is preferable, and the molar ratio of the primary alkyl group to the secondary alkyl group (primary alkyl group: secondary alkyl group) is preferably 0: 100 to 30:70. ..
  • This ratio may be a combination ratio of alkyl chains in the molecule, or may be a mixing ratio of ZnDTP having only a primary alkyl group and ZnDTP having only a secondary alkyl group. By mainly using the secondary alkyl group, it is possible to improve fuel economy.
  • the method for producing the zinc dialkyldithiophosphate is not particularly limited.
  • it can be synthesized by reacting an alcohol having an alkyl group corresponding to R 14 to R 17 with diphosphorus pentasulfide to synthesize dithiophosphoric acid, and neutralizing this with zinc oxide.
  • the content of the antiwear agent is, based on the total amount of the lubricating oil composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 5.0% by mass or less. Yes, and more preferably 3.0% by mass or less. When the content of the antiwear agent is within the above numerical range, a sufficient antiwear effect can be obtained.
  • the antioxidant is not particularly limited, and compounds that are commonly used as antioxidants for lubricating oils can be used.
  • examples of the antioxidant include amine-based antioxidants and phenol-based antioxidants, and amine-based antioxidants are preferable.
  • amine-based antioxidant known amine-based antioxidants such as alkylated diphenylamine, alkylated phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, and phenyl- ⁇ -naphthylamine can be used.
  • phenolic antioxidant examples include known phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol (DBPC) and 4,4′-methylenebis (2,6-di-tert-butylphenol). Antioxidants can be used.
  • DBPC 2,6-di-tert-butyl-4-methylphenol
  • Antioxidants can be used.
  • the content of the antioxidant is, based on the total amount of the lubricating oil composition, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5% by mass or less, It is more preferably 3% by mass or less. When the content of the antioxidant is within the above numerical range, a sufficient antioxidant effect can be obtained.
  • the lubricating oil composition is a rust preventive agent, pour point depressant, demulsifier, metal deactivator, defoaming agent that is commonly used in lubricating oil compositions. You may further contain other components, such as an agent.
  • the rust inhibitor examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
  • the content of the rust inhibitor is, based on the total amount of the lubricating oil composition, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 10% by mass or less, It is more preferably 5% by mass or less.
  • the pour point depressant for example, a polymethacrylate-based polymer compatible with the lubricating base oil used can be used.
  • the content of the pour point depressant, based on the total amount of the lubricating oil composition, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 10% by mass or less. , And more preferably 5 mass% or less.
  • demulsifiers include polyalkylene glycol-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene alkylnaphthyl ether.
  • the content of the demulsifier is, based on the total amount of the lubricating oil composition, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 10% by mass or less, It is preferably 5% by mass or less.
  • the defoaming agent examples include silicone oil having a kinematic viscosity of 1,000 to 100,000 mm 2 / s at 25 ° C., an alkenylsuccinic acid derivative, an ester of a polyhydroxy aliphatic alcohol and a long chain fatty acid, and methyl salicylate. , And o-hydroxybenzyl alcohol.
  • the content of the antifoaming agent is, based on the total amount of the lubricating oil composition, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 10% by mass or less, It is more preferably 5% by mass or less.
  • Kinematic viscosity at 40 ° C. of the lubricating oil composition is preferably 20.0 mm 2 / s or more, more preferably 25.0 mm 2 / s or more, even more preferably 30.0 mm 2 / s or more, Even more preferably 35.0 mm 2 / s or more, and less than 80.0 mm 2 / s, more preferably less than 70.0 mm 2 / s, and even more preferably less than 60.0 mm 2 / s. Yes, and even more preferably less than 55.0 mm 2 / s.
  • the kinematic viscosity of the lubricating oil composition at 40 ° C. is within the above numerical range, the low-temperature viscosity characteristic becomes good, sufficient fuel economy is obtained, and the oil film is formed well at the lubrication point for lubrication. Excellent in performance.
  • the viscosity index of the lubricating oil composition is preferably 120 or higher, more preferably 130 or higher, even more preferably 140 or higher, and usually 300 or lower.
  • the viscosity index of the lubricating oil composition is within the above numerical range, fuel economy can be improved while maintaining the HTHS viscosity at 150 ° C.
  • the HTHS viscosity of the lubricating oil composition at 150 ° C. is preferably 1.7 mPa ⁇ s or more, more preferably 1.8 mPa ⁇ s or more, even more preferably 1.9 mPa ⁇ s or more, and even more preferably Is 2.0 mPa ⁇ s or more, preferably 3.5 mPa ⁇ s or less, more preferably 3.2 mPa ⁇ s or less, even more preferably 2.9 mPa ⁇ s or less, and even more preferably Is 2.6 mPa ⁇ s or less.
  • HTHS viscosity at 150 ° C. means the high temperature high shear viscosity at 150 ° C. measured according to ASTM D-4683.
  • the content of sulfur in the lubricating oil composition is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass based on the total amount of the lubricating oil composition. It is not more than mass%.
  • heat / oxidation stability can be improved.
  • the nitrogen content in the lubricating oil composition is 700 mass ppm or more, preferably 800 mass ppm or more, more preferably 900 mass ppm or more, and further preferably, based on the total amount of the lubricating oil composition. It is 1000 mass ppm or more, preferably 3000 mass ppm or less, more preferably 2500 mass ppm or less, and further preferably 2000 mass ppm or less.
  • content of nitrogen component in the lubricating oil composition is within the above numerical range, it is possible to improve fuel economy while maintaining coking resistance.
  • the evaporation loss amount of the lubricating oil composition is preferably 15% by mass or less in NOACK evaporation amount, more preferably 14% by mass or less, further preferably 13% by mass or less, and particularly preferably 12% by mass or less. Is.
  • NOACK evaporation amount of the lubricating oil composition By setting the NOACK evaporation amount of the lubricating oil composition to be equal to or less than the above upper limit value, it is possible to suppress the evaporation loss of the lubricating oil and suppress the increase in viscosity and the like.
  • the NOACK evaporation amount mentioned here is a measurement of the evaporation amount of the lubricating oil measured according to ASTM D5800.
  • Lubricating base oils and various additives shown below were used to prepare the lubricating oil compositions of the present invention (Examples 1 to 10) and comparative lubricating oil compositions (Comparative Examples) in the formulations shown in Tables 1 and 2. 1 to 6) were prepared respectively.
  • “immass%” represents mass% based on the total amount of lubricating base oil
  • “mass%” represents mass% based on the total amount of lubricating oil composition
  • “massppm” represents lubricating oil. Indicates mass ppm based on the total amount of the composition.
  • A-1 hydrocracked base oil (Group III, YUBASE (registered trademark) 4 manufactured by SK Lubricants, density (15 ° C.): 0.836, kinematic viscosity (40 ° C.): 19.6 mm 2 / s, kinematic viscosity (100 ° C.): 4.2 mm 2 / s, viscosity index: 122, pour point: ⁇ 15 ° C., sulfur content: less than 10 mass ppm,% C P : 80.7,% C N : 19.3,% C A : 0)
  • the amount of the lubricating base oil is 100% by mass of the total amount of the lubricating oil composition and the balance after subtracting each additive.
  • B-1 overbased calcium carbonate salicylate (alkyl group chain length 14-18, Ca content: 8.0 mass%, total base number 220 mgKOH / g)
  • G-1 Molybdenum amine (Mo content: 10 mass%, N content: 1.2 mass%)
  • the lubricating oil composition was subjected to a hot tube test according to JPI-5S-55-99. The details of the test method are described below.
  • the lubricating oil composition was continuously flowed in a glass tube having an inner diameter of 2 mm at 0.3 ml / hour and air at 10 ml / sec for 16 hours while maintaining the temperature of the glass tube at 280 ° C.
  • the lacquer adhered in the glass tube and the color sample were compared, and a score was given as 10 points for transparent and 0 point for black. The higher the score, the better the high temperature cleanability. If the rating is 7.0 or more, it can be said that the high temperature cleanability is good.
  • the lubricating oil compositions of Examples 1 to 10 showed good results in coking resistance, LSPI inhibiting ability, and high temperature detergency.
  • the lubricating oil compositions of Comparative Examples 1 and 2 which used the same poly (meth) acrylate-based viscosity index improver as the conventional engine oil as the viscosity index improver showed poor results in coking resistance. ..
  • the lubricating oil composition of Comparative Example 3 having an excessively high calcium content resulted in a poor LSPI inhibiting ability.

