WO2022201845A1 - Composition lubrifiante pour moteur à combustion interne - Google Patents

Composition lubrifiante pour moteur à combustion interne Download PDF

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Publication number
WO2022201845A1
WO2022201845A1 PCT/JP2022/003125 JP2022003125W WO2022201845A1 WO 2022201845 A1 WO2022201845 A1 WO 2022201845A1 JP 2022003125 W JP2022003125 W JP 2022003125W WO 2022201845 A1 WO2022201845 A1 WO 2022201845A1
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Prior art keywords
mass
component
content
composition
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PCT/JP2022/003125
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English (en)
Japanese (ja)
Inventor
翔瑚 江龍
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Eneos Corp
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Eneos Corp
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Priority to US18/279,123 priority Critical patent/US20240301314A1/en
Priority to CN202280019723.9A priority patent/CN116964180B/zh
Publication of WO2022201845A1 publication Critical patent/WO2022201845A1/fr
Anticipated expiration legal-status Critical
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/12—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 monocarboxylic
    • C10M145/14—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
    • 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
    • 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
    • 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
    • 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
    • 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
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    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • 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
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • 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
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—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
    • C10N2030/43—Sulfur free or low sulfur 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
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to a lubricating oil composition for internal combustion engines.
  • Patent Document 1 discloses a lubricating base oil, (A) a metallic detergent containing calcium borate, and (B) a metallic detergent containing magnesium.
  • the component (A) is one or more calcium-based detergents overbased with calcium borate, or one or more calcium-based detergents overbased with calcium borate and one or more calcium-based detergents not overbased with calcium borate, the total boron content B (in mol) derived from the metallic detergents in the lubricating oil composition, and the lubricating
  • a lubricating oil composition for internal combustion engines is disclosed in which the molar ratio B/Ca to the total calcium content Ca (unit: mol) derived from metallic detergents in the oil composition is 0.52 or more.
  • Patent Document 2 discloses a lubricating base oil, (A) a metallic detergent containing calcium borate, and (B) a metallic detergent containing magnesium.
  • the total boron content B (unit: mol) derived from the metallic detergent in the lubricating oil composition and lubricating It is disclosed that the molar ratio B/Ca to the total calcium content Ca (unit: mol) derived from the metallic detergent in the oil composition is preferably 0.52 or more.
  • Patent Document 3 JP 2017-226793 A (Patent Document 3), (A) a lubricating base oil, (B) (B1) a metallic detergent containing calcium and (B2) a metallic detergent containing magnesium and a metallic detergent containing 500 to 2500 ppm by mass of calcium and 100 to 1000 ppm by mass of magnesium based on the total amount of the composition.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and aims to provide a lubricating oil composition for internal combustion engines capable of improving both LSPI suppression ability and fuel saving performance. aim.
  • the lubricating oil composition for internal combustion engines contains (A) a lubricating base oil and (B) a metallic detergent; B) components are (B1) a calcium-based detergent having a calcium content in the range of 1650 mass ppm or more and 2500 mass ppm or less based on the total mass of the composition, and (B2) based on the total mass of the composition.
  • the content of boron based on the total mass of the composition is 1000 ppm by mass or less; and the content of boron in the component (B1) based on the total mass of the composition (mass ratio) is represented as B (B1) , the content (mass ratio) of calcium in the component (B1) based on the total mass of the composition is represented as Ca (B1) , and the total mass of the composition is represented as (B2 )
  • the ratio of B ( B1) to Ca ( B1) (B (B1) / Ca (B1) ) is 0.15 or more
  • the ratio ( B ( B1 ) / [Ca ( B1 ) +Mg (B2) ]) is 0.13 or more and 0.29 or less, the LSPI suppression ability of the lubricating oil composition for internal combustion engines can be
  • the lubricating oil composition for internal combustion engines of the present invention is (A) a lubricating base oil, and (B) a metallic detergent
  • the component (B) is (B1) a calcium-based detergent having a calcium content in the range of 1650 mass ppm or more and 2500 mass ppm or less based on the total mass of the composition; (B2) a magnesium-based detergent having a magnesium content in the range of 20 mass ppm or more and 400 mass ppm or less based on the total mass of the composition; contains
  • the component (B1) contains (B1-1) a calcium-based detergent containing boron and calcium,
  • the boron content based on the total mass of the composition is 1000 ppm by mass or less
  • the content of boron in the component (B1) based on the total mass of the composition is represented as B (B1)
  • the content of calcium in the component (B1) based on the total mass of the composition is represented by Ca (B1 )
  • the component (B1) preferably contains calcium borate salicylate as the component (B1-1).
  • the lubricating oil composition for internal combustion engines of the present invention preferably further contains (C) a poly(meth)acrylate viscosity index improver.
  • the component (C) preferably contains a comb-shaped poly(meth)acrylate polymer.
  • a lubricating oil composition for internal combustion engines capable of improving both the LSPI suppression ability and the fuel economy performance.
  • the lubricating oil composition for internal combustion engines of the present invention is (A) a lubricating base oil, and (B) a metallic detergent,
  • the component (B) is (B1) a calcium-based detergent having a calcium content in the range of 1650 mass ppm or more and 2500 mass ppm or less based on the total mass of the composition; (B2) a magnesium-based detergent having a magnesium content in the range of 20 mass ppm or more and 400 mass ppm or less based on the total mass of the composition; contains
  • the component (B1) contains (B1-1) a calcium-based detergent containing boron and calcium,
  • the boron content based on the total mass of the composition is 1000 ppm by mass or less,
  • the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1)
  • the content of calcium in the component (B1) based on the total mass of the composition (mass ratio) is represented as Ca (B
  • lubricant base oil lubricant base oil
  • the lubricating base oil used as the component (A) in the present invention is not particularly limited, and known base oils available in the field of lubricating oils can be appropriately used.
  • one or more mineral base oils, or One or more synthetic base oils, or mixed base oils thereof, can be used.
  • Mineral base oils that can be used as lubricating base oils include group II base oils, group III base oils, and group IV base oils in the classification of base oils by API (American Petroleum Institute). , Group V base oils, or a mixture of two or more of these base oils (mixed base oils) can be preferably used (hereinafter, the group of base oils classified by API is simply referred to as "API group"). called).
  • API group II base oil is a mineral oil base oil having a sulfur content of 0.03 mass % or less, a saturate content of 90 mass % or more, and a viscosity index of 80 or more and less than 120.
  • API Group III base oils are mineral base oils having a sulfur content of 0.03% by weight or less, a saturates content of 90% by weight 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 base oils other than API Groups I to IV, and preferred examples thereof include ester base oils.
  • the mineral base oil for example, a lubricating oil fraction obtained by atmospheric distillation and / or vacuum distillation of crude oil, solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing , Hydrorefining, sulfuric acid washing, paraffinic mineral oil refined by one or a combination of two or more selected from refining treatments such as clay treatment, normal paraffinic base oil, isoparaffinic base oil, and mixtures thereof can.
  • a lubricating oil fraction obtained by atmospheric distillation and / or vacuum distillation of crude oil, solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing , Hydrorefining, sulfuric acid washing, paraffinic mineral oil refined by one or a combination of two or more selected from refining treatments such as clay treatment, normal paraffinic base oil, isoparaffinic base oil, and mixtures thereof can.
  • mineral base oils include base oils (1) to (8) shown below as raw materials, and this raw material oil and/or a lubricating oil fraction recovered from this raw material oil is purified by a predetermined refining method. Base oils obtained by refining and recovering lubricating oil fractions may be mentioned.
  • Distillate oil obtained by atmospheric distillation of paraffin-based crude oil and/or mixed-base crude oil (2) Distillate oil obtained by vacuum distillation of atmospheric distillation residue oil of paraffin-based crude oil and/or mixed-base crude oil ( WVGO) (3) Waxes (such as slack waxes) obtained by lubricating oil dewaxing processes and/or synthetic waxes (such as Fischer-Tropsch waxes and GTL waxes) obtained by gas-to-liquid (GTL) processes, etc.
  • Waxes such as slack waxes obtained by lubricating oil dewaxing processes and/or synthetic waxes (such as Fischer-Tropsch waxes and GTL waxes) obtained by gas-to-liquid (GTL) processes, etc.
