WO2016152993A1 - Composition d'huile lubrifiante pour moteur à combustion interne de type à allumage par étincelle, son procédé de production, moteur à combustion interne de type à allumage par étincelle l'utilisant, et procédé de lubrification de moteur à combustion interne - Google Patents

Composition d'huile lubrifiante pour moteur à combustion interne de type à allumage par étincelle, son procédé de production, moteur à combustion interne de type à allumage par étincelle l'utilisant, et procédé de lubrification de moteur à combustion interne Download PDF

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WO2016152993A1
WO2016152993A1 PCT/JP2016/059450 JP2016059450W WO2016152993A1 WO 2016152993 A1 WO2016152993 A1 WO 2016152993A1 JP 2016059450 W JP2016059450 W JP 2016059450W WO 2016152993 A1 WO2016152993 A1 WO 2016152993A1
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oil composition
lubricating oil
internal combustion
combustion engine
mass
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PCT/JP2016/059450
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English (en)
Japanese (ja)
Inventor
俊匡 宇高
和志 田村
秀樹 鎌野
晃良 飯島
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出光興産株式会社
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Priority to EP16768896.9A priority Critical patent/EP3275980B1/fr
Priority to CN201680017329.6A priority patent/CN107406795B/zh
Priority to US15/560,035 priority patent/US20180072961A1/en
Publication of WO2016152993A1 publication Critical patent/WO2016152993A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—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
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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
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
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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—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to a lubricating oil composition for a spark ignition internal combustion engine, a method for producing the lubricating oil composition, a spark ignition internal combustion engine using the lubricating oil composition, and a lubricating method for the internal combustion engine.
  • FIG. 1 is a configuration diagram illustrating a spark ignition internal combustion engine 1 according to an embodiment of the present invention.
  • the lubricating oil composition that has entered the combustion chamber due to rising oil is exposed to high heat, the base oil is evaporated, and the metallic additive blended in the lubricating oil composition is concentrated.
  • a calcium-based detergent is added as a metal-based additive.
  • this metal-based additive is concentrated, the combustion state is deteriorated and knocking is prevented. It is thought to be a cause.
  • the present invention provides a lubricating oil composition for an internal combustion engine having excellent cleanliness after determining the additive and the amount of the additive that improve the combustion state even in a spark ignition type internal combustion engine in which oil rise is likely to occur.
  • An object of the present invention is to provide a product, a method for producing the lubricating oil composition, a spark ignition type internal combustion engine using the lubricating oil composition, and a method for lubricating the internal combustion engine.
  • a lubricating oil composition having the following constitution can improve the combustion state and obtain an excellent cleanliness even when oil rises.
  • a lubricating oil composition for use in a spark ignition internal combustion engine having a total tension per piston of 100 N or less of the tension applied to the piston ring comprising a base oil, (A) a calcium-based detergent, and (B1 And (B2) a lubricating oil composition comprising at least one selected from a magnesium-based additive and (C) an ashless sulfur-based additive, wherein the component (A) is converted to calcium atoms.
  • the total amount of the lubricating oil composition is 0.15% by mass or less, and the total content of the component (B1) in terms of sodium atom and the content in terms of magnesium atom of the component (B2) Formulated so that it is 0.2% by mass or less based on the total amount of the oil composition, and the content in terms of sulfur atom of the component (C) is 0.01% or more based on the total amount of the lubricating oil composition
  • a spark ignition type internal combustion engine having a total tension per piston of 100 N or less of the tension applied to the piston ring, and a base oil, (A) a calcium-based detergent, (B1) a sodium-based additive, and (B2) A lubricating oil composition comprising at least one selected from magnesium-based additives and (C) an ashless sulfur-based additive, and the content of the component (A) in terms of calcium atoms is the lubricating oil composition
  • the total amount of the oil composition is 0.15% by mass or less, and the total of the content in terms of sodium atom of the component (B1) and the content in terms of magnesium atom of the component (B2) is the lubricating oil composition
  • the lubricating oil composition which is 0.2% by mass or less based on the total amount of the product, and the content of the component (C) in terms of sulfur atom is 0.01% by mass or more based on the total amount of the lubricating oil composition
  • a spark ignition internal combustion engine in which the total tension per piston of the tension applied to the piston ring is 100 N or less, a base oil, (A) a calcium-based detergent, (B1) a sodium-based additive, and (B2) A lubricating oil composition comprising at least one selected from magnesium-based additives and (C) an ashless sulfur-based additive, and the content of the component (A) in terms of calcium atoms is the lubricating oil composition
  • the total amount of the oil composition is 0.15% by mass or less, and the total of the content in terms of sodium atom of the component (B1) and the content in terms of magnesium atom of the component (B2) is the lubricating oil composition
  • the lubricating oil composition which is 0.2% by mass or less based on the total amount of the product, and the content of the component (C) in terms of sulfur atom is 0.01% by mass or more based on the total amount of the lubricating oil composition Spark ignition internal combustion engine Method of lubrication, Is to provide.
  • a lubricating oil composition for an internal combustion engine having excellent cleanliness and excellent cleanliness even when oil rises a method for producing the lubricating oil composition, and the lubricating oil composition are provided.
  • the spark ignition internal combustion engine used and a method for lubricating the internal combustion engine can be provided.
  • the lubricating oil composition for a spark ignition internal combustion engine is selected from a base oil, (A) a calcium-based detergent, (B1) a sodium-based additive, and (B2) a magnesium-based additive. And (C) an ashless sulfur-based additive, and the content of the component (A) in terms of calcium atoms is 0.00 on the basis of the total amount of the lubricating oil composition.
  • the total of the content in terms of sodium atom of the component (B1) and the content in terms of magnesium atom of the component (B2) is 0.2 mass based on the total amount of the lubricating oil composition.
