WO2022209540A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2022209540A1
WO2022209540A1 PCT/JP2022/008757 JP2022008757W WO2022209540A1 WO 2022209540 A1 WO2022209540 A1 WO 2022209540A1 JP 2022008757 W JP2022008757 W JP 2022008757W WO 2022209540 A1 WO2022209540 A1 WO 2022209540A1
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Prior art keywords
mass
lubricating oil
oil composition
component
less
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PCT/JP2022/008757
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English (en)
Japanese (ja)
Inventor
竜也 楠本
杜継 葛西
Original Assignee
出光興産株式会社
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Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to EP22779765.1A priority Critical patent/EP4317385A1/fr
Priority to US18/553,020 priority patent/US20240191154A1/en
Priority to JP2022532875A priority patent/JP7118327B1/ja
Publication of WO2022209540A1 publication Critical patent/WO2022209540A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines

Definitions

  • the present invention relates to a lubricating oil composition, a gas engine to which the lubricating oil composition is applied, and a method of using the lubricating oil composition.
  • Gas engine heat pump systems and gas engine cogeneration systems have been put to practical use for air conditioning in houses and buildings. These systems generally use gas engines fueled by natural gas, liquefied petroleum gas (LPG), or the like. Various gas engine oils that are applied to such gas engines have also been developed.
  • LPG liquefied petroleum gas
  • Patent Document 1 for the purpose of providing a lubricating oil composition for a gas engine capable of suppressing premature ignition, a lubricating oil base oil containing phosphorus as a constituent element and a sulfur-free wear-preventing agent, organic molybdenum-based friction modifier, calcium salicylate-based detergent, and magnesium salicylate-based detergent; % or less is described.
  • the present invention provides an antioxidant containing a base oil, at least one overbased calcium detergent selected from calcium salicylate and calcium phenate, an alkenyl succinimide that may be boron-modified, and a hindered amine antioxidant. Calcium carbonate content, calcium atom content, boron atom content, and hindered amine antioxidant content contained in the overbased calcium detergent are adjusted to specific ranges.
  • a lubricating oil composition of That is, in one aspect of the present invention, at least one overbased calcium detergent (B) selected from base oil (A), calcium salicylate (B1) and calcium phenate (B2), alkenylsuccinimide ( C), and a lubricating oil composition for a gas engine containing a hindered amine antioxidant (D),
  • the content (X) of calcium atoms derived from component (B) is less than 0.090% by mass based on the total amount of the lubricating oil composition
  • the content (Y) of calcium carbonate contained in the component (B) is 0.060% by mass or more based on the total amount of the lubricating oil composition
  • the content of boron atoms derived from component (C) is less than 0.020% by mass based on the total amount of the lubricating oil composition
  • the content of component (D) is more than 0.20% by mass based on the total amount of the lubricating oil composition.
  • a lubricating oil composition is provided. Another aspect of the present invention provides a gas engine to which the lubricating oil composition is applied. Another aspect of the present invention provides a method for lubricating a gas engine, wherein the lubricating oil composition is applied to the gas engine.
  • the lubricating oil composition of a preferred aspect of the present invention is excellent in at least one of the various properties required for lubricating a gas engine, and in a more preferred aspect, it has an effect of suppressing premature ignition. Since it can also improve long drain properties, it can be suitably used for lubricating gas engines.
  • the upper and lower limits can be combined arbitrarily.
  • the numerical range is described as "preferably 30 to 100, more preferably 40 to 80”
  • the range of "30 to 80” and the range of "40 to 100” are also described in this specification. included in the specified numerical range.
  • the description of "60 to 100” means a range of "60 or more and 100 or less”.
  • kinematic viscosity and viscosity index mean values measured and calculated according to JIS K2283:2000.
  • the contents of calcium atoms (Ca), magnesium atoms (Mg), phosphorus atoms (P), zinc atoms (Zn), boron atoms (B), and molybdenum atoms (Mo) are specified in JPI-5S-38-92.
  • the content of nitrogen atoms (N) means a value measured according to JIS K2609:1998.
  • the lubricating oil composition of the present invention comprises a base oil (A), at least one overbased calcium detergent (B) selected from calcium salicylate (B1) and calcium phenate (B2), and It contains a good alkenyl succinimide (C) and a hindered amine antioxidant (D). Then, the lubricating oil composition of the present invention contains the content of calcium atoms and calcium carbonate derived from component (B), the content of boron atoms derived from component (C), and the content of component (D). It is adjusted to a specific range so that it can be suitably applied as a lubricating oil composition for gas engines.
  • the lubricating oil composition of the present invention adjusts the content of calcium atoms derived from component (B) and the content of boron atoms derived from component (C) to a predetermined range.
  • the content of the calcium carbonate contained in the component (B) is controlled to a predetermined range while suppressing the accumulation of deposits, the effect of suppressing premature ignition is improved.
  • the decrease in long-drain properties due to the reduction in the content of calcium atoms derived from component (B) and the content of boron atoms derived from component (C) is caused by calcium salicylate (B1) and By containing at least one overbased calcium detergent selected from calcium phenates (B2) and by setting the content of component (D) within a predetermined range, long drain properties are improved.