  • the predetermined refining method includes hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; Clay refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred.
  • hydrorefining such as hydrocracking and hydrofinishing
  • solvent refining such as furfural solvent extraction
  • dewaxing such as solvent dewaxing and catalytic dewaxing
  • Clay refining such as sulfuric acid cleaning and caustic soda cleaning are preferred.
  • One of these purification methods may be used alone, or two or more of them may be used in combination. When combining two or more purification methods, the order is not particularly limited and can be selected as appropriate.
  • the base oil selected from the base oils (1) to (8) or the following base oil obtained by performing a predetermined treatment of the lubricating oil fraction recovered from the base oil ( 9) or (10) are particularly preferred.
  • Hydrocracking base oil (10) obtained by subjecting the lubricating oil fraction to dewaxing treatment such as solvent dewaxing or catalytic dewaxing, or by distillation after the dewaxing treatment (10)
  • the base oil (1) to ( 8) The base oil selected from or the lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic dewaxing.
  • dewaxing treatment those produced through a contact dewaxing treatment (step) are more preferable.
  • a solvent refining treatment and/or hydrofinishing treatment step may be further performed at an appropriate stage, if necessary.
  • the %C P of the mineral base oil is preferably 70-99, more preferably 70-95, even more preferably 75-95, and particularly preferably 75-94.
  • the %C P of the base oil is equal to or higher than the lower limit, it becomes possible to improve the viscosity-temperature characteristics and further improve the fuel economy performance.
  • an additive is blended in the base oil, it becomes possible to sufficiently exhibit the effect of the additive.
  • the %C P of the base oil is equal to or less than the upper limit, it becomes possible to increase the solubility of the additive.
  • the % CA of the mineral base oil is preferably 2 or less, more preferably 1 or less, still more preferably 0.8 or less, and particularly preferably 0.5 or less.
  • the % CA of the base oil is equal to or less than the above upper limit, it becomes possible to improve the viscosity - temperature characteristics and further improve the fuel economy performance.
  • the % C N of the mineral base oil is preferably 1-30, more preferably 4-25.
  • the % CN of the base oil is equal to or less than the above upper limit, it becomes possible to improve the viscosity - temperature characteristics and further improve the fuel saving performance. Further, when % CN is equal to or higher than the lower limit, it becomes possible to increase the solubility of the additive.
  • %C P , %C N and %C A are the percentages of the number of paraffin carbon atoms to the total number of carbon atoms, each determined by a method (ndM ring analysis) according to ASTM D 3238-85. , the percentage of the number of naphthenic carbons to the total number of carbons, and the percentage of the number of aromatic carbons to the total number of carbons. That is, the preferred ranges of %C P , %C N and %C A described above are based on the values obtained by the above method. The %C N sought may show values greater than zero.
  • the content of saturated components in the mineral base oil is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, based on the total amount of the base oil.
  • the viscosity-temperature characteristic can be improved when the content of the saturated component is equal to or higher than the lower limit.
  • saturated content means a value measured according to ASTM D 2007-93.
  • the aromatic content in the mineral base oil is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, particularly preferably 0 to 1% by mass, based on the total amount of the base oil, and in one embodiment It can be 0.1% by mass or more.
  • the content of the aromatic component is equal to or less than the upper limit, it is possible to improve viscosity-temperature characteristics and low-temperature viscosity characteristics, as well as to further improve fuel economy performance, and evaporation of lubricating oil. It becomes possible to reduce the loss and reduce the consumption of lubricating oil. In addition, it becomes possible to effectively exhibit the effect of the additive blended in the lubricating oil.
  • the lubricating base oil may not contain aromatics, but if the content of aromatics is equal to or higher than the above lower limit, the solubility of additives can be enhanced.
  • aromatic content as used herein means a value measured according to ASTM D 2007-93.
  • Aromatic components generally include alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, alkylated products thereof, compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols, naphthols, and the like. Aromatic compounds with heteroatoms and the like are included.
  • the synthetic base oil that can be used as the lubricating base oil is not particularly limited, and known synthetic base oils can be used as appropriate.
  • synthetic base oils include poly- ⁇ -olefins and their hydrides, isobutene oligomers and their hydrides, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate, bis-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, bis-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene Synthetic base oils such as glycols, dialkyldiphenyl
  • poly- ⁇ -olefin base oils include ⁇ -olefin oligomers or co-oligomers (1-octene oligomer, decene oligomer, ethylene-propylene copolymer) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms. oligomers, etc.) and their hydrogenation products.
  • the lubricating base oil has a kinematic viscosity at 100° C. of 2.0 to 5.0 mm 2 /s (more preferably 3.0 to 5.0 mm 2 /s, still more preferably 4.0 to 4.8 mm 2 /s, particularly preferably 4.1 to 4.7 mm 2 /s).
  • a kinematic viscosity at 100° C. of the lubricating base oil is at least the lower limit value, compared to the case of less than the lower limit value, it is possible to efficiently form an oil film at the lubricating location, and the lubricating oil It is possible to reduce the consumption of lubricating oil by reducing the evaporation loss of the composition.
  • kinematic viscosity at 100° C. of the lubricating base oil is equal to or less than the above upper limit, it is possible to make the fuel saving performance even more excellent than when the above upper limit is exceeded.
  • "kinematic viscosity at 100°C” means kinematic viscosity at 100°C measured according to JIS K 2283-2000.
  • the lubricating base oil has a kinematic viscosity at 40° C. of 9.0 to 36.0 mm 2 /s (more preferably 12.6 to 33.2 mm 2 /s, still more preferably 15.8 to 25.2 mm 2 /s, particularly preferably 17.7-21.6 mm 2 /s, most preferably 17.5-22.1 mm 2 /s).
  • a kinematic viscosity at 40° C. of the lubricating base oil is equal to or less than the upper limit, the low-temperature viscosity characteristics and fuel economy performance of the lubricating oil composition are more excellent than when the upper limit is exceeded. It becomes possible to In addition, when the kinematic viscosity of the lubricating base oil at 40 ° C.
  • kinematic viscosity at 40°C means kinematic viscosity at 40°C measured according to JIS K 2283-2000.
  • the lubricating base oil preferably has a viscosity index of 100 or more (more preferably 105 or more, still more preferably 110 or more, particularly preferably 115 or more, most preferably 120 or more).
  • a viscosity index of 100 or more (more preferably 105 or more, still more preferably 110 or more, particularly preferably 115 or more, most preferably 120 or more).
  • the viscosity index is at least the lower limit, it is possible to improve the viscosity-temperature characteristics and wear resistance of the lubricating oil composition compared to the case where it is less than the lower limit, and the fuel economy performance. can be further improved, and furthermore, the evaporation loss of the lubricating oil can be reduced, and the consumption of the lubricating oil can be reduced.
  • the term "viscosity index” means a viscosity index measured according to JIS K 2283-1993.
  • the lubricating base oil preferably has a NOACK evaporation amount of 30% by mass or less (more preferably 15% by mass or less) at 250°C.
  • the lower limit of the NOACK evaporation amount of the lubricating base oil at 250° C. is not particularly limited, but is usually 3% by mass or more.
  • the "NOACK evaporation amount at 250°C” is the evaporation amount of the lubricating base oil or lubricating oil composition at 250°C measured according to ASTM D5800.
  • the lubricating base oil preferably has a pour point of -10°C or lower (more preferably -12.5°C or lower, still more preferably -15°C or lower).
  • pour point means the pour point measured according to JIS K 2269-1987.
  • the sulfur content of the lubricating base oil depends on the sulfur content of the raw material.
  • a raw material containing substantially no sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
  • a lubricating base oil substantially containing no sulfur can be obtained.
  • the term "sulfur content” as used herein means the sulfur content measured according to JPI-5S-38.
  • the sulfur content in the obtained lubricating base oil is usually 100 ppm by mass. That's it.
  • the sulfur content of the lubricating base oil is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, and 10 mass ppm or less. is more preferable, and 5 ppm by mass or less is particularly preferable.
  • the nitrogen content in the lubricating base oil is preferably 10 mass ppm or less (more preferably 5 mass ppm or less, still more preferably 3 mass ppm or less).
  • the nitrogen content means the nitrogen content measured according to JIS K 2609-1990.