  • the content in terms of sulfur atom of the component (C) is 0.01% by mass or more based on the total amount of the lubricating oil composition.
  • any one of mineral oils and synthetic oils conventionally used as base oils for internal combustion engine lubricating oils is appropriately selected.
  • mineral oil for example, a distillate obtained by subjecting paraffin-based crude oil, intermediate-based crude oil or naphthenic-based crude oil to atmospheric distillation, or distilling atmospheric residue oil under reduced pressure, or a conventional method
  • Examples include refined oils obtained by refining according to the above, for example, solvent refined oil, hydrogenated refined oil, dewaxed oil, and clay-treated oil.
  • Synthetic oils include, for example, polybutene and ⁇ -olefin homopolymers or copolymers (for example, ⁇ -olefin homopolymers or copolymers having 8 to 14 carbon atoms such as ethylene- ⁇ -olefin copolymers).
  • Poly- ⁇ -olefins (PAO) various esters such as polyol esters, dibasic acid esters, and phosphoric acid esters; various ethers such as polyphenyl ether; polyglycol; alkylbenzene; alkylnaphthalene; Fischer-Tropsch method, etc.
  • the base oil the mineral oil and synthetic oil may be used singly or in combination of two or more. Further, a mixture of mineral oil and synthetic oil may be used.
  • kinematic viscosity of the base oil is 2 mm 2 / s or more 30 mm 2 / s or less, preferably 2 mm 2 / s or more 15 mm 2 / s or less, more preferably 2 mm 2 / s or more and 10 mm 2 / s or less.
  • the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small.
  • a viscosity index is 80 or more normally, Preferably it is 100 or more, More preferably, it is 120 or more.
  • a base oil having a viscosity index of 80 or more is preferable because a change in viscosity due to a change in temperature is small.
  • the viscosity after mixing should just be contained in the said range.
  • any oil may be used as long as it contains mineral oil and / or poly- ⁇ -olefin (PAO) having a viscosity index of 120 or more corresponding to API classification group 3.
  • PAO poly- ⁇ -olefin
  • the content of the base oil relative to the total amount of the lubricating oil composition for a spark ignition internal combustion engine is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.
  • 99 mass% is preferable and 95 mass% or less is more preferable.
  • Examples of the (A) calcium detergent used in the lubricating oil composition according to one embodiment of the present invention include sulfonate, phenate, and salicylate calcium salts, which are used alone or in combination of two or more. Can be used. From the viewpoint of cleanliness, a calcium salt of salicylate (calcium salicylate) is preferred.
  • the calcium salt of the sulfonate is preferably one having a molecular weight of 300 to 1,500, more preferably 400 to 700, and a calcium salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound is preferably used. It is done.
  • a calcium salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound is preferably used. It is done.
  • alkylphenol, alkylphenol sulfide, and calcium salt of Mannich reaction product of alkylphenol are preferably used.
  • As the salicylate a calcium salt of alkyl salicylic acid is preferably used.
  • the alkyl group constituting the calcium detergent is preferably an alkyl group having 4 to 30 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms, which may be linear or branched. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.
  • calcium salts of sulfonate, phenate and salicylate the above-mentioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, alkyl salicylic acid, etc.
  • calcium base such as direct calcium oxide or hydroxide Neutral calcium sulfonate, neutral calcium phenate, neutral calcium salicylate, etc.
  • overbased calcium detergents such as overbased calcium sulfonates, overbased calcium phenates and overbased calcium salicylates obtained by treatment.
  • the metal ratio of the calcium-based detergent can be usually used in a mixture of 20 or less, or a mixture of two or more.
  • the metal ratio referred to here is expressed by the valence of the metal element in the metal detergent (in this case, the calcium detergent) ⁇ metal element content (mol%) / soap group content (mol%).
  • the metallic element is calcium, and the soap group means a sulfonic acid group, a phenol group, a salicylic acid group, and the like.
  • the content of calcium atoms contained in the calcium-based detergent is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 10% by mass.
  • the base number of the calcium detergent is preferably 10 to 600 mgKOH / g, more preferably 50 to 300 mgKOH / g, and still more preferably 100 to 250 mgKOH / g from the viewpoints of cleanliness and acid neutralization performance.
  • the base number referred to here is JIS K2501 “Petroleum products and lubricants-Neutralization number test method”. Means the base value by the hydrochloric acid method measured according to the above.
  • the calcium atom content of the calcium detergent is 0.15% by mass or less based on the total amount of the lubricating oil composition.
  • the content of the component (A) is 0.15% by mass or less, the combustion state can be improved even when oil rises.
  • the content of the component (A) is preferably 0.05 to 0.15% by mass, more preferably 0.06 to 0.15% by mass. 0.08 to 0.15 mass% is more preferable.
  • the lubricating oil composition according to an embodiment of the present invention includes at least one selected from (B1) sodium-based additives and (B2) magnesium-based additives.
  • a sodium-based detergent is preferably mentioned.
  • sodium detergents include sulfonates, phenates, and sodium salts of salicylates, and these can be used alone or in combination. From the viewpoint of cleanliness, a sodium salt of sulfonate (sodium sulfonate) is preferable.
  • sodium detergent sulfonate, phenate, and salicylate are the same as described for the sulfonate, phenate, and salicylate in the calcium detergent. Moreover, it is the same as the description in a calcium type detergent that a basic sodium type detergent and an overbased sodium type detergent can be employ
  • the content of sodium atoms contained in the sodium-based detergent is preferably 1 to 25% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass from the viewpoint of cleanliness.
  • the base number of the sodium-based detergent is preferably 10 to 650 mgKOH / g, more preferably 100 to 600 mgKOH / g, and still more preferably 300 to 550 mgKOH / g from the viewpoints of cleanliness and acid neutralization performance.
  • a magnesium-based detergent is preferably exemplified.