  • the lubricating oil composition of the present invention can be a lubricating oil composition having an effect of suppressing premature ignition and improved long drain properties.
  • the lubricating oil composition of one aspect of the present invention preferably further contains zinc dithiophosphate (E).
  • the lubricating oil composition of one aspect of the present invention further contains lubricating oil additives other than the above components (B) to (E), if necessary, within a range that does not impair the effects of the present invention. good too.
  • the total content of components (A), (B), (C) and (D) is based on the total amount (100% by mass) of the lubricating oil composition, preferably is 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, even more preferably 75% by mass or more, particularly preferably 80% by mass or more, and furthermore, 85% by mass or more, 87% by mass % or more, 90% by mass or more, or 92% by mass or more, and 100% by mass or less, 99.99% by mass or less, 99.90% by mass or less, 99.50% by mass or less, 99.0% by mass Below, it is good also as 98.0 mass % or less, or 97.0 mass % or less.
  • the base oil used as component (A) includes one or more selected from mineral oils and synthetic oils.
  • Mineral oils include, for example, atmospheric residual oils obtained by atmospheric distillation of crude oils such as paraffinic crude oils, intermediate crude oils, and naphthenic crude oils; distillates obtained by vacuum distillation of these atmospheric residual oils. a refined oil obtained by subjecting the distillate to one or more refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining; and the like.
  • Synthetic oils include, for example, ⁇ -olefin homopolymers, or ⁇ -olefin copolymers (for example, ⁇ -olefin copolymers having 8 to 14 carbon atoms such as ethylene- ⁇ -olefin copolymers).
  • Synthetic oil (GTL) obtained by isomerizing the manufactured wax (GTL wax (Gas To Liquids WAX)) and the like can be mentioned.
  • the component (A) used in one aspect of the present invention is preferably one or more selected from mineral oils and synthetic oils classified into Group II and Group III of the API (American Petroleum Institute) base oil category.
  • the kinematic viscosity at 40° C. of component (A) used in one embodiment of the present invention is preferably 10 to 130 mm 2 /s, more preferably 20 to 120 mm 2 /s, still more preferably 30 to 110 mm 2 /s, and even more preferably 30 to 110 mm 2 /s. It is preferably 40 to 100 mm 2 /s.
  • the viscosity index of component (A) used in one aspect of the present invention is preferably 70 or higher, more preferably 80 or higher, even more preferably 90 or higher, even more preferably 100 or higher, and particularly preferably 105 or higher.
  • the kinematic viscosity and viscosity index of the mixed oil are preferably within the above ranges.
  • the content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total amount (100% by mass) of the lubricating oil composition. , more preferably 65% by mass or more, even more preferably 70% by mass or more, particularly preferably 75% by mass or more, furthermore, 80% by mass or more, 82% by mass or more, 85% by mass or more, 87% by mass or more, Or it may be 89% by mass or more, and is preferably 99.5% by mass or less, more preferably 99.0% by mass or less, still more preferably 98.0% by mass or less, and even more preferably 97.0% by mass or less. , and particularly preferably 96.0% by mass or less.
  • the lubricating oil composition of one aspect of the present invention contains, as component (B), at least one overbased calcium detergent selected from calcium salicylate (B1) and calcium phenate (B2).
  • Component (B) may be used alone or in combination of two or more.
  • component (B) in the lubricating oil composition of the present invention must satisfy requirements (I) and (II) below.
  • the lubricating oil composition By adjusting the content (X) of calcium atoms derived from the component (B) so as to satisfy the requirement (I), deposition of deposits that can occur with the use of the lubricating oil composition is suppressed, and premature ignition It is possible to obtain a lubricating oil composition with an improved suppression effect. Moreover, when applied to a gas engine, it can also be a lubricating oil composition with good engine efficiency. That is, the lubricating oil composition in which the content (X) of calcium atoms derived from the component (B) is 0.090% by mass or more without satisfying the requirement (I) has an insufficient effect of suppressing premature ignition. easy to become.
  • the content (X) of calcium atoms derived from component (B) is less than 0.090% by mass, but preferably 0.090% by mass, based on the total amount (100% by mass) of the lubricating oil composition. less than 0.085 wt%, more preferably less than 0.080 wt%, more preferably less than 0.075 wt%, even more preferably less than 0.070 wt%, even more preferably less than 0.065 wt%, particularly preferably 0 less than 0.060% by weight.
  • the content (X) of calcium atoms derived from the component (B) is based on the total amount (100% by mass) of the lubricating oil composition. , preferably 0.0010% by mass or more, more preferably 0.0030% by mass or more, more preferably 0.0050% by mass or more, still more preferably 0.0070% by mass or more, still more preferably 0.010% by mass or more , particularly preferably 0.015% by mass or more, furthermore, 0.017% by mass or more, 0.020% by mass or more, 0.022% by mass or more, 0.025% by mass or more, 0.030% by mass or more, It may be 0.032% by mass or more, 0.035% by mass or more, 0.037% by mass or more, or 0.040% by mass or more.
