WO2017099140A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2017099140A1
WO2017099140A1 PCT/JP2016/086429 JP2016086429W WO2017099140A1 WO 2017099140 A1 WO2017099140 A1 WO 2017099140A1 JP 2016086429 W JP2016086429 W JP 2016086429W WO 2017099140 A1 WO2017099140 A1 WO 2017099140A1
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Prior art keywords
lubricating oil
oil composition
molybdenum
mass
magnesium
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PCT/JP2016/086429
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English (en)
Japanese (ja)
Inventor
康 小野寺
鈴木　寛之
豊治 金子
山守　一雄
Original Assignee
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
トヨタ自動車株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 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, トヨタ自動車株式会社 filed Critical 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
Priority to SG11201804612XA priority Critical patent/SG11201804612XA/en
Priority to EP16873033.1A priority patent/EP3388500A4/fr
Priority to US16/060,340 priority patent/US20180355272A1/en
Priority to CN201680071610.8A priority patent/CN108699480A/zh
Publication of WO2017099140A1 publication Critical patent/WO2017099140A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • 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
    • 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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to a lubricating oil composition, and in particular, to a lubricating oil composition for an internal combustion engine, particularly a lubricating oil composition for a gasoline engine.
  • Lubricating oil compositions are widely used in the automotive field such as for internal combustion engines, automatic transmissions, and gear oils.
  • a reduction in viscosity has been demanded in order to improve fuel efficiency, but the oil film becomes thinner due to the reduction in viscosity, and friction cannot be reduced sufficiently. Therefore, molybdenum dithiocarbamate (MoDTC) that can reduce friction by generating molybdenum disulfide under boundary lubrication conditions has been conventionally used.
  • MoDTC molybdenum dithiocarbamate
  • this combination there is a limit to the reduction of friction, and the fuel consumption cannot be sufficiently improved.
  • Patent Documents 2 and 3 It is also known to use a magnesium-based detergent as the detergent (for example, Patent Documents 2 and 3).
  • the use of magnesium-based detergents can reduce friction more than calcium-based detergents, but there is a problem that wear tends to occur.
  • An object of the present invention is to provide a lubricating oil composition capable of reducing friction while ensuring wear resistance even when the viscosity is lowered.
  • the present inventors have found that the above object can be achieved by adding a specific amount of a magnesium-based detergent and a specific amount of a molybdenum-based friction modifier to a lubricating base oil.
  • the present invention provides a lubricating oil composition
  • a lubricating oil composition comprising a lubricating base oil, (A) a magnesium-based detergent, and (B) a molybdenum-based friction modifier, wherein the amount of the (A) component is the lubricating oil.
  • concentration of Mg in the composition in terms of ppm by mass [Mg] is in the range of 200 to 1200 ppm by mass
  • the amount of component (B) is 500 in terms of the concentration of molybdenum in the lubricating oil composition by ppm by mass [Mo].
  • a lubricating oil composition characterized by being in a range of ⁇ 1500 mass ppm.
  • the lubricating oil composition further has at least one of the following features (1) to (7).
  • the amount of component (A) is in the range of 300 to 800 ppm by mass as the amount of magnesium in the lubricating oil composition.
  • the amount of component (B) is in the range of 600 to 1200 ppm by mass as the amount of molybdenum in the lubricating oil composition.
  • [Mg] / [Mo] ⁇ 2.4 is satisfied.
  • a calcium-based detergent (A ′) is further included, and ([Mg] + [Ca]) / [Mo] ⁇ 3.0 ([Ca] is the concentration in terms of ppm by mass of calcium in the lubricating oil composition) Meet).
  • CCS viscosity at ⁇ 35 ° C. is 6.2 Pa ⁇ s or less.
  • the high temperature high shear viscosity (HTHS viscosity) at 150 ° C. is 1.7 to 2.9 mPa ⁇ s.
  • the kinematic viscosity at 100 ° C. is less than 9.3 mm 2 / s.
  • the present invention relates to a method for reducing friction while maintaining low wear by using the lubricating oil composition or the lubricating oil composition of the above embodiments (1) to (8).
  • the lubricating oil composition of the present invention can reduce friction while ensuring wear resistance even when the viscosity is lowered, and can be suitably used particularly as a lubricating oil composition for an internal combustion engine.
  • Lubricating base oil The lubricating base oil in the present invention is not particularly limited. Either a mineral oil or a synthetic oil may be used, and these can be used alone or in combination.
  • mineral oil for example, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, and hydrogen removal. Refined by one or more treatments such as hydrorefining, wax isomerized mineral oil, GTL (Gas to Liquid) base oil, ATL (Asphalt to Liquid) base oil, vegetable oil base oil or a mixture thereof Mention may be made of base oils.
  • Synthetic oils include, for example, polybutene or hydrides thereof; poly- ⁇ -olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; 2-ethylhexyl laurate, 2-ethylhexyl palmitate, 2-stearate Monoesters such as ethylhexyl; diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; neopentyl glycol di-2-ethylhexanoate, neopentyl Glycol di-n-octanoate, neopentyl glycol di-n-decanoate, trimethylolpropane tri-n-octanoate, trimethylolpropane tri
  • the kinematic viscosity (mm 2 / s) at 100 ° C. of the lubricating base oil is not particularly limited, but is preferably 2 to 15 mm 2 / s, more preferably 3 to 10 mm 2 / s, and even more preferably 3 to 8 mm 2 / s, and most preferably 3 to 6 mm 2 / s.
