EP3275980A1 - 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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Publication number
EP3275980A1
EP3275980A1 EP16768896.9A EP16768896A EP3275980A1 EP 3275980 A1 EP3275980 A1 EP 3275980A1 EP 16768896 A EP16768896 A EP 16768896A EP 3275980 A1 EP3275980 A1 EP 3275980A1
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Prior art keywords
oil composition
lubricating oil
mass
internal combustion
combustion engine
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EP16768896.9A
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German (de)
English (en)
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EP3275980B1 (fr
EP3275980A4 (fr
Inventor
Toshimasa Utaka
Kazushi TAMURA
Hideki Kamano
Akira Iijima
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/045Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
    • C10M2207/262Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
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    • C10M2227/00Organic 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
    • C10M2227/09Complexes with metals
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    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
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    • C10N2010/04Groups 2 or 12
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    • C10N2010/12Groups 6 or 16
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10Inhibition of oxidation, e.g. anti-oxidants
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74Noack Volatility
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/255Gasoline engines

Definitions

  • the present invention relates to a lubricating oil composition for 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 method for lubricating the internal combustion engine.
  • the fuel consumption performance may also be improved by setting a viscosity of a lubricating oil composition to be used for an internal combustion engine low.
  • FIG. 1 is a constitutional view explaining a spark-ignition internal combustion engine 1 according to an embodiment of the present invention.
  • the lubricating oil composition which has invaded into the combustion chamber due to the oil loss through piston is exposed to high heat, a base oil evaporates, and a metal-based additive blended in the lubricating oil composition is concentrated.
  • a metal-based additive blended in the lubricating oil composition is concentrated.
  • a calcium-based detergent is added as the metal-based additive.
  • this metal-based additive is concentrated, a deterioration of the combustion state is caused, resulting in causing knocking.
  • an object of the present invention is to provide a lubricating oil composition for spark-ignition internal combustion engine, which has excellent detergency, a method for producing the lubricating oil composition, a spark-ignition internal combustion engine using the lubricating oil composition, and a method for lubricating the internal combustion engine.
  • the present inventors have found that according to a lubricating oil composition having the following constitution, even if the oil loss through piston is generated, not only the combustion state is made favorable, but also excellent detergency is obtained.
  • the present invention provides the following.
  • a lubricating oil composition for internal combustion engine in which even if the oil loss through piston is generated, not only the combustion state is made favorable, but also excellent detergency is revealed, a method for producing the lubricating oil composition, a spark-ignition internal combustion engine using the lubricating oil composition, and a method for lubricating the internal combustion engine.
  • the lubricating oil composition for spark-ignition internal combustion engine is a lubricating oil composition including a base oil, (A) a calcium-based detergent, at least one selected from (B1) a sodium-based additive and (B2) a magnesium-based additive, and (C) an ash-free sulfur-based additive, wherein the content of the component (A) as expressed in terms of a calcium atom is 0.15% by mass or less on a basis of the total amount of the lubricating oil composition; a sum total of the content of the component (B1) as expressed in terms of a sodium atom and the content of the component (B2) as expressed in terms of a magnesium atom is 0.2% by mass or less on a basis of the total amount of the lubricating oil composition; and the content of the component (C) as expressed in terms of a sulfur atom is 0.01% by mass or more on a basis of the total amount of the lubricating oil composition.
  • an arbitrary material may be properly selected and used among mineral oils and synthetic oils which have been conventionally used as the base oil of lubricating oil for internal combustion engine.
  • Examples of the mineral oil may include distillates obtained through atmospheric distillation of paraffin-base crude oil, intermediate-base crude oil, or naphthene-base crude oil, or distillates obtained through vacuum distillation of a residual oil of atmospheric distillation, or refined oils obtained through refining of such a distillate according to a conventional method, for example, solvent refined oil, hydrogenated refined oil, dewaxing treated oil, white clay treated oil, etc.
  • the synthetic oil examples include poly- ⁇ -olefins (PAO), such as polybutene, homopolymers or copolymers of an ⁇ -olefin (for example, homopolymers or copolymers of an ⁇ -olefin having 8 to 14 carbon atoms, e.g., an ethylene- ⁇ -olefin copolymer, etc.), etc.; various esters, such as polyol esters, dibasic acid esters, phosphate esters, etc.; various ethers, such as polyphenyl ether, etc.; polyglycols; alkylbenzenes; alkylnaphthalenes; synthetic oils obtained through isomerization of a wax (GTL wax) produced by the Fischer-Tropsch process, etc.; and the like.
  • PAO poly- ⁇ -olefins
  • the base oil a single kind of each of the aforementioned mineral oils and synthetic oils may be used, or a combination of two or more kinds thereof may be used.
  • a mixture of the mineral oil and the synthetic oil may also be used.
  • the kinematic viscosity at 100°C is generally 2 mm 2 /s or more and 30 mm 2 /s or less, preferably 2 mm 2 /s or more and 15 mm 2 /s or less, and 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, an evaporation loss is small; whereas when it is 30 mm 2 /s or less, a power loss to be caused due to viscous resistance is not so large, and hence, a fuel consumption improving effect is obtained.