  • component (B) used in the present invention is an overbased calcium detergent, and is composed of soap and calcium carbonate.
  • the requirement (II) defines the content (Y) of calcium carbonate contained in the component (B). Calcium carbonate contained in component (B) contributes to further improvement in the effect of suppressing premature ignition. Therefore, as stipulated in requirement (II), the content (Y) of calcium carbonate contained in component (B) is 0.060% by mass or more, thereby further improving the effect of suppressing premature ignition.
  • It can be an oil composition. That is, the lubricating oil composition in which the content (Y) of calcium atoms contained in the component (B) is less than 0.060% by mass without satisfying the requirement (II) has an insufficient effect of suppressing premature ignition. easy to become.
  • the content (Y) of calcium carbonate contained in the component (B) is 0.060% by mass or more, preferably 0.060% by mass or more, based on the total amount (100% by mass) of the lubricating oil composition.
  • 065% by mass or more more preferably 0.070% by mass or more, more preferably 0.075% by mass or more, still more preferably 0.080% by mass or more, still more preferably 0.085% by mass or more, still more preferably 0 0.090% by mass or more, particularly preferably 0.095% by mass or more, and 0.10% by mass or more, 0.11% by mass or more, 0.12% by mass or more, or 0.13% by mass or more good.
  • the content (Y) of calcium carbonate contained in the component (B) is based on the total amount (100% by mass) of the lubricating oil composition. , preferably 2.00% by mass or less, more preferably 1.80% by mass or less, more preferably 1.50% by mass or less, even more preferably 1.20% by mass or less, still more preferably 1.00% by mass or less, More preferably 0.80% by mass or less, particularly preferably 0.60% by mass or less, furthermore 0.50% by mass or less, 0.45% by mass or less, 0.40% by mass or less, 0.35% by mass % or less, 0.30% by mass or less, 0.25% by mass or less, 0.20% by mass or less, 0.18% by mass or less, 0.17% by mass or less, 0.16% by mass or less, or 0.15% by mass % or less.
  • the content (X) of calcium atoms derived from the component (B) is preferably 0.20 or more, more preferably is 0.25 or more, more preferably 0.30 or more, still more preferably 0.35 or more, still more preferably 0.38 or more, particularly preferably 0.40 or more, and preferably 0.90 or less, More preferably 0.80 or less, more preferably 0.70 or less, still more preferably 0.60 or less, still more preferably 0.55 or less, even more preferably 0.52 or less, particularly preferably 0.50 or less .
  • the content of soap contained in component (B) used in one aspect of the present invention is preferably 0.050% by mass or more, more preferably 0.050% by mass or more, based on the total amount (100% by mass) of the lubricating oil composition.
  • 060% by mass or more more preferably 0.070% by mass or more, still more preferably 0.080% by mass or more, still more preferably 0.090% by mass or more, even more preferably 0.100% by mass or more, particularly preferably 0 .110% by mass or more, preferably 3.00% by mass or less, more preferably 2.00% by mass or less, more preferably 1.50% by mass or less, still more preferably 1.20% by mass or less, and further It is preferably 1.00% by mass or less, more preferably 0.80% by mass or less, particularly preferably 0.60% by mass or less, and further preferably 0.50% by mass or less, 0.45% by mass or less, and 0.50% by mass or less. It may be 40% by mass or less, 0.35% by mass or less, 0.30%
  • Component (B) used in the present invention is at least one overbased calcium detergent selected from calcium salicylate (B1) and calcium phenate (B2).
  • a lubricating oil composition containing at least one selected from components (B1) and (B2) as an overbased calcium detergent, thereby having an effect of suppressing premature ignition and improving long drain properties. can be
  • An "overbased" calcium detergent used as component (B) in one aspect of the present invention means a calcium detergent having a base number of 100 mg KOH/g or greater.
  • the base value of component (B) used in one aspect of the present invention may be 100 mgKOH/g or more, 120 mgKOH/g or more, 150 mgKOH/g or more, 170 mgKOH/g or more, or 200 mgKOH/g or more, or 600 mgKOH/g. Hereinafter, it may be 550 mgKOH/g or less, 500 mgKOH/g or less, 450 mgKOH/g or less, or 400 mgKOH/g or less.
  • the base values of components (B1) and (B2) are also within the same ranges as above.
  • the "base number" of component (B) refers to 7. of JIS K2501 "Petroleum products and lubricating oils-neutralization number test method”. Means the base number by the hydrochloric acid method measured in accordance with.
  • the component (B) used in one aspect of the present invention is a mixture of a calcium detergent having a base number of 100 mgKOH/g or more and a calcium detergent having a base number of less than 100 mgKOH/g, and having a base number of 100 mgKOH/g or more.
  • a mixture of calcium detergents may also be used.
  • the component (B) used in one aspect of the present invention is a mixture of two or more calcium detergents, , preferably a calcium detergent mixture obtained by mixing two or more kinds of calcium detergents having a base number of 100 mgKOH/g or more.
  • the component (B) used in one aspect of the present invention may contain at least calcium salicylate (B1). preferable.