  • examples of magnesium detergents include sulfonates, phenates, and magnesium salts of salicylates, and these can be used alone or in combination of two or more. From the viewpoint of cleanliness, a magnesium salt of salicylate (magnesium salicylate) is preferred.
  • magnesium-based detergent sulfonate, phenate, and salicylate are the same as described for the sulfonate, phenate, and salicylate in the calcium-based detergent. Moreover, it is the same as the description in a calcium type detergent that a basic magnesium type detergent and an overbased magnesium type detergent can be employ
  • the content of magnesium atoms contained in the magnesium-based detergent is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, and still more preferably 5 to 20% by mass from the viewpoint of cleanliness.
  • the base number of the magnesium-based detergent is preferably 10 to 650 mgKOH / g, more preferably 100 to 600 mgKOH / g, and still more preferably 200 to 550 mgKOH / g from the viewpoints of cleanliness and acid neutralization performance.
  • At least one selected from (B1) sodium-based additive and (B2) magnesium-based additive includes a content in terms of sodium atom and a content in terms of magnesium atom.
  • the total content of the lubricating oil composition is 0.2% by mass or less.
  • the total content of the sodium atom content and the magnesium atom content is preferably 0.005 to 0.20% by mass, and 0.01 to 0.15% by mass. More preferred is 0.01 to 0.10% by mass.
  • magnesium atoms (Mg) contained in the magnesium-based additive and / or the sodium-based additive magnesium atoms (Mg) contained in the magnesium-based additive and / or the sodium-based additive.
  • the mass ratio [(Mg and / or Na) / Ca] of sodium atoms (Na) and calcium atoms (Ca) contained in the additive is preferably 0.03 to 3.5.
  • the content of the calcium-based detergent and the content of (B1) the sodium-based additive and (B2) the magnesium-based additive have the above relationship, whereby excellent cleanliness is obtained and combustion A state can be made favorable.
  • the mass ratio [(Mg and / or Na) / Ca] of magnesium atom (Mg) and / or sodium atom (Na) to calcium atom (Ca) is 0.05 to 2.5. Is preferable, 0.05 to 1 is more preferable, and 0.06 to 0.8 is still more preferable.
  • the lubricating oil composition according to an embodiment of the present invention includes (C) an ashless sulfur-based additive.
  • the ashless sulfur-based additive is not particularly limited as long as it contains sulfur and does not contain a metal atom.
  • thiazines, dithiazines, imidazolethiones, imidazoledithiones, and thiazoles are examples of thiazines, dithiazines, imidazolethiones, imidazoledithiones, and thiazoles.
  • antioxidants, oxygen scavengers, antiwear agents, extreme pressure agents, etc. can be used in combination these alone, or plural kinds.
  • sulfur-containing heterocycles such as benzothiophene ring, naphthothiophene ring, dibenzothiophene ring, thienothiophene ring, dithienobenzene ring, thiophene ring, naphthothiazole ring, It has a sulfur-containing heterocycle such as an isothiazole ring, naphthisothiazole ring, phenothiazine ring, phenoxathiin ring, dithiaphthalene ring, thianthrene ring, thioxanthene ring, bithiophene ring, preferably on the carbon atom of the heterocycle
  • An additive mainly used as an antiwear agent having a structure in which at least one sulfur atom is bonded is also preferred.
  • dithiocarbamates such as dialkyldithiocarbamate having a linear or branched alkyl group having 1 to 20 carbon atoms; for example, didodecylthiopropionate, dioctadecylthiopropionate, dimyristylthiopro Thiopropionates such as dialkylthiopropionate having a linear or branched alkyl group having 1 to 20 carbon atoms such as pionate and dodecyloctadecylthiopropionate; corresponding to the thiopropionates Thiodipropionates such as dialkylthiodipropionate; alkyl thiazole, aminoalkyl thiazole, alkyl benzothiazole, alkyl mercapto thiazole, amino thiazole, benzo having a linear or branched alkyl group having 1 to 20 carbon atoms Thiazo such as thiazole Benzyl sulf
  • a nitrogen-containing organic group such as an amino group, an imino group, an amide group, an imide group, a pyridyl group, a pyrazine group, a triazine group, and a benzimidazole group, a nitrogen-containing heterocyclic group, and a carbon number of 1 to 20
  • a linear or branched alkyl group of the above, and these groups are divalent organic groups such as an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, -NH-, Sulfur-containing phenols which may be linked by —O—, —S—, —COO— or the like are preferable.
  • the ashless sulfur-based additive used in the present invention may or may not have a cyclic structure in the molecule, and has a sulfur-containing heterocyclic ring. It may or may not have.
  • the content of sulfur atoms contained in the ashless sulfur-based additive is usually 1 to 40% by mass, preferably 3 to 35% by mass, although it depends on the additive used.
  • the thiopropionate additive, sulfides, and disulfides are more preferably 3 to 15% by mass.
  • the sulfur atom content of the ashless sulfur-containing additive is 0.01% by mass or more based on the total amount of the lubricating oil composition.
  • the sulfur atom content of the component (C) is preferably 0.01 to 3% by mass, more preferably 0.03 to 1% by mass, and 0.03 to 0.5% by mass. Is more preferable.
  • the lubricating oil composition according to an embodiment of the present invention may contain (D) an organic molybdenum-based additive.
  • an organic molybdenum-based additive for example, a molybdenum-based friction modifier and a molybdenum-based antioxidant can be used.
  • molybdenum-based friction modifier any compound usually used as a friction modifier for lubricating oil for internal combustion engines can be used.
  • molybdenum amine complex and / or sulfurized oxymolybdenum dithiocarbamate, trinuclear molybdenum At least one selected from sulfur compounds and molybdenum dithiophosphates, more specifically, at least one selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and amine salts of molybdic acid.