  • the content of the lubricating base oil (total base oil) in the lubricating oil composition is preferably 70-95% by mass (more preferably 75-85% by mass) based on the total mass of the composition.
  • the metallic detergent used as component (B) in the present invention is (B1) the content of calcium based on the total mass of the composition (the content of calcium derived from the component (B1) based on the total mass of the composition) is in the range of 1650 ppm by mass or more and 2500 ppm by mass or less; a calcium-based detergent and (B2) the content of magnesium based on the total mass of the composition (the content of magnesium derived from the component (B2) based on the total mass of the composition) is in the range of 20 ppm by mass or more and 400 ppm by mass or less; a magnesium-based detergent and It contains
  • the "calcium-based detergent” is a metallic detergent containing calcium as a metal
  • the "magnesium-based detergent” is a metallic detergent containing magnesium as a metal.
  • metallic detergents amounts of calcium, magnesium, and boron are selected from known metallic detergents (for example, sulfonate detergents, phenate detergents, salicylate detergents, etc. containing calcium or magnesium as a metal). may be appropriately selected and used so that each of them has a desired content ratio.
  • the "sulfonate detergent”, “phenate detergent” and “salicylate detergent” exemplified as the known metallic detergents include, for example, paragraphs [0038] to [0054] of JP-A-2020-76004. and those described in paragraphs [0043] to [0054] of International Publication No. 2018/212340 can be used as appropriate.
  • the "calcium-based detergent” used as the component (B1) is a metallic detergent containing calcium as a metal, and containing at least boron and calcium in its components ((B1- 1) Contains component).
  • the "calcium-based detergent" used as the component (B1) must contain the component (B1-1) containing boron and calcium, but calcium other than the component (B1-1) It may also contain a system detergent.
  • Other calcium-based detergents other than the component (B1-1) include known boron-free calcium-based detergents (known boron-free metallic detergents containing calcium as a metal). ) can be used as appropriate.
  • the component (B1) may consist of only the component (B1-1), or the component (B1-1) and a boron-free calcium-based detergent can be used as appropriate.
  • the type of calcium-based detergent used as the component (B1) is not particularly limited, and examples include sulfonate detergents, phenate detergents, salicylate detergents, etc. containing calcium as a metal.
  • sulfonate detergents phenate detergents
  • salicylate detergents etc. containing calcium as a metal.
  • salicylate detergents containing calcium as a metal are preferable from the viewpoint of friction reduction performance.
  • the sulfonate detergent containing calcium as such a metal is not particularly limited, and known ones can be used as appropriate.
  • a calcium sulfonate detergent for example, a calcium salt of an alkylaromatic sulfonic acid obtained by sulfonating an alkylaromatic compound having a molecular weight of 300 to 1500 (more preferably 400 to 1300) is suitable. can be mentioned.
  • the alkylaromatic sulfonic acid include petroleum sulfonic acid and synthetic sulfonic acid. Further, known petroleum sulfonic acids and synthetic sulfonic acids can be used as appropriate.
  • the calcium sulfonate detergent a known one that can be used for lubricating oil compositions can be used as appropriate.
  • the salicylate detergent containing calcium as a metal is not particularly limited, and known ones can be used as appropriate.
  • Examples of such salicylate detergents include calcium salts of alkylsalicylic acids having 1 to 2 alkyl or alkenyl groups having 4 to 36 carbon atoms (more preferably 14 to 30 carbon atoms) as substituents, and mixtures thereof. can be mentioned.
  • the calcium salicylate detergent a known one that can be used for lubricating oil compositions can be appropriately used.
  • component (B1-1) calcium-based detergent containing boron and calcium contained in component (B1)
  • calcium borate and more preferably a calcium-based detergent overbased with calcium borate calcium salicylate detergent overbased with calcium borate (calcium borate salicylates) are particularly preferred.
  • component (B1) a mixture of the component (B1-1) and a calcium-based detergent containing calcium carbonate (B1-2) is preferable from the viewpoint of improving fuel economy performance according to application conditions.
  • available for Component (B1-2) is not particularly limited, and is more preferably a calcium-based detergent overbased with calcium carbonate. Calcium salicylate detergents are particularly preferred.
  • component (B1) is a mixture of component (B1-1) and a calcium-based detergent other than component (B1-1) (preferably component (B1-2))
  • the content of component (B1-1) is not particularly limited, but the amount of component (B1-1) is 30 to 100% by mass (more preferably 45 to 100% by mass) relative to the total amount of component (B1). %, more preferably 67 to 100 mass %).
  • the content of the component (B1-1) is equal to or higher than the lower limit, it is possible to further improve the friction reduction performance under particularly severe sliding conditions compared to when the content is less than the lower limit.
  • the content of boron in the (B1-1) component is 1.0 to 5.0 mass relative to the total amount of the (B1-1) component. % (more preferably 1.3 to 4.5 mass %, still more preferably 2.0 to 3.0 mass %).
  • the content of B in the component (B1-1) is at least the lower limit, it is possible to further improve the friction reduction performance and the LSPI suppression performance compared to when it is less than the lower limit.
  • it is equal to or less than the upper limit it is possible to improve the stability of the lubricating oil composition compared to when the upper limit is exceeded.
  • the calcium-based detergent used as the component (B1) is selected for each calcium-based detergent contained in the component (B1) (when the component (B1) consists of one type, one of them).
  • a calcium (Ca) content of 2.0 to 11.5% by mass (more preferably 4.0 to 10.0% by mass, still more preferably 5.7 to 7.2% by mass) is preferred.
  • the content of calcium (Ca) in each calcium-based detergent is equal to or higher than the lower limit, it is possible to improve the reduction of friction loss under low-temperature conditions compared to when the content is less than the lower limit.
  • it is equal to or less than the upper limit it is possible to improve the stability of the lubricating oil composition compared to when the upper limit is exceeded.
  • the base number (TBN) of each calcium-based detergent used as component (B1) is not particularly limited, but is 50 to 500 mgKOH/g, more preferably 100, for each calcium-based detergent. ⁇ 500 mg KOH/g, particularly preferably 150-500 mg KOH/g.
  • base number of each calcium-based detergent used as component (B1) is at least the lower limit, it is possible to improve the acid neutralization performance compared to when it is less than the lower limit. If it is equal to or less than the upper limit, it becomes possible to improve the solubility of each additive in the lubricating oil composition compared to the case that the upper limit is exceeded.
  • base number (TBN) means a base number measured by the perchloric acid method in accordance with JIS K2501.
  • the component (B1) has a calcium content (Ca (B1) ) derived from the component (B1) based on the total mass of the composition of 1650 mass ppm or more and 2500 mass ppm or less (more preferably 1650 mass ppm or more and 2200 mass ppm). mass ppm or less, more preferably 1700 mass ppm or more and 1900 mass ppm or less, particularly preferably 1750 mass ppm or more and 1900 mass ppm or less).
  • the calcium content (Ca (B1) ) is at least the lower limit, it is possible to improve the cleanliness compared to when it is less than the lower limit. It is possible to improve both the LSPI suppression capability and the fuel economy performance compared to when the upper limit is exceeded.
  • the content of boron derived from the (B1) component (B (B1) ) is based on the total mass of the composition (based on the total mass of the lubricating oil composition), and is 50 mass ppm or more and 1000 mass ppm or less (more preferably is 200 mass ppm or more and 700 mass ppm or less, more preferably 400 mass ppm or more and 700 mass ppm or less, particularly preferably 400 mass ppm or more and 650 mass ppm or less).
  • the boron content (B (B1) ) is at least the lower limit, it is possible to further improve the friction reduction performance and the LSPI suppression performance compared to the case where it is less than the lower limit. When it is below, it becomes possible to improve friction reduction performance further compared with the case where the said upper limit is exceeded.
  • the content of the component (B1) is 1.5 to 3.5% by mass (more preferably 2.0 to 3.2% by mass, more preferably 2.4 to 2.5% by mass) based on the total amount of the lubricating oil composition. 9% by mass).
  • the content of the component (B1) is at least the lower limit, it is possible to improve the detergency compared to when it is less than the lower limit. It is possible to further improve the friction reduction performance as compared with the case of exceeding.