  • the content of the component (B1) in the component (B) is the total amount (100% by mass) of the component (B) contained in the lubricating oil composition , preferably 30 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass. .
  • a compound represented by the following general formula (b-1) is preferable as the component (B1) used in one aspect of the present invention. Further, as the component (B2) used in one embodiment of the present invention, a compound represented by the following general formula (b-2) is preferable.
  • each R is independently a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
  • hydrocarbon groups that can be selected as R include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 1 to 18 carbon atoms, cycloalkyl groups having 3 to 18 ring carbon atoms, and 6 to 18 ring carbon atoms.
  • y is an integer of 0 or more, preferably an integer of 0-3.
  • the lubricating oil composition of one aspect of the present invention may contain a metallic detergent other than component (B) within a range that does not impair the effects of the present invention.
  • Metallic detergents other than component (B) include one or more selected from metal salicylates, metal phenates, and metal sulfonates containing alkali metal atoms or alkaline earth metal atoms other than calcium atoms. .
  • a metallic detergent other than the component (B) The content of is 0 to 50 parts by mass, 0 to 40 parts by mass, 0 to 30 parts by mass, 0 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (B) contained in the lubricating oil composition, 0 to 10 parts by mass, 0 to 5.0 parts by mass, 0 to 2.0 parts by mass, 0 to 1.0 parts by mass, 0 to 0.1 parts by mass, 0 to 0.01 parts by mass, or 0 to 0 It is good also as .001 mass part.
  • the lubricating oil composition of one embodiment of the present invention includes the following requirements (i) and (ii) ), and more preferably a lubricating oil composition that satisfies both requirements (i) and (ii) below.
  • the metal sulfonate defined in requirement (i) is more preferably calcium sulfonate, that is, it is more preferably substantially free of calcium sulfonate.
  • Magnesium detergents described in requirement (i) above also include magnesium salicylates, magnesium phenates, and magnesium sulfonates.
  • the provision of (i) above "substantially does not contain a metal sulfonate” is a provision that denies the mode of blending and containing a metal sulfonate for a given purpose, and is unintentional. Alternatively, it is not a rule that denies even a mode in which a metal sulfonate is inevitably mixed or present.
  • the content of the metal sulfonate in that case is With respect to 100 parts by mass of the total amount of component (B) contained in the oil composition, it is usually less than 20 parts by mass, but less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, less than 0.1 parts by mass, It may be less than 0.01 parts by weight, less than 0.001 parts by weight, or less than 0.0001 parts by weight.
  • the definition of (ii) above is the same, and is interpreted by replacing "metal sulfonate" in the above description with "magnesium detergent".
  • the lubricating oil composition of the present invention contains alkenyl succinimide (C) as component (C).
  • Component (C) may be used alone or in combination of two or more.
  • Component (C) may be a boron-modified alkenylsuccinimide or a non-boron-modified alkenylsuccinimide.
  • Component (C) used in one aspect of the present invention may be at least one selected from non-boron-modified alkenyl succinimide (C1) and boron-modified alkenyl succinimide (C2). It is preferred to include component (C2) together. However, the component (C2) tends to become a cause of deposit formation and, by extension, premature ignition as it is used for a long period of time. Therefore, from the viewpoint of providing a lubricating oil composition having an improved effect of suppressing premature ignition, the lubricating oil composition of the present invention must satisfy the following requirement (III). Requirement (III): The content of boron atoms derived from component (C) is less than 0.020% by mass based on the total amount of the lubricating oil composition.
  • the amount of deposits that can occur with the use of the lubricating oil composition is reduced, and premature ignition is suppressed.
  • It can be a lubricating oil composition obtained. That is, a lubricating oil composition in which the content of boron atoms derived from component (C) is 0.020% by mass or more without satisfying the requirement (III) tends to have an insufficient effect of suppressing premature ignition.
  • the content of boron atoms derived from component (C) is less than 0.020% by mass, preferably 0.018% by mass, based on the total amount (100% by mass) of the lubricating oil composition.
  • more preferably 0.016% by mass or less, more preferably 0.015% by mass or less, still more preferably 0.014% by mass or less, still more preferably 0.013% by mass or less, still more preferably 0.012% by mass % or less, particularly preferably 0.011 mass % or less, and further 0.010 mass % or less, 0.0080 mass % or less, 0.0070 mass % or less, 0.0060 mass % or less, 0.0050 mass % or less, or 0.0040% by mass or less, or 0.0001% by mass or more, 0.0005% by mass or more, 0.0010% by mass or more, 0.0015% by mass or more, or 0.0020% by mass or more may be
  • Examples of the component (C1) used in one embodiment of the present invention include an alkenylsuccinic acid bisimide represented by the following general formula (c-1) and an alkenylsuccinic acid monoimide represented by the following general formula (c-2). mentioned.
  • R A1 , R A2 and R A3 are each independently an alkenyl group having a weight average molecular weight (Mw) of 500 to 3000 (preferably 900 to 2500). is.
  • alkenyl groups that can be selected as R A1 , R A2 and R A3 include polybutenyl groups, polyisobutenyl groups, ethylene-propylene copolymers, etc. Among these, polybutenyl groups and polyisobutenyl groups are preferred.