  • MoDTC molybdenum dithiocarbamate
  • MoDTP molybdenum dithiophosphate
  • amine salts of molybdic acid Can do.
  • a molybdenum amine complex is preferable, and as the molybdenum amine complex, a hexavalent molybdenum compound, specifically, molybdenum trioxide and / or molybdic acid is reacted with an amine compound.
  • a compound obtained by the production method described in JP-A-2003-252887 can be used.
  • the reaction ratio between the hexavalent molybdenum compound and the amine compound is preferably such that the molar ratio of the Mo atom of the molybdenum compound to 0.7 mol is 1 to 4 mol with respect to 1 mol of the amine compound. More preferred is 1 to 2.5.
  • reaction method a conventionally known method, for example, a method described in JP-A No. 2003-252887 can be employed.
  • a molybdenum-based antioxidant in addition to the molybdenum amine complex, a sulfur-containing molybdenum complex of succinimide described in JP-B-3-22438, JP-A-2004-2866, and the like is used. It can also be used.
  • the component (D) is preferably a molybdenum friction modifier from the viewpoint of fuel efficiency, and among them, at least one selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and an amine salt of molybdic acid. Is preferable, and molybdenum dithiocarbamate (MoDTC) is particularly preferable.
  • the content of the component (D) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.3 to 1.5% by mass based on the total amount of the lubricating oil composition. Further, the content of the component (D) in terms of molybdenum atoms is preferably 0.005 to 0.20 mass% based on the total amount of the lubricating oil composition. From the viewpoint of maintaining wear resistance, 0.01 to 0.15% by mass is more preferable, and 0.03 to 0.15% by mass is even more preferable.
  • the lubricating oil composition according to an embodiment of the present invention further contains at least one additive selected from a viscosity index improver, a dispersant, an extreme pressure agent, a non-sulfur antioxidant, and an antifoaming agent. It is preferable.
  • viscosity index improver examples include poly (meth) acrylate (dispersion type, non-dispersion type), olefin copolymer (for example, ethylene-propylene copolymer, etc.), dispersion olefin copolymer, styrene type, and the like. Examples thereof include copolymers (for example, styrene-diene copolymers, styrene-isoprene copolymers, etc.), among which poly (meth) acrylates are preferred.
  • these viscosity index improvers preferably have a weight average molecular weight (Mw) of 10,000 to 1,000,000, more preferably 30,000 to 600,000, and still more preferably 100,000 to 600,000.
  • Mw weight average molecular weight
  • the weight average molecular weight is a value obtained by measuring by GPC and using polystyrene as a calibration curve, and is specifically measured under the following conditions. Column: Two TSK gel GMH6 Measurement temperature: 40 ° C Sample solution: 0.5 mass% THF solution Detector: Refractive index detector Standard: Polystyrene
  • the blending amount of these viscosity index improvers may be appropriately determined according to the desired viscosity (for example, 150 ° C. HTHS viscosity), and is preferably 0.01 to 10 on the basis of the lubricating oil composition from the viewpoint of blending effect. It is 0.000% by mass, more preferably 0.05 to 5.00% by mass, and still more preferably 0.05 to 2.00% by mass.
  • the content of poly (meth) acrylate means the content of only the resin component composed of poly (meth) acrylate, and does not include the mass of diluent oil or the like contained together with the poly (meth) acrylate, for example. Content based on solid content.
  • a non-borated imide dispersant As the dispersant, a non-borated imide dispersant can be used. Non-boronated imide dispersants are usually referred to as imide dispersants.
  • imide dispersant succinimide is preferably used. Examples of the succinimide include a monotype represented by the following general formula (1) and a bistype compound represented by (2).
  • R 1 , R 3 and R 4 are each an alkenyl group or alkyl group having a number average molecular weight of 500 to 4,000, and R 3 and R 4 are the same or different. May be.
  • the number average molecular weight of R 1 , R 3 and R 4 is preferably 1,000 to 4,000. If the number average molecular weight of R 1 , R 3 and R 4 is 500 or more, the solubility in the base oil is good, and if it is 4,000 or less, good dispersibility is obtained and excellent cleanliness. Is obtained.
  • R 2 , R 5 and R 6 are each an alkylene group having 2 to 5 carbon atoms, and R 5 and R 6 may be the same or different.
  • m is an integer of 1 to 10, preferably an integer of 2 to 5, more preferably 3 or 4. When m is 1 or more, the dispersibility is good, and when it is 10 or less, the solubility in the base oil is also good, and excellent cleanliness is obtained.
  • N is an integer of 0 to 10, preferably an integer of 1 to 4, more preferably 2 or 3. When n is within the above range, it is preferable in terms of dispersibility and solubility in base oil, and excellent cleanliness can be obtained.
  • Succinimide is usually produced by reacting an alkenyl succinic anhydride obtained by the reaction of a polyolefin and maleic anhydride, or an alkyl succinic anhydride obtained by hydrogenating it with a polyamine. it can.
  • Monotype succinimide compounds and bis type succinimide compounds can be produced by changing the reaction ratio of alkenyl succinic anhydride or alkyl succinic anhydride and polyamine.
  • Polyamines include single diamines such as ethylenediamine, propylenediamine, butylenediamine, polyalkylenes such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine, and butylenetetramine.
  • Examples include piperazine derivatives such as polyamine and aminoethylpiperazine.
  • the content of succinimide is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and more preferably 0.5 to 5% by mass, based on the total amount of the lubricating oil composition, in consideration of cleanliness. Further, the content of the succinimide based on the total amount of the lubricating oil composition in terms of nitrogen atom is preferably 0.005 to 0.3% by mass, more preferably 0.01 to 0.1% by mass.
  • a boronated succinimide can be produced, for example, by reacting an alkenyl succinic anhydride or alkyl succinic anhydride obtained by the reaction of the above-mentioned polyolefin with maleic anhydride with the above polyamine and boron compound. It can.