  • the base oil its viscosity index is generally 80 or more, preferably 100 or more, and more preferably 120 or more.
  • the base oil having a viscosity index of 80 or more is small in a change of viscosity to be caused due to a change of temperature, and hence, it is preferred.
  • the viscosity after mixing has only to fall within the aforementioned range.
  • the base oil containing a mineral oil having a viscosity index of 120 or more which is corresponding to Group 3 of the API classification and/or a poly- ⁇ -olefin (PAO) may be used.
  • the content of the base oil on a basis of the total amount of the lubricating oil composition for 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.
  • an upper limit of the content is preferably 99% by mass, and more preferably 95% by mass or less.
  • Examples of the calcium-based detergent (A) which is used in the lubricating oil composition according to an embodiment of the present invention include calcium salts of a sulfonate, a phenate, and a salicylate. These may be used alone or in combination of plural kinds thereof. From the viewpoint of detergency, a calcium salt of salicylate (calcium salicylate) is preferred.
  • the calcium salt of sulfonate has a molecular weight of preferably 300 to 1,500, and more preferably 400 to 700.
  • Calcium salts of an alkyl aromatic sulfonic acid obtained through sulfonation of an alkyl aromatic compound are preferably used.
  • phenate calcium salts of an alkylphenol, an alkylphenol sulfide, or a Mannich reaction product of an alkylphenol are preferably used.
  • salicylate calcium salts of an alkylsalicylic acid are preferably used.
  • the alkyl group constituting the calcium-based detergent is an alkyl group having preferably 4 to 30 carbon atoms, and more preferably 6 to 18 carbon atoms, and the alkyl group may be either linear or branched.
  • the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group.
  • Examples of the calcium salts of a sulfonate, a phenate, and a salicylate include not only a neutral calcium-based detergent, such as a neutral calcium sulfonate, a neutral calcium phenate, and a neutral calcium salicylate, each of which is obtained by allowing the aforementioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of an alkylphenol, or alkylsalicylic acid, or the like to react directly with a calcium salt base, such as an oxide or hydroxide, etc., of calcium, or once forming into an alkali metal salt, such as a sodium salt, a potassium salt, etc., and then substituting with a calcium salt, or other means; but also a basic calcium-based detergent, such as a basic calcium sulfonate, a basic calcium phenate, and a basic calcium salicylate, each of which is obtained by heating a neutral calcium-based detergent and an excess
  • a material having a metal ratio of generally 20 or less may be used alone or in admixture of two or more thereof.
  • the metal ratio as referred to herein is expressed by (valence of metal element) x (metal element content (mol%))/(soap group content (mol%)) in the metal-based detergent (in this case, the calcium-based detergent);
  • the metal element as referred to herein means calcium;
  • the soap group as referred to herein means a sulfonic acid group, a phenol group, a salicylic acid group, or the like.
  • the content of the calcium atom contained in the calcium-based detergent is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 10% by mass.
  • a base number of the calcium-based detergent is preferably 10 to 600 mgKOH/g, more preferably 50 to 300 mgKOH/g, and still more preferably 100 to 250 mgKOH/g.
  • the base number as referred to herein means a base number as measured by the hydrochloric acid method in conformity with JIS K2501, the 7th section of "Petroleum products and lubricating oils-neutralization number test method".
  • the content of the calcium-based detergent (A) as expressed in terms of a calcium atom is 0.15% by mass or less on a basis of the total amount of the lubricating oil composition.
  • the content of the component (A) is preferably 0.05 to 0.15% by mass, more preferably 0.06 to 0.15% by mass, and still more preferably 0.08 to 0.15% by mass.
  • the lubricating oil composition according to an embodiment of the present invention contains at least one selected from (B1) a sodium-based additive and (B2) a magnesium-based additive.
  • sodium-based additive (B1) which is used in the present invention
  • a sodium-based detergent is preferably exemplified.
  • the sodium-based detergent include sodium salts of a sulfonate, a phenate, and a salicylate. These may be used alone or in combination of plural kinds thereof. From the viewpoint of detergency, a sodium salt of sulfonate (sodium sulfonate) is preferred.
  • the sulfonate, phenate, and salicylate are the same as in the explanation of the sulfonate, phenate, and salicylate for the aforementioned calcium-based detergent.
  • the matter that a basic sodium-based detergent and an overbased sodium-based detergent may be adopted is the same as in the explanation for the calcium-based detergent.
  • the content of the sodium atom 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.
  • a 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.
  • a magnesium-based detergent is preferably exemplified.
  • the magnesium-based detergent include magnesium salts of a sulfonate, a phenate, and a salicylate. These may be used alone or in combination of plural kinds thereof. From the viewpoint of detergency, a magnesium salt of salicylate (magnesium salicylate) is preferred.
  • the sulfonate, phenate, and salicylate are the same as in the explanation of the sulfonate, phenate, and salicylate for the aforementioned calcium-based detergent.
  • the matter that a basic magnesium-based detergent and an overbased magnesium-based detergent may be adopted is the same as in the explanation for the calcium-based detergent.
  • the content of the magnesium atom 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.
  • a 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.