  • R B1 , R B2 and R B3 are each independently an alkylene group having 2 to 5 carbon atoms.
  • x1 is an integer of 0-10, preferably an integer of 1-4, more preferably 2 or 3.
  • x2 is an integer of 1-10, preferably an integer of 2-5, more preferably 3 or 4.
  • the component (C2) used in one embodiment of the present invention includes, for example, a boron-modified form of the alkenyl succinate bisimi represented by the general formula (c-1), and a compound represented by the following general formula (c-2). Among them, boron-modified alkenylsuccinic monoimide represented by the following general formula (c-2) is preferred.
  • the ratio [B/N] of boron atoms and nitrogen atoms constituting component (C2) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3. Above, more preferably 0.5 or more, particularly preferably 0.7 or more.
  • the content ratio [N / Ca] of the nitrogen atoms derived from the component (C) and the calcium atoms derived from the component (B) is the dispersion of the component (B)
  • the mass ratio is preferably 1.20 or less, more preferably 1.17.
  • the content ratio [B / N] of the boron atoms derived from the component (C2) and the nitrogen atoms derived from the component (C) is a mass ratio, preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, still more preferably 0.04 or more, particularly preferably 0.05 or more, and preferably 0.90 or less, more It is preferably 0.60 or less, more preferably less than 0.30, still more preferably 0.28 or less, still more preferably 0.25 or less, even more preferably 0.23 or less, and particularly preferably 0.20 or less.
  • the content of component (C) in terms of nitrogen atoms is based on the total amount (100% by mass) of the lubricating oil composition, preferably 0.005 to 0.15 % by mass, more preferably 0.010 to 0.10% by mass, more preferably 0.020 to 0.090% by mass, even more preferably 0.025 to 0.070% by mass, particularly preferably 0.030 to 0.060.
  • the amount (content) of component (C) is based on the total amount (100% by mass) of the lubricating oil composition, preferably 0.10 to 15.0% by mass, more preferably 0.50 to 12% 0% by mass, more preferably 0.7 to 10.0% by mass, still more preferably 1.0 to 8.0% by mass, still more preferably 1.5 to 7.0% by mass, still more preferably 2.0% by mass. 0 to 6.0% by weight, particularly preferably 2.5 to 5.0% by weight.
  • the amount (content) of the component (C2) is the total amount (100% by mass) of the lubricating oil composition
  • it is preferably less than 1.05% by mass, more preferably 1 0.00% by mass or less, more preferably 0.90% by mass or less, even more preferably 0.80% by mass or less, even more preferably 0.70% by mass or less, even more preferably 0.60% by mass or less, particularly preferably 0.50% by mass or less, preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.07% by mass or more, More preferably 0.10% by mass or more, particularly preferably 0.12% by mass or more.
  • the lubricating oil composition of the present invention contains a hindered amine antioxidant as component (D).
  • the content of component (D) in the lubricating oil composition of the present invention must satisfy requirement (IV) below.
  • the hindered amine antioxidant (D) does not contain a metal atom, it contributes to the improvement of antioxidant performance without increasing the content of sulfated ash in the lubricating oil composition and the content of calcium atoms in the component (B). Oxidative deterioration of the lubricating oil composition during use can be suppressed.
  • the content of calcium atoms derived from the component (B) is reduced as in the above requirement (I) to improve the effect of suppressing premature ignition, but the long drain property is a problem.
  • the lubricating oil composition of the present invention contains at least one overbased calcium detergent (B) selected from component (B1) and component (B2), and satisfies the above requirement (IV).
  • B overbased calcium detergent
  • the lubricating oil composition has an effect of suppressing premature ignition while improving long drain properties.
  • the content of the component (D) is based on the total amount (100% by mass) of the lubricating oil composition.
  • 0.20% by mass is more than 0.20% by mass, preferably 0.25% by mass or more, more preferably 0.30% by mass or more, even more preferably 0.32% by mass or more, and even more preferably 0.35% by mass or more, Even more preferably 0.37% by mass or more, particularly preferably 0.40% by mass or more, and although there is no particular upper limit, 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less % by mass or less, 2.0% by mass or less, 1.5% by mass or less, or 1.0% by mass or less.
  • the hindered amine antioxidant used as the component (D) may be an antioxidant containing a structure represented by the following formula (d).
  • component (D) may be used independently and may use 2 or more types together.
  • *1 and *2 indicate bonding positions with other atoms.
  • component (D) include compounds represented by any of the following general formulas (d-1) to (d-4).
  • R D1 is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R D2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 18 ring carbon atoms, an aryl group having 6 to 18 ring carbon atoms, and a hydroxyl group.
  • an amino group, or a group represented by —O—CO—R D3 R D3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • Z is an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 6 to 18 ring carbon atoms, an arylene group having 6 to 18 ring carbon atoms, an oxygen atom, a sulfur atom. , or a group represented by —O—CO—(CH 2 ) n —CO—O— (n is an integer of 1 to 20).
  • R D3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • n is an integer of 1-20.
  • the lubricating oil composition of one aspect of the present invention may contain antioxidants other than component (D) as other additives.