  • the boron compound include boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, ammonium salt of boric acid, and the like.
  • the mass ratio of boron content B to nitrogen content N, B / N is preferably 0.1 to 3, and preferably 0.2 to 1.
  • the content of the boronated succinimide is preferably from 0.1 to 10% by mass, more preferably from 0.3 to 8% by mass, more preferably from 0.5 to 5% based on the total amount of the lubricating oil composition in consideration of cleanliness.
  • the content in terms of boron atom based on the total amount of the lubricating oil composition of the boronated succinimide is preferably 0.005 to 0.3% by mass, more preferably 0.01 to 0.1% by mass. More preferred.
  • modified polybutenyl succinimide obtained by reacting the succinimide described above with alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate, epoxy compound, organic acid or the like is used. You can also.
  • Antiwear agent Preferred examples of the antiwear agent include zinc dithiophosphates such as zinc dialkyldithiophosphate and zinc dialkyldioxyphosphate represented by the following general formula (3).
  • each X is independently an oxygen atom or a sulfur atom, and at least two are the same atoms.
  • R 7 and R 8 each independently represents a primary or secondary alkyl group having 3 to 22 carbon atoms, or an alkylaryl group substituted with an alkyl group having 3 to 18 carbon atoms.
  • primary or secondary alkyl group having 3 to 22 carbon atoms primary or secondary propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group
  • Examples include decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group and the like.
  • alkylaryl group substituted with an alkyl group having 3 to 18 carbon atoms examples include a propylphenyl group, a pentylphenyl group, an octylphenyl group, a nonylphenyl group, and a dodecylphenyl group.
  • the zinc dithiophosphate may be used singly or in combination of two or more, but from the viewpoint of improving the wear resistance, it is particularly preferable to use zinc dithiophosphate having a secondary alkyl group. preferable.
  • antiwear agents such as ashless friction modifiers such as aliphatic amines, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols and aliphatic ethers should be used as the antiwear agent. You can also.
  • the content of the antiwear agent is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass based on the total amount of the lubricating oil composition.
  • the content of the zinc dithiophosphate based on the total composition is preferably 0.005 to 0.2% by mass in terms of phosphorus atom, and 0.01 to 0.001. 15 mass% is more preferable.
  • extreme pressure agents include thiophosphate ester extreme pressure agents such as trialkyl trithiophosphates, triaryl trithiophosphates, triaralkyl trithiophosphates; trialkyl phosphates, triaryl phosphates, trialkyl phosphonates, trialkyl phosphites Phosphoric esters such as triaryl phosphites and dialkyl hydrogen phosphites, phosphorous esters, and amine salts thereof, etc. Phosphorus extreme pressure agents; C 3-60 carboxylic acids or alkali metals of dicarboxylic acids Examples thereof include organic metal extreme pressure agents such as salts and alkaline earth metal salts, and these can be used alone or in combination.
  • the content of the extreme pressure agent is preferably 0.001 to 5 mass%, more preferably 0.005 to 3 mass%, based on the total amount of the lubricating oil composition, from the viewpoint of lubricity and stability.
  • Non-sulfur antioxidant As the non-sulfur-based antioxidant, a molybdenum-based antioxidant, a phenol-based antioxidant, an amine-based antioxidant, and the like can be suitably used.
  • the molybdenum-based antioxidant include molybdenum amine complex formed by reacting molybdenum trioxide and / or molybdic acid with an amine compound.
  • phenolic antioxidant any one of known phenolic antioxidants conventionally used as an antioxidant for lubricating oil for internal combustion engines can be appropriately selected and used.
  • Monophenolic antioxidants such as alkylphenolic antioxidants such as 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol) ) And the like; hindered phenolic antioxidants and the like.
  • any one of known amine-based antioxidants conventionally used as an antioxidant for lubricating oil for internal combustion engines can be appropriately selected and used, for example, Diphenylamine, diphenylamine-based antioxidants such as alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms; ⁇ -naphthylamine, naphthylamine-based antioxidants such as alkyl-substituted phenyl- ⁇ -naphthylamine having 3 to 20 carbon atoms, etc. Can be mentioned.
  • Non-sulfur antioxidants may be used alone or in combination of the above.
  • the content of the non-sulfur antioxidant is preferably 0.05 to 7% by mass, more preferably 0.05 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of balance between effects and economy. .
  • antifoaming agents examples include silicone-based antifoaming agents, fluorosilicol-based antifoaming agents, and fluoroalkyl ether-based antifoaming agents, and these can be used alone or in combination of two or more.
  • the content of the antifoaming agent is preferably 0.005 to 2% by mass, and more preferably 0.01 to 1% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of balance between effect and economy.
  • additives In the spark ignition type internal combustion engine lubricating oil composition of the present invention, other additives can be further blended as necessary within the range not impairing the object of the present invention.
  • Other additives include, for example, rust inhibitors such as petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester; corrosion inhibitors; polyoxyethylene alkyl ether, poly Surfactants such as polyalkylene glycol-based nonionic surfactants such as oxyethylene alkyl phenyl ether and polyoxyethylene alkyl naphthyl ether; metal-free compounds such as benzotriazole-based, tolyltriazole-based, thiadiazole-based and imidazole-based compounds Activating agent; Ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, con
  • the Noack evaporation loss of the lubricating oil composition according to the embodiment of the present invention is preferably 10% by mass or more, and more preferably 10 to 15% by mass.
  • the Noack evaporation loss is 10% by mass or more, a sufficiently low viscosity that contributes to low fuel consumption performance is obtained, and when it is 15% by mass or less, excessive oil rise can be suppressed, and combustion of an ignition type internal combustion engine An excellent prevention effect of deterioration of the state is obtained.
  • Noack evaporation loss is a value measured according to JPI-5S-41-2004.