  • the lubricating oil composition according to an embodiment of the present invention contains at least one selected from (B1) a sodium-based additive and (B2) a magnesium-based additive in the content of a sum total of the content as expressed in terms of a sodium atom and the content as expressed in terms of a magnesium atom of 0.2% by mass or less on a basis of the total amount of the lubricating oil composition.
  • B1 a sodium-based additive
  • B2 a magnesium-based additive in the content of a sum total of the content as expressed in terms of a sodium atom and the content as expressed in terms of a magnesium atom of 0.2% by mass or less on a basis of the total amount of the lubricating oil composition.
  • the content of a sum total of the content as expressed in terms of a sodium atom and the content as expressed in terms of a magnesium atom is preferably 0.005 to 0.20% by mass, more preferably 0.01 to 0.15% by mass, and still more preferably 0.01 to 0.10% by mass.
  • a mass ratio of the magnesium atom (Mg) contained in the magnesium-based additive and/or the sodium atom (Na) contained in the sodium-based additive to the calcium atom (Ca) [(Mg and/or Na)/Ca] is preferably 0.03 to 3.5.
  • the mass ratio of the magnesium atom (Mg) and/or the sodium atom (Na) to the calcium atom (Ca) [(Mg and/or Na)/Ca] is preferably 0.05 to 2.5, more preferably 0.05 to 1, and still more preferably 0.06 to 0.8.
  • the lubricating oil composition according to an embodiment of the present invention contains (C) an ash-free sulfur-based additive.
  • the ash-free sulfur-based additive (C) is not particularly limited so long as it is an additive containing sulfur but not containing a metal atom.
  • sulfur-containing amine-based additives such as a thiazine, a dithiazine, an imidazolethione, an imidazoledithione, a thiazole, a dithiazole, a thiadiazole, a dithiadiazole, a dithiocarbamate, etc.
  • aromatic mercaptan-based additives such as a thiocresol, a dithiocresol, a thiophenol, a dithiophenol, etc.
  • thiopropionate-based additives such as a thiopropionate, a dithiopropionate, a thiodipropionate, a dithiodipropionate, etc.
  • additives chiefly used as an anti-wear agent having a structure in which a heterocyclic ring containing sulfur, for example, a sulfur-containing heterocyclic ring, such as a benzothiophene ring, a naphthothiophene ring, a dibenzothiophene ring, a thienothiophene ring, a dithienobenzene ring, a thiophene ring, a naphthothiazole ring, an isothiazole ring, a naphthoisothiazole ring, a phenothiazine ring, a phenoxathine ring, a dithianaphthalene ring, a thianthrene ring, a thioxanthene ring, a bithiophene ring, etc., is included, and at least one sulfur
  • dithiocarbamates such as dialkyl dithiocarbamates having a linear or branched alkyl group having 1 to 20 carbon atoms, etc.
  • thiopropionates such as dialkyl thiopropionates having a linear or branched alkyl group having 1 to 20 carbon atoms, for example, didodecyl thiopropionate, dioctadecyl thiopropionate, dimyristyl thiopropionate, dodecyloctadecyl thiopropionate, etc., etc.
  • thiodipropionates such as dialkyl thiodipropionates corresponding to the foregoing thiopropionates, etc.
  • thiazoles such as alkyl thiazoles, aminoalkyl thiazoles, alkyl benzothiazoles, and alkyl mercaptothiazoles, each having a linear or branched alkyl
  • the content of the sulfur atom contained in the ash-free sulfur-based additive varies with the additive to be used, it is generally 1 to 40% by mass, and preferably 3 to 35% by mass.
  • the thiopropionate-based additive, the sulfide, or the disulfide the content of the sulfur atom is more preferably 3 to 15% by mass.
  • the content of the ash-free sulfur-containing additive (C) as expressed in terms of a sulfur atom is 0.01% by mass or more on a basis of the total amount of the lubricating oil composition.
  • the content of the component (C) is less than 0.01% by mass, the detergency is not obtained, and the combustion state may not be made favorable.
  • the content of the component (C) as expressed in terms of a sulfur atom is preferably 0.01 to 3% by mass, more preferably 0.03 to 1% by mass, and still more preferably 0.03 to 0.5% by mass.
  • 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 may be used.
  • molybdenum-based friction modifier all of arbitrary compounds which are generally used as a friction modifier of lubricating oil for internal combustion engine may be used.
  • a molybdenum amine complex and/or oxymolybdenum dithiocarbamate sulfide, a trinuclear molybdenum-sulfur compound, and molybdenum dithiophosphate More specifically, at least one selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and an amine salt of molybdic acid may be used.
  • molybdenum-based antioxidant there is preferably exemplified a molybdenum amine complex.
  • molybdenum amine complex hexavalent molybdenum compounds, specifically those obtained through a reaction of molybdenum trioxide and/or molybdic acid with an amine compound, for example, compounds obtained by the production method described in JP 2003-252887A , may be used.
  • a molar ratio of the Mo atom of the molybdenum compound is preferably 0.7 to 5, more preferably 0.8 to 4, and still more preferably 1 to 2.5 relative to one mole of the amine compound.