  • Antioxidants other than component (D) include, for example, amine antioxidants other than component (D), phenol antioxidants, sulfur antioxidants, and phosphorus antioxidants. These other antioxidants may be used alone or in combination of two or more.
  • amine-based antioxidants other than component (D) include diphenylamine-based antioxidants such as diphenylamine and alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms; ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, carbon naphthylamine-based antioxidants such as substituted phenyl- ⁇ -naphthylamine having alkyl groups of numbers 3 to 20;
  • Phenolic antioxidants include, for example, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, Monophenol antioxidants such as isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate agents; diphenol antioxidants such as 4,4′-methylenebis(2,6-di-t-butylphenol) and 2,2′-methylenebis(4-ethyl-6-t-butylphenol); .
  • the content of antioxidants other than the component (D) is based on the total amount (100% by mass) of the lubricating oil composition, 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, 0.70% by mass or more, or 1.00% by mass or more; 0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, 5.0% by mass or less, 4.5% by mass or less, or 4.0% by mass or less .
  • the content of antioxidants other than the component (D) is relative to the total amount of 100 parts by mass of the component (D) contained in the lubricating oil composition , 0 to 1000 parts by mass, 0 to 950 parts by mass, 0 to 900 parts by mass, 0 to 850 parts by mass, 0 to 800 parts by mass, and 0 to 750 parts by mass.
  • the lubricating oil composition of one aspect of the present invention preferably contains zinc dithiophosphate (ZnDTP) (E) as component (E).
  • Component (E) may be used alone or in combination of two or more.
  • Component (E) functions as an antiwear agent.
  • Component (E) used in one aspect of the present invention is preferably a compound represented by the following general formula (e-1).
  • R 1 to R 4 each independently represent a hydrocarbon group and may be the same or different.
  • the number of carbon atoms in the hydrocarbon group that can be selected as R 1 to R 4 is preferably 1-20, more preferably 1-16, still more preferably 3-12, still more preferably 3-10.
  • Specific hydrocarbon groups that can be selected as R 1 to R 4 include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl.
  • octenyl group nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group , alkenyl groups such as pentadecenyl group; cyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, methylcyclohexylmethyl group, cyclohexylethyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclohexyl group and other cycloalkyl groups; phenyl group, naphthyl group , anthracenyl group, biphenyl group, terphenyl group; alkylaryl groups such as tolyl group, dimethylphenyl group, butylphenyl group, nonylphenyl group, methylbenzyl group, dimethylnaphth
  • the content of component (E) in terms of zinc atoms is based on the total amount (100% by mass) of the lubricating oil composition, preferably 0.001 to 1.0 % by mass, more preferably 0.005 to 0.80 mass %, still more preferably 0.01 to 0.60 mass %, even more preferably 0.02 to 0.50 mass %, particularly preferably 0.03 to It is 0.40% by mass.
  • the content (blended amount) of component (E) may be adjusted so that the content in terms of zinc atoms falls within the above range, but the total amount (100% by mass) of the lubricating oil composition , preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, still more preferably 0.10 to 2.0% by mass, still more preferably 0.20 to 1.0% by mass. It is 0% by mass.
  • the lubricating oil composition of one aspect of the present invention may further contain lubricating oil additives other than components (B) to (E), if necessary, as long as the effects of the present invention are not impaired.
  • lubricating oil additives include pour point depressants, viscosity index improvers, demulsifiers, friction modifiers, corrosion inhibitors, metal deactivators, antistatic agents, antifoaming agents, and the like. be done.
  • Each of these lubricating oil additives may be used alone, or two or more of them may be used in combination.
  • each of these lubricating oil additives can be adjusted as appropriate within a range that does not impair the effects of the present invention. It is usually 0.001 to 15% by mass, preferably 0.005 to 10% by mass, more preferably 0.01 to 5% by mass, independently for each agent.
  • the method for producing the lubricating oil composition of one aspect of the present invention is not particularly limited, but from the viewpoint of productivity, the base oil (A), together with the above components (B) to (D), if necessary
  • the method comprises the step of blending component (E) and other lubricating oil additives.
  • the kinematic viscosity at 40° C. of the lubricating oil composition of one aspect of the present invention is preferably 10 to 200 mm 2 /s, more preferably 30 to 170 mm 2 /s, still more preferably 50 to 150 mm 2 /s, still more preferably is 60 to 130 mm 2 /s, particularly preferably 80 to 120 mm 2 /s.
  • the kinematic viscosity at 100° C. of the lubricating oil composition of one embodiment of the present invention is preferably 2.5 to 20.0 mm 2 /s, more preferably 4.0 to 18.0 mm 2 /s, still more preferably 5.0 mm 2 /s. 5 to 16.0 mm 2 /s, more preferably 7.0 to 15.0 mm 2 /s, particularly preferably 8.0 to 14.0 mm 2 /s.
  • the viscosity index of the lubricating oil composition of one embodiment of the present invention is preferably 80 or higher, more preferably 85 or higher, even more preferably 90 or higher, even more preferably 95 or higher, and particularly preferably 100 or higher.