  • the kinematic viscosity at 100 ° C. of the lubricating oil composition according to the embodiment of the present invention is preferably 10 mm 2 / s or less, more preferably 3 to 10 mm 2 / s.
  • the kinematic viscosity at 100 ° C. is a value measured according to “Petroleum product kinematic viscosity test method” defined in JIS K 2283.
  • the sulfated ash content of the lubricating oil composition according to the embodiment of the present invention is based on the total amount of the composition from the viewpoint of obtaining a sufficiently low fuel consumption performance or obtaining an excellent preventive effect on the deterioration of the combustion state of the ignition internal combustion engine. It is preferably 1.0% by mass or less, more preferably 0.4 to 1.0% by mass, and still more preferably 0.5 to 1.0% by mass.
  • the sulfated ash is JIS K 2272 5. This is a value measured by the method specified in “Testing method for sulfated ash”. It refers to the ash content that is heated by adding sulfuric acid to the carbonized residue generated by burning the sample. Used to know the approximate amount of metallic additive.
  • the HTHS viscosity at 150 ° C. of the lubricating oil composition according to the embodiment of the present invention is preferably 1.0 to 5 mPa ⁇ s, more preferably 1.0 to 4 mPa ⁇ s, and still more preferably 1.5 to 3 mPa ⁇ s. . If the HTHS viscosity at 150 ° C. is 1.0 mPa ⁇ s or more, the lubricating performance can be improved. If the HTHS viscosity is 5 mPa ⁇ s or less, excellent viscosity characteristics at low temperature can be obtained, and excellent fuel economy can be achieved. Sex is also obtained. The HTHS viscosity at 150 ° C.
  • the HTHS viscosity at 150 ° C. is a value of a high temperature high viscosity at 150 ° C. measured according to ASTM D 4741, and specifically, a value obtained by the measurement method described in the examples.
  • a method for producing a lubricating oil composition according to an embodiment of the present invention includes a piston having a piston ring, and is used for a spark ignition internal combustion engine in which a total tension per piston of the piston ring is 100 N or less.
  • a method for producing a lubricating oil composition comprising: (C) a base oil comprising (A) a calcium detergent, (B1) a sodium additive, and (B2) a magnesium additive; Ashless sulfur-based additive, the content of the component (A) in terms of calcium atom is 0.15% by mass or less on the basis of the total amount of the lubricating oil composition, and the amount in terms of sodium atom of the component (B1) And the total content of the component (B2) in terms of magnesium atoms is 0.2% by mass or less based on the total amount of the lubricating oil composition, and the content in terms of sulfur atoms of the component (C) The amount is In the total amount of 0.01 mass or more Namerayu composition, characterized in that blended so that the.
  • At least the component (A), the component (B1), the component (B2), and the component (C) are blended in the above content range.
  • an organic molybdenum-based additive, and a viscosity index improver, a dispersant, an antiwear agent, an extreme pressure agent, a non-sulfur antioxidant, and an antifoaming agent as long as the effects of the present invention are not hindered.
  • At least one kind of additive, and other additives may be blended.
  • (A) component, (B1) component, (B2) component, (C) component, (D) component added as needed, and other additives are mixed separately, and then this mixture is used as a base oil. They may be introduced into the base oil, or each may be sequentially added to the base oil and mixed. In this case, the order of addition is not limited.
  • spark ignition internal combustion engine 1 includes a gasoline engine.
  • Fuels used in spark ignition internal combustion engines include fuel oils classified as Class 1 petroleum, petroleum, biomass ethanol, alcohol fuel, liquefied petroleum gas, natural gas, synthetic gas, hydrogen fuel, bifuel, etc. Is mentioned.
  • the spark ignition internal combustion engine 1 includes a cylinder block 11, a piston crank mechanism 12 incorporated in the cylinder block 11, and a valve mechanism 13 that performs intake of air-fuel mixture into the cylinder block 11 and exhaust of combustion gas.
  • the cylinder block 11 includes a cylinder 21 and a crankcase 22.
  • the spark ignition internal combustion engine 1 has a spark plug F at the top of a cylinder 21.
  • the piston crank mechanism 12 has a piston 23 and a crankshaft 24.
  • a piston ring 30 is disposed on the piston 23.
  • the piston ring 30 includes a top ring 31, a second ring 32, and an oil ring 33. In the spark ignition internal combustion engine 1, the total tension per piston of the tension applied to the piston ring 30 is set to 100 N or less.
  • the total tension per piston of the tension applied to the piston ring 30 is the sum of the tension applied to each of the plurality of rings.
  • the tensions (n) relating to the piston rings of the top ring 31, the second ring 32 and the oil ring 33 are totaled.
  • the tension applied to the piston ring is a value measured in accordance with “Measuring method of tangential tension” of JIS B 8032-2.
  • the spark ignition internal combustion engine 1 has a lubricating oil composition L.
  • the lubricating oil composition L is stored in an oil pan 41 or an oil tank (not shown) in the crankcase 22, and the piston crank mechanism 12 and the valve mechanism 13 are associated with the operation of the spark ignition internal combustion engine 1. Etc., and these parts are lubricated and cooled.
  • the above-described lubricating oil composition for a spark ignition internal combustion engine according to the embodiment of the present invention is applied.
  • the present invention includes a method of lubricating the spark ignition internal combustion engine 1 in which the total tension per piston of the tension applied to the piston ring 30 is 100 N or less by the above-described spark ignition internal combustion engine lubricating oil composition. .
  • the total tension per piston of the tension applied to the piston ring 30 is 100 N or less.
  • the spark-ignition internal combustion engine lubricating oil composition according to the present embodiment can delay the generation timing of the cool flame even when oil rises. Further, if the total tension per piston of the tension applied to the piston ring of the spark ignition internal combustion engine can be reduced, the fuel efficiency performance of the automobile is improved when the spark ignition internal combustion engine is installed in an automobile. be able to.