  • the content of boron derived from the component (B1) (B (B1) ) is preferably 50% by mass or more, and preferably 60% by mass to 100% by mass, with respect to the total amount of boron contained in the composition. %, and particularly preferably 70% by mass to 100% by mass.
  • the ratio of B 2 (B1) to the total amount of boron in the composition is equal to or higher than the lower limit, the LSPI suppressing ability can be further improved compared to the case where it is lower than the lower limit.
  • the content of calcium derived from the component (B1) (Ca (B1) ) is preferably 50% by mass or more, and preferably 75% by mass to 100% by mass, relative to the total amount of calcium contained in the composition. %, and particularly preferably 90% by mass to 100% by mass.
  • the ratio of Ca (B1) to the total amount of calcium in the composition is equal to or higher than the lower limit, it is possible to further improve the LSPI inhibitory ability compared to when it is lower than the lower limit.
  • the content of boron derived from the component (B1) based on the total mass of the composition (B (B1) ) and the content of calcium derived from the component (B1) based on the total mass of the composition (Ca (B1) ) can be measured by the measurement method specified in JPI-5S-38.
  • the "magnesium-based detergent" used as the component (B2) is not particularly limited, and any known metallic detergent containing magnesium as a metal can be appropriately used.
  • examples of such magnesium-based detergents include sulfonate detergents, phenate detergents, salicylate detergents, etc. containing magnesium as a metal.
  • sulfonate detergents containing magnesium as a metal and salicylate detergents containing magnesium as a metal are preferable from the viewpoint of friction reduction performance.
  • the sulfonate detergent containing magnesium as such a metal is not particularly limited, and known ones can be used as appropriate.
  • a magnesium sulfonate detergent for example, a magnesium salt of an alkylaromatic sulfonic acid obtained by sulfonating an alkylaromatic compound having a molecular weight of 300 to 1500 (more preferably 400 to 1300) is suitable. can be mentioned.
  • the alkylaromatic sulfonic acid include petroleum sulfonic acid and synthetic sulfonic acid. Further, known petroleum sulfonic acids and synthetic sulfonic acids can be used as appropriate.
  • the magnesium sulfonate detergent a known one that can be used for lubricating oil compositions can be appropriately used.
  • the salicylate detergent containing magnesium as a metal is not particularly limited, and known ones can be used as appropriate.
  • Examples of such salicylate detergents include magnesium salts of alkylsalicylic acids having 1 to 2 alkyl or alkenyl groups having 4 to 36 carbon atoms (more preferably 14 to 30 carbon atoms) as substituents, and mixtures thereof. can be mentioned.
  • the magnesium salicylate detergent a known one that can be used for lubricating oil compositions can be appropriately used.
  • the magnesium-based detergent is preferably a magnesium-based detergent containing magnesium carbonate.
  • the magnesium-based detergent containing magnesium carbonate is not particularly limited, and is more preferably a magnesium-based detergent overbased with magnesium carbonate.
  • Magnesium sulfonate detergents overbased with magnesium carbonate are particularly preferred from the viewpoint of suppressing coarsening of magnesium-based detergents and loss of base number due to sedimentation and precipitation.
  • the content of magnesium (Mg) in component (B2) is 6.0 to 10.0% by mass (more preferably 7.5 to 9.5% by mass, more preferably 7.5 to 9.1% by mass).
  • the content of magnesium in the component (B2) is at least the lower limit, it is possible to reduce the viscous resistance compared to when it is less than the lower limit. It is possible to improve the stability of the lubricating oil composition compared to when the above upper limit is exceeded.
  • each magnesium-based detergent used as component (B2) is not particularly limited, it is preferably 50 to 500 mgKOH/g, more preferably 100 to 500 mgKOH/g, particularly preferably 100 to 500 mgKOH/g. is 150-500 mg KOH/g.
  • the base number of component (B2) is equal to or higher than the lower limit, it is possible to further improve the reduction of viscous resistance compared to when it is lower than the lower limit. It is possible to improve the stability of the lubricating oil composition compared to when the upper limit is exceeded.
  • the (B2) component has a magnesium content (Mg (B2) ) derived from the (B2) component based on the total mass of the composition of 20 mass ppm or more and 400 mass ppm or less (more preferably 20 mass ppm or more and 300 mass ppm). mass ppm or less, more preferably 100 mass ppm or more and 300 mass ppm or less, particularly preferably 100 mass ppm or more and 200 mass ppm or less).
  • the magnesium content (Mg (B2) ) is at least the lower limit, it is possible to improve the LSPI suppression ability compared to when it is less than the lower limit. can improve the fuel economy performance as compared with the case where the above upper limit is exceeded.
  • the magnesium content (Mg (B2) ) derived from the component (B2) based on the total mass of the composition can be measured by the measuring method described in JPI-5S-38.
  • the content of component (B2) is 0.01 to 0.60% by mass (more preferably 0.01 to 0.40% by mass, more preferably 0.10 to 0.40% by mass) based on the total amount of the lubricating oil composition. 27% by mass).
  • the content of component (B2) is at least the lower limit, it is possible to improve the acid neutralization performance compared to when it is less than the lower limit. It is possible to further improve the friction reduction performance compared to when the upper limit is exceeded.
  • the content of magnesium derived from the component (B2) is preferably 50% by mass or more, and preferably 75% by mass to 100% by mass, with respect to the total amount of magnesium contained in the composition. %, and particularly preferably 90% by mass to 100% by mass.
  • the ratio of Mg (B2) to the total amount of magnesium in the composition is at least the above lower limit, it is possible to further improve the fuel economy performance compared to the case where it is below the above lower limit.
  • the (B) component may contain other metal-based detergents other than the (B1) component and the (B2) component, if necessary.
  • the ratio of the total amount of components (B1) and (B2) to the total amount of component (B) is 50 to 100% by mass (more preferably 75 to 100% by mass, particularly preferably 90 to 100% by mass). Preferably.
  • Metal-based detergents other than components (B1) and (B2) are not particularly limited, and known metal-based detergents can be used as appropriate. From the viewpoint of achieving both LSPI suppression ability and friction reduction performance, the (B) component is more preferably a mixture of the (B1) component and the (B2) component.
  • the content of component (B) is 1.0 to 4.0% by mass (more preferably 2.2 to 3.0% by mass, more preferably 2.6 to 3.0% by mass) based on the total amount of the lubricating oil composition. 0% by mass).
  • the content of component (B) is at least the lower limit, it is possible to improve the acid neutralization performance compared to when it is less than the lower limit. It is possible to further improve the friction reduction performance compared to when the upper limit is exceeded.
  • the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1)
  • the total mass of the composition When the content (mass ratio) of calcium in the (B1) component based on mass is represented as Ca ( B1 ), the ratio of B ( B1) to Ca (B1) (B (B1) / Ca (B1 ) ) is 0.15 or more and 0.35 or less (more preferably 0.21 or more and 0.30 or less, particularly preferably 0.26 or more and 0.29 or less).
  • B (B1) /Ca (B1) is equal to or higher than the lower limit
  • the LSPI inhibitory ability can be improved as compared with the case where it is less than the lower limit. It is possible to achieve both excellent fuel saving performance, and on the other hand, when it is equal to or less than the upper limit, it is possible to reduce the friction coefficient to a lower value than when the upper limit is exceeded. It is possible to achieve both the LSPI suppression ability and the excellent fuel saving performance.
  • the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1)
  • the total mass of the composition is
  • the content (mass ratio) of calcium in the standard (B1) component is represented as Ca (B1)
  • the content (mass ratio) of magnesium in the (B2) component based on the total mass of the composition is Mg (B2)
  • the ratio of B (B1) to the total amount of Ca (B1) and Mg (B2) (Ca (B1) + Mg (B2) ) (B (B1) / [Ca (B1) + Mg (B2) ]) is 0.13 or more and 0.29 or less (more preferably 0.23 or more and 0.29 or less, particularly preferably 0.25 or more and 0.29 or less).
  • the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1)
  • the total mass of the composition When the total amount of calcium in the composition based on mass (content of total calcium:mass ratio) is represented as Ca, the ratio of B ( B1 ) to Ca (B (B1) /Ca) is 0.15 It is preferably 0.35 or less (more preferably 0.21 or more and 0.31 or less, particularly preferably 0.26 or more and 0.30 or less).