  • the acid value of the lubricating oil composition of one aspect of the present invention is preferably 0.10 to 2.00 mgKOH/g, more preferably 0.15 to 1.50 mgKOH/g, still more preferably 0.20 to 1.20 mgKOH. /g, more preferably 0.25 to 1.00 mgKOH/g, particularly preferably 0.30 to 0.80 mgKOH/g.
  • the acid value of a lubricating oil composition means the value measured based on JISK2501:2003 (potentiometric method).
  • the base number of the lubricating oil composition of one aspect of the present invention is preferably 1.0 to 10.0 mgKOH/g, more preferably 1.5 to 8.0 mgKOH/g, still more preferably 2.0 to 6.5 mgKOH. /g, more preferably 2.3 to 5.0 mgKOH/g, particularly preferably 2.5 to 4.0 mgKOH/g.
  • the base number of a lubricating oil composition means the value measured based on JISK2501:2003 (hydrochloric acid method).
  • the sulfated ash content of the lubricating oil composition of one embodiment of the present invention is preferably less than 0.50 wt%, more preferably less than 0.40 wt%, even more preferably less than 0.30 wt%, even more preferably less than 0.30 wt%. It is less than 27% by mass.
  • sulfated ash means the value measured based on JISK2272:1998.
  • the content of phosphorus atoms is based on the total amount (100% by mass) of the lubricating oil composition, preferably 0.01 to 0.15% by mass, more preferably 0 0.015 to 0.12 mass %, more preferably 0.02 to 0.10 mass %, still more preferably 0.025 to 0.08 mass %.
  • the content of nitrogen atoms is based on the total amount (100% by mass) of the lubricating oil composition, preferably 0.01 to 1.00% by mass, more preferably 0 0.02 to 0.80% by mass, more preferably 0.03 to 0.50% by mass, even more preferably 0.05 to 0.30% by mass, particularly preferably 0.07 to 0.20% by mass .
  • the content of magnesium atoms is the lubricating oil Based on the total amount of the composition, preferably less than 0.04% by weight, more preferably less than 0.02% by weight, even more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, particularly preferably It is less than 0.0005% by mass.
  • the content of molybdenum atoms is the lubricating oil
  • Preferably less than 0.01% by weight, more preferably less than 0.005% by weight, even more preferably less than 0.001% by weight, and even more preferably 0.0005% by weight, based on the total amount (100% by weight) of the composition is less than
  • the maximum calorific value (maximum calorific value) measured by heating from ° C. to 600 ° C. at a heating rate of 10 ° C./min is preferably 25.0 mW or less, more preferably 20.0 mW or less, and more preferably is 18.0 mW or less, more preferably 16.0 mW or less, even more preferably 12.0 mW or less, and particularly preferably 8.0 mW or less.
  • the exothermic start temperature which is the temperature when the calorific value reaches 0.5 mW, is preferably 220° C. or higher, more preferably 255° C. or higher, more preferably 270° C. or higher, and even more preferably. is 280° C. or higher, more preferably 300° C. or higher, particularly preferably 320° C. or higher. It can be said that the lower the maximum heat generation amount and the higher the exothermic start temperature, the higher the effect of suppressing early ignition of the lubricating oil composition.
  • the base number (hydrochloric acid method) of the lubricating oil composition is measured in the process of deterioration by NOx, and the base number is 1 "NOx-ISOT life time", which is the time to decrease to 0 mgKOH/g, is preferably 100 hours or more, more preferably 105 hours or more, still more preferably 110 hours or more, and still more preferably 115 hours or more. . It can be said that the longer the NOx-ISOT life time, the more excellent the long drain property of the lubricating oil composition.
  • the lubricating oil composition of one aspect of the present invention is excellent in properties such as an effect of suppressing premature ignition and long drain properties. Therefore, the lubricating oil composition of one aspect of the present invention can be applied to various devices capable of exhibiting the above properties, but is preferably applied to lubrication of gas engines.
  • the present invention can also provide the following [I] and [II].
  • [I] A gas engine to which the lubricating oil composition of one aspect of the present invention described above is applied.
  • [II] A method for lubricating a gas engine, in which the lubricating oil composition of one embodiment of the present invention described above is applied to the gas engine.
  • a lubricating oil composition for a gas engine containing an antioxidant (D) The content (X) of calcium atoms derived from component (B) is less than 0.090% by mass based on the total amount of the lubricating oil composition, The content (Y) of calcium carbonate contained in the component (B) is 0.060% by mass or more based on the total amount of the lubricating oil composition, The content of boron atoms derived from component (C) is less than 0.020% by mass based on the total amount of the lubricating oil composition, The content of component (D) is more than 0.20% by mass based on the total amount of the lubricating oil composition.
  • Ratio of content (X) (unit: mass %) of calcium atoms derived from component (B) to content (Y) (unit: mass %) of calcium carbonate contained in component (B) [ (X)/(Y)] is from 0.20 to 0.90, the lubricating oil composition according to [1] above.
  • lubricating oil composition [4] The lubricating oil composition according to any one of [1] to [3] above, wherein component (B) contains at least calcium salicylate (B1).
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.