  • the total tension per piston of the tension applied to the piston ring 30 can be preferably used for a low-tension spark ignition internal combustion engine of 95 N or less, and further 90 N or less.
  • the lower limit value of the total tension per piston of the tension applied to the piston ring 30 is not particularly limited, but is preferably 5N or more, more preferably 10N or more, and further preferably 15N or more. If the lower limit is 5N or more, it is difficult for oil to rise.
  • the above engine was provided with a small quartz window in the cylinder head, and light absorption from the xenon light source was transmitted to the right end of the combustion chamber to measure the absorbance at the end.
  • the xenon light transmitted through the combustion chamber was guided to a spectroscope by an optical fiber and split into a wavelength of 293.1 nm. This wavelength is a wavelength at which strong absorption occurs in formaldehyde.
  • Formaldehyde is an important chemical species that is produced when cold flames occur and decreases rapidly with the transition to blue flames and the occurrence of hot flames.
  • the dispersed light is converted into an electrical signal by a photomultiplier tube, and the transmitted light intensity E0 in a state where no reaction occurs and the transmitted light intensity E1 at an arbitrary crank angle are used to determine the absorbance (E0-E1) / Calculated by defining E0.
  • the time when the absorbance started to increase was defined as the cold flame generation timing, and the timing when the absorbance decreased rapidly was defined as the autoignition timing.
  • a pressure sensor was provided in the combustion chamber, and the amplitude of pressure vibration generated at the time of knocking was measured and used as an index of knock strength.
  • an air-fuel mixture composed of fuel and oxidant is compressed by the piston inside the cylinder, and the temperature and pressure rise.
  • the combustion in which the air-fuel mixture ignites by compression that is, low-temperature self-ignition, occurs before the original ignition with clear heat generation occurs.
  • This low temperature self-ignition includes a stage in which a low temperature flame called a cold flame or a blue flame appears, and active chemical species are generated, leading to the generation and propagation of a hot flame with rapid heat generation.
  • an active chemical species is forcibly provided by an ignition source such as an electric spark, and the generation and propagation of a thermal flame is reached.
  • the sample blended with the sample compositions of Test Examples 1 to 13 shown in Tables 1 to 3 is forcibly introduced into the combustion chamber through the fuel injector.
  • the fuel oil was replaced with the sample and burned.
  • the lubricating base oil has a higher viscosity than the fuel oil and it is difficult to spray the lubricating oil composition with the fuel injector, instead of the lubricating base oil, PRF50, which is a fuel oil having an octane number of 50, is used. Additives were mixed to prepare a sample blended with the sample compositions of Test Examples 1 to 13 shown in Tables 1 to 3.
  • the amount of the lubricating oil composition entering the combustion chamber due to the oil rising from the crank chamber is not constant and is largely governed by the probability.
  • the influence of the lubricating oil composition on the combustion is maximized. Therefore, the maximum influence that the composition can have can be evaluated by forcibly splashing droplets having specific properties into the combustion chamber and analyzing the combustion state. Therefore, in this combustion test, in a spark ignition internal combustion engine that has a low tension such that the total tension per cylinder of the piston ring is 100 N or less and is prone to oil rising, a large amount of lubricating oil is accidentally generated.
  • the sample was forcibly introduced into the combustion chamber as described above.
  • the spark ignition type internal combustion engine used for the flammability test is filled with a general lubricating oil composition in a crank chamber or the like, but entry of the lubricating oil composition from the crank chamber into the combustion chamber is restricted. Therefore, it is not necessary to consider the impact on this study.
  • both lubricant base oil and fuel oil are hydrocarbons, the difference in reactivity with additives is small, and the effect of fuel oil droplets containing a certain concentration of organometallic additives on combustion Is considered to be close to the case where the droplets of the lubricating base oil containing the additive are scattered in the combustion chamber. Therefore, as a result of the test, if the fuel oil containing the predetermined additive does not affect combustion, even if the lubricating oil composition containing the predetermined additive enters the combustion chamber, It can be judged that it does not affect combustion. On the other hand, if it affects combustion, it can be determined that there is a possibility of affecting combustion if it enters the combustion chamber as a lubricating oil composition in an actual machine.
  • B Although the generation time of the cool flame is advanced as compared with the reference sample, the increase in pressure vibration is 0.04 or less compared to the reference.
  • C The generation time of the cool flame is advanced compared to the reference sample, and the increase in pressure vibration is more than 0.04 compared to the reference.
  • Fuel oil Equivalent mixture of normal heptane and isooctane (PRF50) -(A) component: Calcium type detergent: Ca salicylate (Ca content 7.8 mass%, base number 225 mgKOH / g) Component (B1): Sodium-based detergent: Na sulfonate (Na content: 16.3% by mass, base number: 460 mgKOH / g) Component (B2): Magnesium-based detergent: Mg salicylate (Mg content: 6.9% by mass, base number: 300 mgKOH / g)
  • (B1) sodium-based additive has a sodium atom equivalent content of 0.21% by mass or less, and the occurrence of cold flame is not accelerated, and the increase in pressure oscillation is suppressed.
  • (B2) Magnesium-based additive has a magnesium atom equivalent content of less than 0.22% by mass, the occurrence of cold flame is not accelerated, and the increase in pressure oscillation is suppressed.
  • (A) Calcium-based detergent has an early generation of cold flame when the content in terms of calcium atom is less than 0.22% by mass, but the increase in pressure vibration is suppressed. I understand that.
  • test temperature was set at 280 ° C.
  • test time was 16 hours
  • other conditions were measured according to JPI-5S-55-99.
  • the lacquer adhering to the test tube is evaluated every 0.5 points from 0 points (black) to 10 points (colorless) according to JPI-5S-55-99. It indicates that there are few deposits and cleanliness is good. A score of 7 or higher is acceptable.