  • a reaction method a conventionally known method, for example, a method described in JP 2003-252887A , may be adopted.
  • molybdenum-based antioxidant besides the aforementioned molybdenum amine complex, a sulfur-containing molybdenum complex of succinimide, as described in JP 3-22438B , JP 2004-2866A , etc., may also be used.
  • the component (D) is preferably a molybdenum-based friction modifier.
  • the component (D) is preferably a molybdenum-based friction modifier.
  • at least one selected from molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), and an amine salt of molybdic acid is preferred, and molybdenum dithiocarbamate (MoDTC) is especially preferred.
  • the content of the component (D) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.3 to 1.5% by mass on a basis of the total amount of the lubricating oil composition.
  • the content of the component (D) as expressed in terms of a molybdenum atom is preferably 0.005 to 0.20% by mass on a basis of the total amount of the lubricating oil composition. From the viewpoint of maintaining the wear resistant properties, the content of the component (D) is more preferably 0.01 to 0.15% by mass, and still more preferably 0.03 to 0.15% by mass.
  • lubricating oil composition it is preferred to further contain at least one additive selected from a viscosity index improver, a dispersant, an extreme pressure agent, a non-sulfur-based antioxidant, and a defoaming agent.
  • the viscosity index improver examples include a poly(meth)acrylate (a dispersion type and a non-dispersion type), an olefin-based copolymer (for example, an ethylene-propylene copolymer, etc.), a dispersion type olefin-based copolymer,, a styrene-based copolymer (for example, a styrene-diene copolymer, a styrene-isoprene copolymer, etc.), and the like. Above all, a poly(meth)acrylate is preferred.
  • a weight average molecular weight (Mw) of such a viscosity index improver is preferably 10,000 to 1,000,000, more preferably 30,000 to 600,000, and still more preferably 100,000 to 600,000. When the molecular weight falls within the aforementioned range, an excellent fuel consumption performance is obtained.
  • the weight average molecular weight is a value as measured by means of GPC and obtained while making polystyrene as a calibration curve, and in detail, it is measured under the following condition.
  • a blending amount of such a viscosity index improver may be properly determined according to a desired viscosity (for example, HTHS viscosity at 150°C), and from the standpoint of a blending effect, it is preferably 0.01 to 10.00% by mass, more preferably 0.05 to 5.00% by mass, and still more preferably 0.05 to 2.00% by mass on a basis of the lubricating oil composition.
  • a desired viscosity for example, HTHS viscosity at 150°C
  • the content of the poly(meth)acrylate means the content of only the resin component composed of a poly(meth)acrylate and is the content on a basis of the solid component in which a mass of, for example, a diluent oil, etc. contained together with the poly(meth)acrylate is not included.
  • a non-boronated imide-based dispersant may be used as the dispersant.
  • the non-boronated imide-based dispersant is one generally called an imide-based dispersant.
  • an imide-based dispersant it is suitable to use a succinimide.
  • the succinimide include compounds of a mono-type represented by the following general formula (1) and a bis-type represented by the following general formula (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 may be the same as or different from each other.
  • the number average molecular weight of each of R 1 , R 3 , and R 4 is preferably 1,000 to 4,000.
  • the solubility in the base oil is favorable, and when it is 4,000 or less, favorable dispersibility is obtained, and excellent detergency 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 as or different from each other.
  • n is an integer of 0 to 10, preferably an integer of 1 to 4, and more preferably 2 or 3. When n falls within the aforementioned range, such is preferred from the standpoints of dispersibility and solubility in the base oil, and excellent detergency is obtained.
  • the succinimide may be produced by allowing an alkenylsuccinic anhydride obtained through a reaction of a polyolefin with maleic anhydride, or an alkylsuccinic anhydride obtained through hydrogenation of the alkenylsuccinic anhydride, to react with a polyamine.
  • the succinimide compound of a mono-type and the succinimide compound of a bis-type may be produced by altering a reaction ratio of the alkenylsuccinic anhydride or alkylsuccinic anhydride to the polyamine,
  • polyamine examples include single diamines, such as ethylenediamine, propylenediamine, butylenediamine, etc.; polyalkylenepolyamines, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, etc.; and piperazine derivatives, such as aminoethylpiperazine, etc.
  • single diamines such as ethylenediamine, propylenediamine, butylenediamine, etc.
  • polyalkylenepolyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, etc.
  • piperazine derivatives such as aminoethylpiperazine, etc.
  • the content of the succinimide is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and still more preferably 0.5 to 5% by mass on a basis of the total amount of the lubricating oil composition; and the content of the succinimide as expressed in terms of a nitrogen atom is preferably 0.005 to 0.3% by mass, and more preferably 0.01 to 0.1% by mass on a basis of the total amount of the lubricating oil composition.
  • a boronated succinimide may be, for example, produced by allowing the aforementioned alkenylsuccinic anhydride obtained through a reaction of a polyolefin with maleic anhydride, or the alkylsuccinic anhydride, to react with the aforementioned polyamine and a boron compound.
  • boron compound examples include boron oxide, a boron halide, boric acid, boric anhydride, a boric acid ester, an ammonium salt of boric acid, and the like.