  • B (B1) /Ca is at least the lower limit, it is possible to further improve the LSPI inhibitory ability compared to when it is less than the lower limit. It is possible to further improve the fuel economy performance as compared with the case of exceeding.
  • the content (mass ratio) of boron in the component (B1) based on the total mass of the composition is represented as B (B1)
  • the total mass of the composition is
  • the total amount of calcium in the standard composition (content of total calcium: mass ratio) is represented as Ca
  • the total amount of magnesium in the composition based on the total mass of the composition (content of total magnesium: mass ratio ) is represented as Mg
  • the ratio of B (B1) to the total amount of Ca and Mg (Ca + Mg) (B (B1) / [Ca + Mg]) is 0.13 or more and 0.29 or less (more preferably 0.29).
  • B (B1) / [Ca + Mg] is at least the lower limit, it is possible to further improve the LSPI inhibitory ability compared to when it is less than the lower limit. It is possible to further improve the fuel economy performance compared to when the upper limit is exceeded.
  • the method for preparing the metal-based detergent used as the component (B) is not particularly limited, and known methods can be employed as appropriate.
  • the lubricating oil composition for internal combustion engines of the present invention further includes: Depending on the purpose, known additives generally used in lubricating oil compositions for internal combustion engines may be included as appropriate. Components that can be preferably used as such additives are described below.
  • the lubricating oil composition for an internal combustion engine of the present invention preferably contains (C) a poly(meth)acrylate-based viscosity index improver, since it is possible to further improve fuel economy performance.
  • the "poly(meth)acrylate viscosity index improver” is a known poly(meth)acrylate compound used as a viscosity index improver (for example, described in International Publication No. 2019/221295).
  • Viscosity index improver described in 2016/159006, “Viscosity index improver” described in WO 2017/099052, “Viscosity index improver” described in JP 2017-110196 agent”, “(co)polymer (A)” described in JP-A-2017-110196, etc.) can be used as appropriate.
  • the poly(meth)acrylate-based polymer used as the component (C) its structure is not particularly limited. It may be a poly(meth)acrylate-based polymer.
  • the component (C) more preferably contains a comb-shaped poly(meth)acrylate-based polymer from the viewpoint of improving viscosity-temperature characteristics and improving oil film forming properties and thereby improving fuel efficiency.
  • the poly(meth)acrylate-based viscosity index improver is a comb-shaped poly(meth)acrylate-based polymer.
  • a known poly(meth)acrylate-based polymer having a so-called comb-shaped structure for example, a "comb-shaped polymer” described in JP-A-2017-101211) , “Comb-shaped poly (meth) acrylate” described in JP 2018-177986, “Comb-shaped poly (meth) acrylate” described in WO 2016/159006, JP 2017-110196 to "Viscosity index improver” described, "(co)polymer (A)” described in JP-A-2017-110196, etc.) can be used as appropriate.
  • a comb-shaped poly(meth)acrylate-based polymer there is a poly(meth)acrylate-based polymer having a comb-shaped structure, which is a copolymer of (meth)acrylate and a (meth)acrylate-based macromonomer. Any suitable polymer can be used. Further, such a comb-shaped poly(meth)acrylate-based polymer includes (meth)acrylate, a (meth)acrylate-based macromonomer, and other monomers (e.g., ethylene, styrene, 1-butene, etc.). It may be a polymer. In this specification, "(meth)acrylate” means acrylate and/or methacrylate.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a linear or branched hydrocarbon group having 2 to 10 carbon atoms.
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents a hydrocarbon group having 12 or more and 24 or less carbon atoms.
  • a copolymer of a (meth)acrylate macromonomer represented by (hereinafter, sometimes simply referred to as “macromonomer (M-2)”) can be mentioned as a suitable one.
  • R 2 in formula (1) is a linear or branched hydrocarbon group (more preferably an alkyl group) having 2 to 10 carbon atoms.
  • the number of carbon atoms in the hydrocarbon group selected as R 2 is preferably 4 or more and 10 or less (more preferably 4 or more and 8 or less, particularly preferably 4 or more and 6 or less).
  • the number of carbon atoms in the hydrocarbon group selected as R 4 in formula (2) is 12 or more and 24 or less (more preferably 12 or more and 20 or less, particularly preferably 12 or more and 18 or less). When the number of carbon atoms is above the lower limit, the viscosity index can be increased, and when the number of carbon atoms is below the upper limit, good fluidity can be obtained under low-temperature conditions.
  • Such hydrocarbon groups may be linear or branched.
  • the macromonomer (M-2) for example, a macromonomer derived from a hydrogenated polyolefin obtained by copolymerizing butadiene and isoprene may be used.
  • macromonomers (M-2) include, for example, known macromonomers (e.g., macromonomers described in JP-A-2018-177986, and JP-A-2017-110196. (such as “monomer (a)”) may be used as appropriate.
  • the copolymerization molar ratio of these monomers is not particularly limited, but the monomer (M-1):monomer ( M-2) is preferably about 20:80 to 90:10 (more preferably 30:70 to 80:20, still more preferably 40:60 to 70:30).
  • the weight average molecular weight (Mw) of the poly(meth)acrylate polymer (preferably comb-shaped poly(meth)acrylate polymer) contained in the poly(meth)acrylate viscosity index improver is 100,000 to 1,000,000 ( More preferably 300,000 to 1,000,000, still more preferably 600,000 to 800,000).
  • Mw weight average molecular weight
  • the viscosity index when dissolved in the lubricating base oil is improved compared to the case where the weight average molecular weight is less than the lower limit, and fuel saving performance and low temperature viscosity characteristics are further improved.
  • the content of the comb-shaped poly(meth)acrylate-based polymer with respect to the total amount of the component (C) is It is preferably 30% by mass or more (more preferably 50 to 100% by mass, still more preferably 95 to 100% by mass, particularly preferably 98 to 100% by mass).
  • the content of the comb-shaped poly(meth)acrylate polymer in the component (C) is at least the above lower limit, compared with the case where it is below the above lower limit, the viscosity-temperature characteristics and oil film formation are improved, thereby saving It is possible to further improve the fuel consumption performance.
  • the component (C) it is more preferable to use a comb-shaped poly(meth)acrylate polymer alone from the viewpoint of improving viscosity-temperature characteristics and oil film formation.
  • the content of component (C) is preferably 5 to 15% by mass (more preferably 7 to 11% by mass, still more preferably 9 to 11% by mass) based on the total amount of the lubricating oil composition.
  • the content of component (C) is at least the lower limit, the viscosity-temperature characteristics are improved compared to the case where the content is less than the lower limit.
  • it is equal to or less than the upper limit it is possible to further improve the fuel economy performance by suppressing excessive thickening as compared with the case where the upper limit is exceeded.
  • the method for preparing the poly(meth)acrylate-based polymer used for component (C) is not particularly limited, and known methods can be employed as appropriate.
  • a preparation method includes, for example, a monomer (M-1), a macromonomer (M-2), and, if necessary, other monomers in the presence of a polymerization initiator (such as benzoyl peroxide).
  • a polymerization initiator such as benzoyl peroxide
  • the lubricating oil composition for an internal combustion engine of the present invention can highly disperse metal powder generated by wear during use, and can improve wear resistance and oxidation stability. Since it becomes possible, it is preferable to further contain (D) an ashless dispersant.
  • an ashless dispersant As the component (D), known compounds used as ashless dispersants in the field of lubricating oil compositions (e.g., "nitrogen-containing ashless dispersants” described in WO 2019/221295, Ashless dispersants described in JP-A-2003-155492, JP-A-2020-76004, WO 2013/147162, etc.) can be suitably used.
  • the ashless dispersant examples include mono- or bissuccinimide having at least one linear or branched alkyl group or alkenyl group in the molecule, and benzylamine having at least one alkyl group or alkenyl group in the molecule. , or polyamines having at least one alkyl group or alkenyl group in the molecule, or modified products thereof with boron compounds, carboxylic acids, phosphoric acids, or the like.
  • the linear or branched alkyl or alkenyl group is a linear or branched alkyl or alkenyl group having 40 to 400 (more preferably 60 to 350) carbon atoms. is preferably
  • (D1) boro-succinimide (above-mentioned boron-modified mono- or bis-succinimide compound, etc.), (D2) Non-boronated succinimides (such as the mono- or bis-succinimides mentioned above) and mixtures thereof can be suitably utilized.