  • mass% (Ca), mass% (Na), mass% (Mg), and mass% (S) are respectively converted into calcium (Ca) atoms, converted into sodium (Na) atoms, converted into magnesium atoms (Mg).
  • And sulfur (S) atom-based lubricating oil composition based on the total amount.
  • the amount at which 150 ° C. HTHS viscosity was 2.3 mPa ⁇ s.
  • Base oil paraffinic mineral oil (kinematic viscosity at 100 ° C .: 4.1 mm 2 / s, kinematic viscosity at 40 ° C .: 17.8 mm 2 / s, viscosity index: 134)
  • component Calcium type detergent: Ca salicylate (Ca content 7.8 mass%, base number 225 mgKOH / g)
  • component (B1) Sodium-based detergent: Na sulfonate (Na content: 16.3% by mass, base number: 460 mgKOH / g)
  • B2 Magnesium-based detergent: Mg salicylate (Mg content: 6.9% by mass, base number: 320 mgKOH / g)
  • Component 1 Dialkyldithiocarbamate (sulfur content: 30.3% by mass, nitrogen content: 6.6% by mass)
  • Component 2 Dialkylthiodipropionate (Sulfur
  • Lubricating oil compositions of Examples 1-8 shown in Table 4 (A) a calcium-based detergent, (B1) a sodium additive and / or (B2) a magnesium additive, various (C ) Lubricating oil composition blended with ashless sulfur-based additive at a predetermined blending ratio has excellent cleanliness, and the results shown in Tables 1 to 3 indicate that the combustion state of the ignition internal combustion engine has deteriorated. It was confirmed to have an excellent prevention effect.

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

Abstract

L'invention concerne : une composition d'huile lubrifiante pour moteur à combustion interne qui empêche la détérioration de l'état de combustion d'un moteur à combustion interne du type à allumage, plus spécifiquement, une composition d'huile lubrifiante qui est destinée à un moteur à combustion interne du type à allumage par étincelle et est une composition d'huile lubrifiante utilisée dans un moteur à combustion interne du type à allumage par étincelle dans lequel la force de traction appliquée à un segment de piston est une force de traction totale de 100 N ou moins par piston, et qui est caractérisée en ce qu'elle contient des teneurs prédéfinies en huile de base, agent de nettoyage à base de calcium (A), au moins un additif choisi parmi un additif à base de sodium (B1) et un additif à base de magnésium (B2), et un additif à base de soufre (C) sans cendres; un procédé de production de ladite composition d'huile lubrifiante; un moteur à combustion interne du type à allumage par étincelle l'utilisant; et un procédé de lubrification de moteur à combustion interne.
PCT/JP2016/059450 2015-03-24 2016-03-24 Composition d'huile lubrifiante pour moteur à combustion interne de type à allumage par étincelle, son procédé de production, moteur à combustion interne de type à allumage par étincelle l'utilisant, et procédé de lubrification de moteur à combustion interne WO2016152993A1 (fr)

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EP16768896.9A EP3275980B1 (fr) 2015-03-24 2016-03-24 Composition d'huile lubrifiante pour moteur à combustion interne de type à allumage par étincelle, son procédé de production, moteur à combustion interne de type à allumage par étincelle l'utilisant, et procédé de lubrification de moteur à combustion interne
CN201680017329.6A CN107406795B (zh) 2015-03-24 2016-03-24 火花点火式内燃机用润滑油组合物、该润滑油组合物的制造方法、使用该润滑油组合物的火花点火式内燃机、以及该内燃机的润滑方法
US15/560,035 US20180072961A1 (en) 2015-03-24 2016-03-24 Lubricant oil composition for spark ignition type internal combustion engine, method for producing lubricant oil composition, spark ignition type internal combustion engine using lubricant oil composition, and method for lubricating internal combustion engine

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JP2015-061748 2015-03-24
JP2015061748A JP6572581B2 (ja) 2015-03-24 2015-03-24 火花点火式内燃機関用潤滑油組成物、該潤滑油組成物の製造方法、該潤滑油組成物を用いた火花点火式内燃機関、及び該内燃機関の潤滑方法

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EP3279294A4 (fr) * 2015-03-31 2018-08-22 Idemitsu Kosan Co.,Ltd. Composition d'huile lubrifiante pour moteur à essence et son procédé de fabrication
EP3279299A4 (fr) * 2015-03-31 2018-12-12 Idemitsu Kosan Co.,Ltd. Composition d'huile lubrifiante pour moteur à combustion interne

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JP6895387B2 (ja) * 2015-12-07 2021-06-30 Ｅｎｅｏｓ株式会社 内燃機関用潤滑油組成物
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CN114174480B (zh) * 2019-07-26 2022-08-23 株式会社Adeka 润滑油添加剂以及包含该润滑油添加剂的润滑油组合物
WO2021132518A1 (fr) * 2019-12-27 2021-07-01 出光興産株式会社 Composition d'huile lubrifiante
JP7493373B2 (ja) * 2020-03-31 2024-05-31 出光興産株式会社 潤滑油組成物
JP2023004315A (ja) * 2021-06-25 2023-01-17 Ｅｎｅｏｓ株式会社 内燃機関用潤滑油組成物

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EP3279294A4 (fr) * 2015-03-31 2018-08-22 Idemitsu Kosan Co.,Ltd. Composition d'huile lubrifiante pour moteur à essence et son procédé de fabrication
EP3279299A4 (fr) * 2015-03-31 2018-12-12 Idemitsu Kosan Co.,Ltd. Composition d'huile lubrifiante pour moteur à combustion interne
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CN107406795A (zh) 2017-11-28
EP3275980B1 (fr) 2023-05-03
US20180072961A1 (en) 2018-03-15
JP6572581B2 (ja) 2019-09-11
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