  • a mass ratio of the boron content B to the nitrogen content N (B/N) in the boronated succinimide is generally 0.1 to 3, and preferably 0.2 to 1.
  • the content of the boronated succinimide is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and still more preferably 0.5 to 5% by mass on a basis of the total amount of the lubricating oil composition; and the content of the boronated succinimide as expressed in terms of a boron atom is preferably 0.005 to 0.3% by mass, and more preferably 0.01 to 0.1% by mass on a basis of the total amount of the lubricating oil composition.
  • a modified polybutenyl succinimide obtained by allowing the aforementioned succinimide to react with an alcohol, an aldehyde, a ketone, an alkylphenol, a cyclic carbonate, an epoxy compound, an organic acid, or the like may also be used.
  • a zinc dithiophosphate represented by the following general formula (3) such as a zinc dialkyldithiophosphate, a zinc dialkyldioxyphosphate, etc., is preferably exemplified.
  • Xs are each independently an oxygen atom or a sulfur atom, and at least two of them are the same atom; and R 7 and R 8 are each independently 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.
  • examples of the primary or secondary alkyl group having 3 to 22 carbon atoms include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group, each of which is primary or secondary, and the like.
  • examples of the alkylaryl group substituted with an alkyl group having 3 to 18 carbon atoms include a propylphenyl group, a pentylphenyl group, an octylphenyl group, a nonylphenyl group, a dodecylphenyl group, and the like.
  • the aforementioned zinc dithiophosphate may be used alone or in combination of plural kinds thereof; however, from the viewpoint of enhancing the wear resistant properties, it is especially preferred to use a zinc dithiophosphate of a secondary alkyl group.
  • anti-wear agent other anti-war agent than the aforementioned dithiophosphoric acid, such as an ash-free friction modifier, e.g., an aliphatic amine, a fatty acid ester, a fatty acid amide, a fatty acid, an aliphatic alcohol, an aliphatic ether, etc., etc., may also be used.
  • an ash-free friction modifier e.g., an aliphatic amine, a fatty acid ester, a fatty acid amide, a fatty acid, an aliphatic alcohol, an aliphatic ether, etc., etc.
  • the content of the anti-wear agent is preferably 0.1 to 10% by mass, and more preferably 0.3 to 5% by mass on a basis of the total amount of the lubricating oil composition.
  • the content of the zinc dithiophosphate as expressed in terms of a phosphorus atom is preferably 0.005 to 0.2% by mass, and more preferably 0.01 to 0.15% by mass on a basis of the total amount of the composition.
  • the extreme pressure agent examples include thiophosphoric acid ester-based extreme pressure agents, such as a trialkyl trithiophosphate, a triaryl trithiophosphate, a triaralkyl trithiophosphate, etc.; phosphorus-based extreme pressure agents, such as phosphoric acid esters or phosphorous acid esters, e.g., a trialkyl phosphate, a triaryl phosphate, a trialkyl phosphonate, a trialkyl phosphite, a triaryl phosphite, a dialkyl hydrogenphosphite, etc., or amine salts thereof, etc.; organic metal-based extreme pressure agents, such as alkali metal salts or alkaline earth metal salts of a carboxylic acid or dicarboxylic acid having 3 to 60 carbon atoms; and the like. These may be used alone or in combination of plural kinds thereof.
  • the content of the extreme pressure agent is preferably 0.001 to 5% by mass, and more preferably 0.005 to 3% by mass on a basis of the total amount of the lubricating oil composition.
  • non-sulfur-based antioxidant a molybdenum-based antioxidant, a phenol-based antioxidant, an amine-based antioxidant, and so on may be suitably used.
  • molybdenum-based antioxidant examples include molybdenum amine complexes obtained through a reaction of molybdenum trioxide and/or molybdic acid with an amine compound; and the like.
  • phenol-based antioxidant an arbitrary material may be properly selected and used among known phenol-based antioxidants which have been conventionally used as the antioxidant of lubricating oil for internal combustion engine.
  • monophenol-based antioxidants such as alkylphenol-based antioxidants, e.g., 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, etc., etc.; diphenol-based antioxidants, e.g., 4,4'-methylenebis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), etc.; hindered phenol-based antioxidants; and the like.
  • amine-based antioxidant an arbitrary material may be properly selected and used among known amine-based antioxidants which have been conventionally used as the antioxidant of lubricating oil for internal combustion engine.
  • amine-based antioxidants such as diphenylamine, an alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms, etc.
  • naphthylamine-based antioxidants such as ⁇ -naphthylamine, a phenyl- ⁇ -naphthylamine substituted with an alkyl group having 3 to 20 carbon atoms, etc.; and the like.
  • the non-sulfur-based antioxidant may be used alone or in combination of plural kinds among those described above.
  • the content of the non-sulfur-based antioxidant is preferably 0.05 to 7% by mass, and more preferably 0.05 to 5% by mass on a basis of the total amount of the lubricating oil composition.
  • defoaming agent examples include a silicone-based defoaming agent, a fluorosilicone-based defoaming agent, a fluoroalkyl ether-based defoaming agent, and the like. These may be used alone or in combination of plural kinds thereof.