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

Abstract

Le problème décrit par la présente invention concerne la fourniture d'une composition lubrifiante pour moteur suralimenté qui est en mesure de présenter un bon équilibre entre la résistance du calfatage, l'aptitude à la suppression du préallumage à basse vitesse (LSPI) et la nettoyabilité à haute température. La solution selon l'invention porte sur une composition lubrifiante de moteur suralimenté qui comprend (A) une huile de base lubrifiante, (B) 1100 à 1900 ppm en masse d'un détergent à base de calcium en termes de calcium sur la base de la quantité totale de la composition lubrifiante, (C) un détergent à base de magnésium, (D) au moins un agent d'amélioration d'indice de viscosité choisi parmi un copolymère de styrène-diène et un copolymère éthylène-α-oléfine et (E) un dispersant contenant de l'azote, la teneur en azote étant de 700 ppm en masse ou plus sur la base de la quantité totale de la composition lubrifiante.
PCT/JP2019/043464 2018-11-07 2019-11-06 Composition lubrifiante WO2020095943A1 (fr)

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EP19881130.9A EP3878931B1 (fr) 2018-11-07 2019-11-06 Composition lubrifiante
CN201980069747.3A CN112888769B (zh) 2018-11-07 2019-11-06 润滑油组合物

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JP2018209912A JP7320935B2 (ja) 2018-11-07 2018-11-07 潤滑油組成物
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CN114250098A (zh) * 2020-09-23 2022-03-29 长城汽车股份有限公司 一种润滑油和一种制备润滑油的方法
WO2022250018A1 (fr) * 2021-05-25 2022-12-01 Ｅｎｅｏｓ株式会社 Composition lubrifiante pour moteur à combustion interne

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US20200277541A1 (en) * 2019-02-28 2020-09-03 Afton Chemical Corporation Lubricating compositions for diesel particulate filter performance
JP2023004315A (ja) * 2021-06-25 2023-01-17 Ｅｎｅｏｓ株式会社 内燃機関用潤滑油組成物
WO2023190100A1 (fr) * 2022-03-29 2023-10-05 Ｅｎｅｏｓ株式会社 Composition d'huile lubrifiante pour machine à combustion interne
WO2023190101A1 (fr) * 2022-03-29 2023-10-05 Ｅｎｅｏｓ株式会社 Composition d'huile lubrifiante pour machine à combustion interne

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CN114250098A (zh) * 2020-09-23 2022-03-29 长城汽车股份有限公司 一种润滑油和一种制备润滑油的方法
WO2022250018A1 (fr) * 2021-05-25 2022-12-01 Ｅｎｅｏｓ株式会社 Composition lubrifiante pour moteur à combustion interne

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EP3878931B1 (fr) 2024-02-21
EP3878931A1 (fr) 2021-09-15
CN112888769B (zh) 2022-09-27
JP2020076004A (ja) 2020-05-21
EP3878931A4 (fr) 2022-07-27
JP7320935B2 (ja) 2023-08-04

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