  • each of the (D1) component and the (D2) component has a nitrogen atom content of 0.5 to 3.0% by mass based on the total amount of the component ((D1) component or (D2) component). things are preferred.
  • the (D1) component preferably has a boron content of 0.1 to 5.0% by mass (more preferably 0.1 to 3.0% by mass) based on the total amount of the component (D1).
  • component (D1) and component (D2) is preferably 1,000 to 20,000 (more preferably 2,000 to 20,000, still more preferably 4,000 to 15,000).
  • (D) component may be utilized individually by 1 type or in combination of 2 or more types.
  • the content of the (D) component is not particularly limited, but is 0.1 to 5.0% by mass based on the total amount of the lubricating oil composition ( more preferably 1.0 to 2.5% by mass).
  • the content of boron derived from the component (D1) (B (D1) ) is 90% by mass or less with respect to the total amount of boron contained in the composition. (More preferably 70% by mass or less, still more preferably 27% by mass or less).
  • B (D1) the ratio of B (D1) to the total amount of boron in the composition is equal to or less than the above upper limit, it is possible to suppress excessive generation of ash as compared with the case where the above upper limit is exceeded.
  • the lubricating oil composition of the present invention further contain (E) an antioxidant because it is possible to improve the oxidation stability.
  • the component (E) is not particularly limited, and known antioxidants that are used as antioxidants in the field of lubricating oil compositions can be used as appropriate. antioxidants, (E3) metal antioxidants (copper-based antioxidants, molybdenum-based antioxidants, etc.), and the like.
  • component (E1) known components can be used as appropriate, such as 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters; methyl-3-(3,5-di Hindered phenol compounds and bisphenol compounds such as -tert-butyl-4-hydroxyphenyl)propanoate can be mentioned.
  • the (E2) component includes, for example, aromatic amine antioxidants and compounds known as amine antioxidants such as hindered amine antioxidants (for example, compounds exemplified in International Publication No. 2020/095970). compounds, etc.) can be used as appropriate.
  • aromatic amine-based antioxidant alkylated diphenylamine and alkylated phenyl- ⁇ -naphthylamine can be preferably used.
  • hindered amine-based antioxidant for example, compounds having a 2,2,6,6-tetraalkylpiperidine skeleton (2,2,6,6-tetraalkylpiperidine derivatives) can be preferably used.
  • aromatic amine-based antioxidants can be used more preferably.
  • component (E3) examples include oxymolybdenum sulfide or alkylamine complexes of oxymolybdenum, oxymolybdenum sulfide or alkenylsuccinimide complexes of oxymolybdenum, oxymolybdenum sulfide dithiocarbamate, and organic molybdenum oxides such as oxymolybdenum sulfide dithiophosphate. inhibitors and the like.
  • oxymolybdenum sulfide or oxymolybdenum-ditridecylamine complex is preferred because it suppresses viscosity increase and maintains fuel efficiency performance over a long period of time and is superior in high-temperature detergency.
  • oxymolybdenum sulfide or oxymolybdenum-alkenylsuccinimide complexes are more preferred.
  • the (E) component may be used alone or in combination of two or more.
  • the (E1) component, the (E2) component, and the (E3) component may be used in combination as appropriate. is possible, it is preferable to use the (E2) component and the (E3) component in combination.
  • the content of the (E) component is 1.5% by mass or more and 2.5% by mass or less (more than preferably 1.7% by mass or more and 2.0% by mass or less).
  • the content of the (E1) component is 2.0% by mass or less (more preferably 0.0% by mass) based on the total amount of the lubricating oil composition. 5% by mass or less).
  • the content of the (E2) component is 1.3% by mass or more and 2.3% by mass or less based on the total amount of the lubricating oil composition. (more preferably 1.5% by mass or more and 1.9% by mass or less).
  • the content of the (E3) component is 0.3% by mass or less (more preferably 0.3% by mass) based on the total amount of the lubricating oil composition. 1% by mass or more and 0.2% by mass or less).
  • the lubricating oil composition for internal combustion engines of the present invention preferably contains (F) a molybdenum-based friction modifier (an oil-soluble organic molybdenum compound).
  • a molybdenum-based friction modifier an oil-soluble organic molybdenum compound.
  • a known molybdenum-based friction modifier that is used in the field of lubricating oil compositions can be appropriately used.
  • molybdenum dithiocarbamate (molybdenum dithiocarbamate sulfide or oxymolybdenum oxymolybdenum dithiocarbamate sulfide) is more preferable as component (F).
  • molybdenum dithiocarbamate (MoDTC) include the following general formula (3):
  • R 10 to R 13 each independently represent an alkyl group having 2 to 24 carbon atoms or an (alkyl)aryl group having 6 to 24 carbon atoms
  • Y 1 to Y 4 each independently represent a sulfur atom or an oxygen atom
  • a compound represented by can be preferably used.
  • R 10 to R 13 in the general formula (3) may be the same or different, and are alkyl groups having 2 to 24 carbon atoms or (alkyl)aryl groups having 6 to 24 carbon atoms (preferably 4 carbon atoms). to 13 alkyl groups or (alkyl)aryl groups having 10 to 15 carbon atoms).
  • Alkyl groups that can be selected as such R 10 to R 13 may be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups, and may be linear or branched.
  • the term "(alkyl)aryl group” used herein means "aryl group or alkylaryl group". In the alkylaryl group, the substitution position of the alkyl group on the aromatic ring is arbitrary.
  • Y 1 to Y 4 in the general formula (3) are each independently a sulfur atom or an oxygen atom, and at least one of Y 1 to Y 4 is a sulfur atom.
  • oil-soluble organic molybdenum compounds other than the molybdenum dithiocarbamate examples include molybdenum dithiophosphate; molybdenum compounds (e.g., molybdenum dioxide, molybdenum trioxide, molybdenum oxide, orthomolybdic acid, paramolybdic acid, (poly)molybdenum sulfide) Molybdic acids such as acids, metal salts of these molybdic acids, molybdates such as ammonium salts, molybdenum sulfides such as molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum polysulfide, molybdenum sulfide, molybdenum sulfide metals salts or amine salts, molybdenum halides such as molybdenum chloride, etc.) and sulfur-containing organic compounds (e.g.
  • oil-soluble organic molybdenum compound other than the molybdenum dithiocarbamate it is possible to use an organic molybdenum compound that does not contain sulfur.
  • sulfur-free organo-molybdenum compounds include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, molybdenum salts of alcohols, among others, molybdenum-amine complexes, molybdenum of organic acids. Molybdenum salts of salts and alcohols are preferred.
  • the content of component (F) in the lubricating oil composition is 100 to 2000 mass ppm (more preferably 300 to 1500 mass ppm, more preferably 500 to 1200 mass ppm) based on the total amount of molybdenum in the lubricating oil composition. ppm, particularly preferably 700 to 1000 mass ppm).
  • content of the component (F) is equal to or higher than the lower limit value, it becomes possible to further improve the fuel economy performance and the LSPI suppression capability.
  • the storage stability of a lubricating oil composition can be improved by content of (F) component being below the said upper limit.
  • the lubricating oil composition for internal combustion engines of the present invention preferably contains (G) an antiwear agent.
  • the antiwear agent is not particularly limited, and known compounds used as antiwear agents in lubricating oil compositions can be used.
  • As the anti-wear agent for example, a sulfur-based, phosphorus-based, sulfur-phosphorus-based anti-wear agent, or the like can be used.
  • antiwear agents include phosphites, thiophosphites, dithiophosphites, trithiophosphites, phosphates, thiophosphates, dithiophosphates, esters, trithiophosphates, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamates, zinc dithiocarbamates, disulfides, polysulfides, sulfurized olefins, sulfurized oils and fats, and the like.
  • phosphorus-based anti-wear agents are preferred, and phosphorus-based anti-wear agents containing zinc are more preferred.
  • R 14 to R 17 each independently represent a linear or branched alkyl group having 1 to 24 carbon atoms.
  • Zinc dialkyldithiophosphate (ZnDTP) represented by is particularly preferred.