  • the content of the defoaming agent is preferably 0.005 to 2% by mass, and more preferably 0.01 to 1% by mass on a basis of the total amount of the lubricating oil composition.
  • lubricating oil composition for spark-ignition internal combustion engine of the present invention other additive(s) may be further blended within the range where the purpose of the present invention is not impaired, as the need arises.
  • the other additive may include a rust inhibitor, such as a petroleum sulfonate, an alkylbenzene sulfonate, dinonylnaphthalene sulfonate, an alkenyl succinate ester, a polyhydric alcohol ester" etc.; an anticorrosive agent; a surfactant, such as a polyalkylene glycol-based nonionic surfactant, e.g., a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene alkylnaphthyl ether, etc., etc.; a metal deactivator, such as a benzotriazole-based compound, a tolyltriazole-based compound, a thiadiazole-based compound, an imidazole-based compound, etc.; a pour point depressant, such as an ethylene-vinyl acetate copolymer, a condensate of a chlorin
  • the aforementioned other additive(s) may be properly blended in an amount falling within the range where the purpose of the present invention is not impaired.
  • a NOACK volatile 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 volatile loss is 10% by mass or more, a low viscosity sufficient for contributing to the low fuel consumption performance is obtained; and when it is 15% by mass or less, excessive oil loss through piston may be inhibited, and an excellent effect for preventing the deterioration of the combustion state of the spark-ignition internal combustion engine is obtained.
  • the NOACK volatile loss is a value as measured in conformity with JPI-5S-41-2004.
  • a 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, and more preferably 3 to 10 mm 2 /s.
  • the kinematic viscosity at 100°C is a value as measured in conformity with "Testing methods for kinematic viscosity of petroleum products" as prescribed in JIS K2283.
  • a sulfated ash content of the lubricating oil composition according to the embodiment of the present invention 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 on a basis of the total amount of the composition.
  • the sulfated ash content is a value as measured by the method as prescribed in JIS K2272, the 5 th section of "Determination of sulfated ash" of and refers to an ash content obtained by adding sulfuric acid to a carbonized residue caused by combustion of a sample and heating so that the residue has a constant mass.
  • the sulfated ash content is generally used to know a rough amount of metal-based additives contained in the lubricating oil composition.
  • An 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.
  • the lubricating performance may be made favorable; and when it is 5 mPa ⁇ s or less, not only excellent viscosity properties at low temperatures are obtained, but also excellent fuel consumption properties are obtained.
  • the HTHS viscosity at 150°C may also be assumed as a viscosity in a high-temperature region at the time of high-speed operation of an engine.
  • the foregoing lubricating oil composition is favorable in various properties, such as viscosity in a high-temperature region assuming the time of high-speed operation of an engine, etc.
  • the HTHS viscosity at 150°C is a value of high temperature high shear viscosity at 150°C as measured in conformity with ASTM D4741, and specifically, it is a value obtained by the measurement method as described in the Examples.
  • the production method of a lubricating oil composition is concerned with a method for producing a lubricating oil composition for spark-ignition internal combustion engine that is a lubricating oil composition to be used for a spark-ignition internal combustion engine including a piston having a piston ring, in which a total tension per piston of tensions applied to the piston ring is 100 N or less, the method including blending a base oil with (A) a calcium-based detergent, at least one selected from (B1) a sodium-based additive, and (B2) a magnesium-based additive, and (C) an ash-free sulfur-based additive in such a manner that the content of the component (A) as expressed in terms of a calcium atom is 0.15% by mass or less on a basis of the total amount of the lubricating oil composition; a sum total of the content of the component (B1) as expressed in terms of a sodium atom and the content of the component (B2) as expressed in terms of a magnesium atom is 0.2% by
  • the aforementioned component (A), component (B1), component (B2), and component (C) have only to be blended within the aforementioned content ranges.
  • the organic molybdenum-based additive (D) and at least one selected from a viscosity index improver, a dispersant, an anti-wear agent, an extreme pressure agent, a non-sulfur-based antioxidant, and a defoaming agent as well as other additive(s) and the like may further be blended within the range where the effects of the present invention are not impaired.
  • the resulting mixture may be introduced into the base oil, or the respective components may be added to and mixed with the base oil one after another. It is to be noted that the addition order does not matter.
  • a spark-ignition internal combustion engine 1 according to the present embodiment is described by reference to FIG. 1 .
  • the spark-ignition internal combustion engine 1 in the present embodiment includes a gasoline engine.
  • a fuel which is used for the spark-ignition internal combustion engine include, in addition to a fuel oil classified into Class I petroleums, petroleum, biomass ethanol, an alcohol fuel, a liquefied petroleum gas, a natural gas, a synthetic gas, a hydrogen fuel, a bi-fuel, and the like.
  • the spark-ignition internal combustion engine 1 includes a cylinder block 11, a piston crank mechanism 12 installed in the cylinder block 11, and a valve mechanism 13 undergoing intake of an air-fuel mixture into the cylinder block 11 and exhaust of a combustion gas.
  • the cylinder block 11 is provided with a cylinder 21 and a crank case 22.