  • the measuring method of various physical properties is as follows.
  • Examples 1-7, Comparative Examples 1-8 A base oil and various additives were added in the amounts shown in Tables 1 and 2 and mixed to prepare lubricating oil compositions.
  • the blending amounts of the calcium-based detergent and additive mixture shown in Tables 1 and 2 are the blending amounts including the diluent oil.
  • the details of each component used in the preparation of the lubricating oil composition are as follows.
  • Ca salicylate (b1-i) Calcium salicylate having a base number of 316 mgKOH/g (hydrochloric acid method) and a Ca atom content of 12.1% by mass, which corresponds to component (B).
  • Ca salicylate (b1-ii) Calcium salicylate having a base value of 219 mgKOH/g (hydrochloric acid method) and a Ca atom content of 8.0% by mass, corresponding to component (B).
  • Ca salicylate (b1-iii) Calcium salicylate having a base value of 223 mgKOH/g (hydrochloric acid method) and a Ca atom content of 7.94% by mass, which corresponds to component (B).
  • Ca salicylate (b1-iv) Calcium salicylate having a base value of 59.8 mg KOH/g (hydrochloric acid method) and a Ca atom content of 2.3% by mass, corresponding to component (B).
  • Ca phenate (b2-i) a calcium phenate having a base number of 218 mgKOH/g (hydrochloric acid method) and a Ca atom content of 9.25% by mass, which corresponds to component (B).
  • Ca sulfonate (1) a calcium sulfonate having a base number of 304 mgKOH/g (hydrochloric acid method) and a Ca atom content of 11.6% by mass.
  • Ca sulfonate (2) a calcium sulfonate having a base value of 11.3 mgKOH/g (hydrochloric acid method) and a Ca atom content of 2.15% by mass.
  • Additive mixture an additive mixture of non-hindered amine amine antioxidants, phenolic antioxidants, pour point depressants, demulsifiers, metal deactivators, and defoamers.
  • the lubricating oil compositions prepared in Examples 1 to 7 have a low maximum calorific value and a high exothermic start temperature, so the effect of suppressing premature ignition is high, and the long drain property is also excellent. This resulted in On the other hand, the lubricating oil compositions prepared in Comparative Examples 1 to 8 were inferior in at least one of the effect of suppressing premature ignition and the long drain property.

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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 qui est destinée à des moteurs à gaz et qui contient : une huile de base (A) ; au moins un agent de nettoyage de calcium surbasique (B) choisi parmi le salicylate de calcium (B1) et le phénate de calcium (B2) ; l'acide alcénylsuccinique imide (C) ; et un antioxydant à base d'amine encombrée (D). La quantité contenue (X) d'atomes de calcium dérivés du composant (B) est inférieure à 0,090 % en masse par rapport à la quantité totale de la composition d'huile lubrifiante. La quantité contenue (Y) de carbonate de calcium inclus dans le composant (B) n'est pas inférieure à 0,060 % en masse par rapport à la quantité totale de la composition d'huile lubrifiante. La quantité contenue d'atomes de bore dérivés du composant (C) est inférieure à 0,020 % en masse par rapport à la quantité totale de la composition d'huile lubrifiante. La quantité de composant contenue (D) est supérieure à 0,20 % en masse par rapport à la quantité totale de la composition d'huile lubrifiante.
PCT/JP2022/008757 2021-03-30 2022-03-02 Composition d'huile lubrifiante WO2022209540A1 (fr)

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JP2018203952A (ja) 2017-06-08 2018-12-27 Ｊｘｔｇエネルギー株式会社 ガスエンジン用潤滑油組成物、及び燃料消費量の改善方法又は異常燃焼の低減方法
WO2020085228A1 (fr) * 2018-10-22 2020-04-30 出光興産株式会社 Composition lubrifiante et son procédé de production
WO2020203525A1 (fr) * 2019-03-29 2020-10-08 出光興産株式会社 Composition d'huile de graissage
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Publication number Priority date Publication date Assignee Title
JPH10219266A (ja) * 1997-02-03 1998-08-18 Tonen Corp 潤滑油組成物
JP2003277783A (ja) * 2002-03-26 2003-10-02 Nippon Oil Corp 潤滑油組成物
JP2007506840A (ja) * 2003-09-25 2007-03-22 ザ　ルブリゾル　コーポレイション 無灰定置ガスエンジン潤滑剤
JP2013518936A (ja) * 2010-02-01 2013-05-23 エクソンモービル リサーチ アンド エンジニアリング カンパニー トラクション係数を低下させることによって大きい低速および中速ガスエンジン用のエンジンオイル組成物の燃料効率を向上させる方法
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JP2018203952A (ja) 2017-06-08 2018-12-27 Ｊｘｔｇエネルギー株式会社 ガスエンジン用潤滑油組成物、及び燃料消費量の改善方法又は異常燃焼の低減方法
WO2020085228A1 (fr) * 2018-10-22 2020-04-30 出光興産株式会社 Composition lubrifiante et son procédé de production
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JP2020164747A (ja) * 2019-03-29 2020-10-08 出光興産株式会社 潤滑油組成物

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