  • R 14 to R 17 in the general formula (4) each independently represent a linear or branched alkyl group having 1 to 24 carbon atoms, and may be a combination of different groups.
  • the number of carbon atoms in R 14 to R 17 is preferably 3 or more, 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.
  • a 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 a mixing ratio of ZnDTP having only primary alkyl groups and ZnDTP having only secondary alkyl groups. Since the secondary alkyl group is the main component, it is possible to further improve the fuel economy performance.
  • the method for producing ZnDTP is not particularly limited, and a known method can be used as appropriate. For example, dithiophosphoric acid is synthesized by reacting an alcohol having an alkyl group corresponding to R 14 to R 17 with phosphorus pentasulfide, A method of synthesizing by neutralizing this with zinc oxide may be employed.
  • the content of the antiwear agent is preferably 0.1 to 5.0% by mass or less (more preferably 0.5 to 3.0% by mass or less) based on the total amount of the lubricating oil composition. If the content of the antiwear agent is within the above numerical range, a sufficient antiwear effect can be obtained.
  • the lubricating oil composition for internal combustion engines of the present invention preferably contains (H) a pour point depressant.
  • a pour point depressant is not particularly limited, and known pour point depressants used in lubricating oil compositions can be appropriately used.
  • Such pour point depressants include, for example, poly(meth)acrylates, ethylene-vinyl acetate copolymers, etc. Among them, polymethacrylates are preferred.
  • the poly(meth)acrylate (more preferably polymethacrylate) used as a pour point depressant has a weight average molecular weight of 20,000 to 100,000 (more than 20,000 to 80,000) are preferred.
  • the pour point depressant may be used singly or in combination of two or more.
  • its content is preferably 0.01 to 1.0% by mass (more preferably 0.03 to 0.6% by mass) based on the total amount of the lubricating oil composition.
  • the lubricating oil composition for internal combustion engines of the present invention may further contain other additives that can be used in lubricating oil compositions, in addition to the components described above.
  • other components include, but are not limited to, antifoaming agents, antirust agents, demulsifiers, metal deactivators, and the like.
  • known ones can be appropriately used.
  • Esters of hydroxy fatty alcohols with long chain fatty acids, methyl salicylate, and o-hydroxybenzyl alcohol can be mentioned.
  • the content of such other components may be appropriately designed for each component so as to be the optimum amount according to the application, and is not particularly limited, but the content of each component can be adjusted to the lubricating oil composition.
  • each component used as component (I) is 0.001 to 0.05 parts by mass when the total mass of the components in the lubricating oil composition other than that component is 100 parts by mass. is preferred.
  • the content of boron based on the total mass of the composition is 1000 mass ppm or less (more preferably 200 mass ppm or more and 700 mass ppm or less, more preferably 400 mass ppm or more and 650 mass ppm or less).
  • the content of calcium based on the total amount of the lubricating oil composition is 1650 mass ppm or more and 2500 mass ppm or less (more preferably 1700 mass ppm or more and 1900 mass ppm or less, more preferably 1750 mass ppm). mass ppm or more and 1900 mass ppm or less).
  • the content of calcium based on the total amount of the composition is 1650 mass ppm or more and 2500 mass ppm or less (more preferably 1700 mass ppm or more and 1900 mass ppm or less, more preferably 1750 mass ppm). mass ppm or more and 1900 mass ppm or less).
  • the content of magnesium based on the total amount of the lubricating oil composition is 20 mass ppm or more and 400 mass ppm or less (more preferably 20 mass ppm or more and 300 mass ppm or less, more preferably 100 mass ppm). mass ppm or more and 200 mass ppm or less).
  • the content of molybdenum based on the total amount of the lubricating oil composition is 100 mass ppm or more and 1200 mass ppm or less (more preferably 700 mass ppm more than 1000 mass ppm).
  • the phosphorus content based on the total amount of the lubricating oil composition is 600 mass ppm or more and 800 mass ppm or less (more preferably 700 mass ppm 800 mass ppm or less).
  • the sulfur content based on the total amount of the lubricating oil composition is 500 mass ppm or more and 3000 mass ppm or less (more preferably 1000 mass ppm more than 2700 mass ppm or less).
  • the zinc content based on the total amount of the lubricating oil composition is 500 mass ppm or more and 1300 mass ppm or less (more preferably 700 mass ppm more than 900 mass ppm or less).
  • the contents of boron, calcium, magnesium, molybdenum, zinc, sulfur and phosphorus in the lubricating oil composition can be measured according to JPI-5S-62.
  • the ratio of the content of boron based on the total amount of the lubricating oil composition to the content of calcium based on the total amount of the lubricating oil composition is preferably 0.15 to 0.35 (more preferably 0.25 to 0.35, still more preferably 0.26 to 0.30).
  • Amount ratio [mass ratio: [boron]/([calcium]+[magnesium])] is 0.13 to 0.29 (more preferably 0.20 to 0.29, more preferably 0.25 to 0.29). 28) is preferred.
  • the lubricating oil composition for internal combustion engines of the present invention more preferably has a kinematic viscosity at 100° C. of 4.0 to 9.3 mm 2 /s (more preferably 6.5 to 8.0 mm 2 /s). . Further, the lubricating oil composition of the present invention more preferably has a kinematic viscosity at 40° C. of 23.0 to 40.0 mm 2 /s (more preferably 26.0 to 30.0 mm 2 /s). When these kinematic viscosities are equal to or less than the upper limit values, it is possible to further improve the fuel economy performance as compared with the case where the above upper limit values are exceeded. On the other hand, when these kinematic viscosities are equal to or higher than the lower limit, it is possible to improve the wear resistance due to oil film retention as compared with the case where the kinematic viscosity is less than the lower limit.
  • the lubricating oil composition for internal combustion engines of the present invention preferably has a viscosity index of 180 or more (more preferably 200 or more, still more preferably 220 or more, and particularly preferably 225 or more).
  • a viscosity index of 180 or more (more preferably 200 or more, still more preferably 220 or more, and particularly preferably 225 or more).
  • the viscosity index is at least the lower limit, it is possible to improve the viscosity-temperature characteristics and wear resistance of the lubricating oil composition compared to the case where it is less than the lower limit, and the fuel economy performance. can be further improved.
  • the viscosity index is equal to or higher than the lower limit, it is possible to reduce the evaporation loss of the lubricating oil, thereby reducing the consumption of the lubricating oil.
  • the HTHS viscosity at 150° C. of the lubricating oil composition for internal combustion engines of the present invention is 1.7 mPa s or more and 2.9 mPa s or less (more preferably 2.3 mPa s or more and 2.8 mPa s or less, further preferably is preferably 2.6 mPa ⁇ s or more and 2.8 mPa ⁇ s or less, particularly preferably 2.6 mPa ⁇ s).
  • the HTHS viscosity at 150° C. is at least the lower limit, it is possible to improve wear resistance under high shear conditions compared to when it is less than the lower limit.
  • HTHS viscosity at 150°C means high-temperature high-shear viscosity at 150°C measured according to ASTM D-4683.
  • the method for producing the lubricating oil composition for an internal combustion engine of the present invention is not particularly limited, and it is possible to obtain the lubricating oil composition of the present invention (to satisfy the above conditions). It may be prepared by appropriately selecting and mixing each component to be used.
  • ⁇ (A) component lubricant base oil> (A-1) API Group II base oil (hydrocracked mineral oil base oil, Yubase (registered trademark) 3 manufactured by SK Lubricants), kinematic viscosity (100°C): 3.05 mm 2 /s, kinematic viscosity (40°C): 12.
  • ⁇ (B) Component Metallic detergent> ⁇ (B1) component: calcium-based detergent> (B1-i) Calcium borate overbased calcium salicylate, calcium content: 6.8% by mass, boron content: 2.7% by mass, base number (perchloric acid method): 190 mgKOH/g (B1-ii) Calcium carbonate overbased calcium salicylate, calcium content: 8.0% by mass, base number (perchloric acid method): 210 mgKOH/g ⁇ (B2) component: magnesium-based detergent> (B2-i) Magnesium carbonate overbased magnesium salicylate, magnesium content: 7.5% by mass, base number (perchloric acid method): 350 mg KOH/g (B2-ii) Magnesium carbonate overbased magnesium sulfonate, content of magnesium: 9.1% by weight, base number (perchloric acid method): 400 mg KOH/g.