  • the spark-ignition internal combustion engine 1 includes a spark plug F in an upper portion of the cylinder 21.
  • the piston crank mechanism 12 includes a piston 23 and a crank shaft 24.
  • a piston ring 30 is disposed in the piston 23, a piston ring 30 is disposed.
  • the piston ring 30 is constituted of a top ring 31, a second ring 32, and an oil ring 33.
  • a total tension per piston of tensions applied to the piston ring 30 is set to 100 N or less.
  • the total tension per piston of tensions applied to the piston ring 30 is a sum total of tensions applied to each of the plural rings.
  • the total tension is a sum total of tensions (n) applied to the each piston ring of the top ring 31, the second ring 32, and the oil ring 33.
  • the tension applied to the piston ring is a value as measured in conformity with "Measurement method of tangent tension" of JIS B8032-2.
  • 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 within the crank case 22 or an oil tank (not shown), and following the operation of the spark-ignition internal combustion engine 1, the lubricating oil composition L is circulated in the piston crank mechanism 12, the valve mechanism 13, and the like and lubricates and cools each of these parts.
  • the aforementioned lubricating oil composition for spark-ignition internal combustion engine according to the embodiment of the present invention is applied as the lubricating oil composition L.
  • the total tension per piston of tensions applied to the piston ring 30 is 100 N or less.
  • the oil loss through piston from the crank case 22 into a combustion chamber C is liable to be generated.
  • the lubricating oil composition for spark-ignition internal combustion engine according to the present embodiment even if the oil loss through piston is generated, the generation timing of a cool flame may be delayed.
  • the total tension per piston of tensions applied to the piston ring of the spark-ignition internal combustion engine can be lowered, in the case where the spark-ignition internal combustion engine is mounted in an automobile, it is possible to contemplate to improve the fuel consumption performance of the automobile.
  • the lubricating oil composition for spark-ignition internal combustion engine may be preferably used for a low-tension spark-ignition internal combustion engine, in which a total tension per piston of tensions applied to the piston ring 30 is 95 N or less, and moreover 90 N or less.
  • a lower limit value of the total tension per piston of tensions applied to the piston ring 30 is not particularly limited, it is preferably 5 N or more, more preferably 10 N or more, and still more preferably 15 N or more.
  • the lower limit value is 5 N or more, the oil loss through piston is hardly generated.
  • Respective properties of a base oil, an additive, and a lubricating oil composition were measured in the following methods.
  • a small-sized quartz window was provided in a cylinder head, and a light from a xenon light source was transmitted through a right end portion of a combustion chamber, thereby carrying out light absorption measurement in the end portion.
  • the xenon light having been transmitted through the combustion chamber was introduced into a spectroscope by optical fibers and spectrally separated in a wavelength of 293.1 nm. This wavelength is a wavelength at which strong absorption occurs in formaldehyde.
  • the formaldehyde is an important chemical species such that it is produced at the time of generation of a cool flame and abruptly reduced with the movement into a blue flame and the generation of a hot flame.
  • the spectrally separated light was converted into an electric signal by a photomultiplier tube, and by using a transmission light intensity E0 in a state where no reaction takes place and a transmission light intensity E1 at an arbitrary crank angle, an absorbance was defined as (E0 - E1)/E0 and calculated.
  • a timing at which an increase of this absorbance started was defined as a generation timing of a cool flame, and a timing at which the absorbance abruptly decreased was defined as an autoignition timing.
  • a pressure sensor was provided within the combustion chamber, and an amplitude of pressure vibration generated at the time of knocking was measured and defined as an index of the knock intensity.
  • a mixed gas composed of a fuel and an oxidizing agent is compressed by the piston in a cylinder interior, whereby the temperature and pressure increase.
  • the mixed gas ignites itself due to the compression, thereby causing combustion.
  • the low-temperature autoignition includes a stage at which a low-temperature flame called a cool flame or a blue flame reveals, and an active chemical species is produced, leading to generation and propagation of a hot flame accompanied by abrupt heat generation.
  • an active chemical species is forcedly provided by an ignition source, such as an electric spark, etc., leading to generation and propagation of a hot flame.
  • an ignition source such as an electric spark, etc.
  • a deterioration of the combustion state or abrupt pressure vibration is generated.
  • an amplitude of pressure vibration generated at the time of knocking was measured and defined as an index of the knock intensity.
  • a sample prepared by blending in each of sample compositions of Test Examples 1 to 13 shown in Tables 1 to 3 was forcedly introduced into the combustion chamber through a fuel injector, and a fuel oil was replaced in the sample and combusted. Since a lubricant base oil is high in viscosity as compared with the fuel oil, it is difficult to spray a lubricating oil composition by a fuel injector.
  • an additive was mixed in PRF50 that is a fuel oil having an octane number of 50 in place of the lubricant base oil, thereby preparing the sample prepared by blending in each of sample compositions of Test Examples 1 to 13 shown in Tables 1 to 3.
  • An amount of the lubricating oil composition which invades into the combustion chamber from a crank chamber due to oil loss through piston is not constant but is largely dominated by the probability.
  • the influence which the lubricating oil composition gives to the combustion becomes maximum. For that reason, by forcedly scattering the droplets having specified properties into the interior of the combustion chamber to analyze the combustion state, the maximum influence which the composition may give can be evaluated.
  • both the lubricant base oil and the fuel oil are a hydrocarbon
  • a difference in reactivity with the additive is small and that the influence which droplets of a fuel oil containing a certain concentration of an organic metal-based additive give to the combustion is close to that in the case where droplets of a lubricant base oil containing the foregoing additive are scattered within the combustion chamber.
  • the fuel oil containing a predetermined additive does not influence the combustion, even in the case where the lubricating oil composition similarly containing the foregoing predetermined additive invaded into the combustion chamber, it may be judged that the combustion is not influenced.
  • so far as the combustion is influenced when the lubricating oil composition invades into the combustion chamber in the actual equipment, it may be judged that there is a possibility that the combustion is influenced.
  • the comprehensive evaluation was made according to the following criteria.
  • the evaluation is A or B
  • the generation timing of a cool flame is equal or close to the timing of usual spark discharge, and the value of pressure vibration is low, and hence, it may be said that the deterioration of the combustion state was inhibited, and the knocking was inhibited.
  • the evaluation is C
  • the generation timing of a flame is faster than the timing of usual spark discharge, and the value of pressure vibration is high, and hence, it may be said that the combustion state was deteriorated, and the knocking was promoted.
  • the hot tube test was carried out by setting a test temperature to 280°C and a test time to 16 hours and making other conditions in conformity with those of JPI-5S-55-99.
  • Conforming to JPI-5S-55-99 a lacquer attached to a test tube after the test was evaluated between Point 0 (black) and Point 10 (colorless) and evaluated at every 0.5 point. It is meant that as the numerical value is large, a deposit is less, and the detergency is favorable. As for the grade point, though Points 7 or more are evaluated to be acceptable.
  • % by mass (Ca) % by mass (Na)
  • % by mass (Mg) % by mass (S)
  • S % by mass
  • the lubricating oil compositions of Examples 1 to 8 as shown in Table 4 it was confirmed that the lubricating oil compositions in which the calcium-based detergent (A), the sodium additive (B1) and/or the magnesium additive (B2), and the various ash-free sulfur-based additives (C) are blended in the predetermined blending ratios have excellent detergency, and that from the results of Tables 1 to 3, they have an excellent effect for preventing the deterioration of the combustion state of the spark-ignition internal combustion engine.

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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)
EP16768896.9A 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 Active EP3275980B1 (fr)

Applications Claiming Priority (2)

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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
PCT/JP2016/059450 WO2016152993A1 (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

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EP3275980A1 true EP3275980A1 (fr) 2018-01-31
EP3275980A4 EP3275980A4 (fr) 2018-10-03
EP3275980B1 EP3275980B1 (fr) 2023-05-03

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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
EP3275978A4 (fr) * 2015-03-24 2019-01-16 Idemitsu Kosan Co.,Ltd. Composition lubrifiante pour moteurs à essence et son procédé de production
EP3388500A4 (fr) * 2015-12-07 2019-05-01 ExxonMobil Research and Engineering Company Composition d'huile lubrifiante
DE112016005592B4 (de) 2015-12-07 2022-07-21 Jxtg Nippon Oil & Energy Corporation Schmierölzusammensetzung für verbrennungsmotor und verfahren zur unterdrückung von lspi eines verbrennungsmotors

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EP3275978A4 (fr) * 2015-03-24 2019-01-16 Idemitsu Kosan Co.,Ltd. Composition lubrifiante pour moteurs à essence et son procédé de production
EP3505607A1 (fr) * 2015-03-24 2019-07-03 Idemitsu Kosan Co., Ltd. Composition lubrifiante pour moteur à essence et son procédé de production
US10781395B2 (en) 2015-03-24 2020-09-22 Idemitsu Kosan Co., Ltd. Lubricant composition for gasoline engine and method for producing same
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
EP3511398A1 (fr) * 2015-03-31 2019-07-17 Idemitsu Kosan Co., Ltd. Composition d'huile lubrifiante de moteur à essence et son procédé de fabrication
EP3388500A4 (fr) * 2015-12-07 2019-05-01 ExxonMobil Research and Engineering Company Composition d'huile lubrifiante
DE112016005592B4 (de) 2015-12-07 2022-07-21 Jxtg Nippon Oil & Energy Corporation Schmierölzusammensetzung für verbrennungsmotor und verfahren zur unterdrückung von lspi eines verbrennungsmotors
DE112016005592B9 (de) 2015-12-07 2022-09-15 Jxtg Nippon Oil & Energy Corporation Schmierölzusammensetzung für verbrennungsmotor und verfahren zur unterdrückung von lspi eines verbrennungsmotors

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US20180072961A1 (en) 2018-03-15
JP2016180070A (ja) 2016-10-13
WO2016152993A1 (fr) 2016-09-29
CN107406795B (zh) 2021-08-17
EP3275980B1 (fr) 2023-05-03
EP3275980A4 (fr) 2018-10-03
CN107406795A (zh) 2017-11-28
JP6572581B2 (ja) 2019-09-11

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