  • ⁇ (C) Component Viscosity Index Improver (Poly(meth)acrylate Viscosity Index Improver)> (C-1) Comb-shaped polymethacrylate-based polymer (manufactured by Sanyo Chemical Industries, Ltd., trade name: Aclube V-7030, Mw: 520,000, Mn: 220,000, Mw/Mn: 2.4) (C-2) Linear polymethacrylate-based polymer (manufactured by Sanyo Chemical Industries, Ltd., trade name: ACLUBE V-5090, Mw: 480,000, Mn: 170,000, Mw/Mn: 2.8).
  • E component antioxidant>
  • Amine antioxidant manufactured by BASF, trade name: IRGANOX (registered trademark) L67, bis(nonylphenyl)amine, nitrogen content: 3.6% by mass
  • E-2 Molybdenum-based antioxidant (dialkylamine molybdate, molybdenum content: 10% by mass, nitrogen content: 3.6% by mass).
  • ⁇ (F) component friction modifier (molybdenum-based friction modifier)> (F-1) Molybdenum dithiocarbamate (MoDTC, manufactured by ADEKA Corporation, trade name: Adeka Sakura Lube 525, molybdenum content (theoretical value): 10.0% by mass).
  • G-1 Zinc dialkyldithiophosphate (ZnDTP, secondary alkyl group type, represented by the above formula (4) and wherein R 14 to R 17 in formula (4) are each a secondary alkyl group having 4 or 6 carbon atoms) any compound, zinc content: 8.0% by mass, phosphorus content: 7.0% by mass, sulfur content: 14% by mass)
  • G-2 Zinc dialkyldithiophosphate (ZnDTP, primary alkyl group type, compound represented by the above formula (4) in which all of R 14 to R 17 in formula (4) are primary alkyl groups having 8 carbon atoms, Zinc content: 8.0% by mass, Phosphorus content: 7.0% by mass, Sulfur content: 15% by mass)
  • G-3 Zinc dialkyl phosphate (ZnP, primary alkyl group type with 8 carbon atoms, zinc content: 5.3% by mass, phosphorus content: 5.2% by mass).
  • ⁇ (H) component pour point depressant> (H-1) Polymethacrylate (manufactured by Evonik Industries, trade name: Viscoplex 1-300, Mw: 60,000, Mn: 32,000, Mw/Mn: 1.9).
  • Lubricating oil compositions of Examples 1 to 5 and Comparative Examples 1 to 10 were prepared using the respective components described above so as to have the compositions shown in Tables 1 to 3.
  • “-" indicates that the component is not used.
  • “mass%” in the unit of content of component (A) represents the content (mass%) of each base oil component with respect to the total amount of lubricating base oil.
  • “inmass%” in the unit of the content of the components (B) to (H) represents the content (% by mass) of each additive with respect to the total amount of the lubricating oil composition
  • “parts by mass” is the component (I-1) Represents the ratio (parts by mass) of the component (I-1) when the total mass of the components in the lubricating oil composition excluding is 100 parts by mass.
  • “mass ppm” in the unit of [B (B1) ] represents the mass parts per million (mass ppm) of boron derived from the (B1) component based on the total amount of the lubricating oil composition.
  • mass ppm in the unit of [Ca (B1) ] represents the mass parts per million (mass ppm) of calcium derived from the (B1) component based on the total amount of the lubricating oil composition, [Mg (B2) ]
  • the unit “massppm” represents the mass parts per million (mass ppm) of magnesium derived from the component (B2) based on the total amount of the lubricating oil composition.
  • the unit “massppm” for the content of B, Ca, Mg, Mo, P, S, Zn is the lubricating oil composition Mass parts per million (mass ppm) of each element (B, Ca, Mg, Mo, P, S, Zn) based on the total amount of the substance are shown.
  • the numerical values of the content of B, Ca, Mg, Mo, P, S and Zn in the item "Content of each element in the composition" in Tables 1 to 3 are based on JPI-5S-62. This is the value measured by
  • LSPI performance evaluation test (LSPI test)> For each lubricating oil composition, evaluation test of LSPI inhibition ability in accordance with ASTM D8291 [test method: sequence nine test (Seq. IX ASTM D8291), engine used: Ford 2012 engine (2000CC, 4-cylinder, GDTI engine)] was performed. The average number of occurrences of LSPI for each lubricating oil composition determined by such measurements is shown in Tables 1 to 3 as the LSPI test results.
  • the LSPI test result (average value of the number of LSPI occurrences) satisfies the condition of "5" or less of the engine oil standard "API SP / ILSAC GF-6" standard value is evaluated.
  • "S” is indicated when the value is below the reference value (when the criterion is met), and "F” when the value exceeds the reference value (when the criterion is not satisfied).
  • the LSPI test result satisfies the condition of 5 or less, which is the reference value of "API SP/ILSAC GF-6"
  • the lubricating oil composition can be evaluated as having excellent LSPI suppression ability.
  • (A) a lubricating base oil and (B) a metal-based detergent are included, and the (B) component is a calcium-based detergent (component (B1)) and a magnesium-based a detergent (component (B2)), the content of calcium derived from component (B1) is in the range of 1650 mass ppm or more and 2500 mass ppm or less based on the total mass of the composition, and component (B2) contains The content of magnesium derived is in the range of 20 mass ppm or more and 400 mass ppm or less based on the total mass of the composition, and (B1-i) component (component containing boron and calcium) in component (B1) is contained, the total amount of B in the composition is 1000 mass ppm or less, B (B1) /Ca (B1) is 0.15 or more and 0.35 or less, and B (B1) / [Ca ( B1) +Mg (B2) ] is 0.13 or more and 0.29 or less
  • B (B1) /[Ca (B1) +Mg (B2) ] is 0.29
  • B (B1) /Ca (B1) is outside the range of 0.15 or more and 0.35 or less.
  • the lubricating oil compositions obtained in Comparative Examples 2 and 9 had a particularly large friction coefficient.
  • the lubricating oil composition for internal combustion engines of the present invention is particularly useful as a lubricating oil composition for engines such as gasoline engines and diesel engines.

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

Abstract

Cette composition lubrifiante destinée à un moteur à combustion interne contient (A) une huile de base lubrifiante et (B) un détergent métallique, (B) contenant (B1) un détergent à base de calcium, dans lequel la teneur en calcium, sur la base de la masse totale de la composition, se situant dans une plage spécifique, et (B2) un détergent à base de magnésium, dans lequel la teneur en magnésium, sur la base de la masse totale de la composition, se situant dans une plage spécifique ; le (B1) constituant contient (B1-1) un détergent à base de calcium qui contient du bore et du calcium, la teneur en bore, sur la base de la masse totale de la composition, étant inférieure ou égale à 1 000 ppm ; qui définit B (B1) en tant que teneur en bore dans le constituant (B1) sur la base de la masse totale de la composition, Ca(B1) en tant que teneur en calcium dans le constituant (B1) sur la base de la masse totale de la composition, et Mg(B2) en tant que teneur en magnésium dans le constituant (B2) sur la base de la masse totale de la composition, le rapport (B(B1)/Ca(B1)) de B(B1) à Ca(B1) est 0,15-0,35, et le rapport (B(B1)/[Ca(B1)+Mg(B2)]) de B(B1) à la teneur totale en (Ca(B1)+Mg(B2)) de Ca(B1) et Mg(B2) est 0,13-0,29.
PCT/JP2022/003125 2021-03-23 2022-01-27 Composition lubrifiante pour moteur à combustion interne Ceased WO2022201845A1 (fr)

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CN202280019723.9A CN116964180B (zh) 2021-03-23 2022-01-27 内燃机用润滑油组合物

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JP2024124061A (ja) * 2023-03-02 2024-09-12 Ｅｎｅｏｓ株式会社 潤滑油組成物

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TW202239954A (zh) 2022-10-16
CN116964180A (zh) 2023-10-27
TWI836351B (zh) 2024-03-21
CN116964180B (zh) 2025-11-07
US20240301314A1 (en) 2024-09-12
JP7650174B2 (ja) 2025-03-24

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