  • a lubricating oil composition that has sufficient oil film formation, excellent lubricity, and low evaporation loss.
  • the viscosity index (VI) of the lubricating base oil is not particularly limited, but is preferably 100 or more, more preferably 120 or more, and most preferably 130 or more. Thereby, the viscosity at low temperature can be reduced while securing an oil film at high temperature.
  • Magnesium-based detergent The magnesium-based detergent is not particularly limited, and conventional ones can be used. Examples include magnesium sulfonate, magnesium phenate, and magnesium salicylate. Among these, magnesium salicylate or magnesium sulfonate is particularly preferable.
  • a magnesium type detergent may be used individually by 1 type, and may mix and use 2 or more types.
  • the concentration [Mg] of magnesium in the lubricating oil composition in terms of mass ppm is in the range of 200 to 1200 mass ppm, preferably 250 to 1000 mass ppm, more preferably 300 to 800 mass ppm. In small amounts. When the amount of the component (A) exceeds the upper limit, wear becomes excessive, and when the amount is lower than the lower limit, the friction reducing effect is low.
  • the amount of component (A) is preferably the following formula (1): [Mg] / [Mo] ⁇ 2.4 (1) ([Mo] indicates the concentration by mass ppm of molybdenum in the lubricating oil composition).
  • the value of [Mg] / [Mo] is more preferably 2.0 or less, still more preferably 1.8 or less, and even more preferably 1.5 or less. If the value is greater than 2.4, wear may be excessive.
  • the lower limit of [Mg] / [Mo] is preferably 0.1, more preferably 0.2, and still more preferably 0.3.
  • the lubricating oil composition of the present invention may contain a calcium-based detergent (A ′) described later as a metal detergent other than the magnesium-based detergent (A).
  • a ′ a calcium-based detergent
  • the component (A ′) is preferably added in an amount that satisfies the following formula (2).
  • [Ca] indicates the concentration by mass ppm of calcium in the lubricating oil composition.
  • the value of ([Mg] + [Ca]) / [Mo] is more preferably less than 2.8, even more preferably less than 2.6, and particularly preferably less than 2.5. If the value exceeds the upper limit, the torque reduction effect may be low.
  • the lower limit of ([Mg] + [Ca]) / [Mo] is preferably 0.2 or more, more preferably 0.5, and even more preferably 1.0.
  • the magnesium-based detergent (A) is particularly preferably an overbased magnesium-based detergent. Thereby, the acid neutralization property required for lubricating oil is securable.
  • an overbased magnesium detergent is used, a neutral magnesium or calcium detergent may be mixed.
  • the total base number of the magnesium-based detergent (A) is not limited, but is preferably 20 to 600 mgKOH / g, more preferably 50 to 500 mgKOH / g, and most preferably 100 to 450 mgKOH / g.
  • the acid neutralization property, high temperature cleanliness, and rust prevention property which are required for lubricating oil are securable.
  • mixing 2 or more types of metal detergents it is preferable that the base number obtained by mixing becomes said range.
  • the magnesium content in the magnesium-based detergent (A) is preferably 0.5 to 20% by mass, more preferably 1 to 16% by mass, and most preferably 2 to 14% by mass. What is necessary is just to add so that magnesium of the quantity of the said range may be contained in a thing.
  • a calcium type detergent (A ') is not specifically limited, A conventional thing can be used. Examples include calcium sulfonate, calcium phenate, and calcium salicylate. These calcium-based detergents may be used alone or in combination of two or more.
  • the calcium-based detergent (A ′) is preferably an overbased calcium-based detergent. Thereby, the acid neutralization property required for lubricating oil is securable.
  • a neutral calcium detergent may be used in combination.
  • the total base number of the calcium detergent (A ′) is not limited, but is preferably 20 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g, and most preferably 100 to 350 mgKOH / g.
  • the acid neutralization property, high temperature cleanliness, and rust prevention property which are required for lubricating oil are securable.
  • the calcium content in the calcium detergent (A ′) is preferably 0.5 to 20% by mass, more preferably 1 to 16% by mass, and most preferably 2 to 14% by mass.
  • the amount of magnesium and calcium in the lubricating oil composition of the present invention preferably satisfies the following formula (3).
  • the value of ⁇ [Mg] / ([Mg] + [Ca]) ⁇ * 100 is more preferably 10 or more, and even more preferably 15 or more. If the value is less than the lower limit, the effect of reducing friction is small.
  • the upper limit of ⁇ [Mg] / ([Mg] + [Ca]) ⁇ * 100 is preferably 100, more preferably 80, still more preferably 60, and still more preferably 50.
  • the lubricating oil composition of the present invention may contain a sodium-based detergent as a metal detergent other than those described above as long as the effects of the present invention are not impaired.
  • a sodium-based detergent sodium sulfonate, sodium phenate and sodium salicylate are preferable.
  • One of these sodium-based detergents may be used alone, or two or more thereof may be mixed and used.
  • Sodium-based detergents can be used in admixture with the magnesium-based detergents described above and optional calcium-based detergents.
  • the total amount of the metal detergent in the lubricating oil composition of the present invention may be an amount such that the amount of magnesium contained in the composition satisfies the specific range described above. Accordingly, the amount of calcium detergent added can be limited.
  • the molybdenum friction modifier is not particularly limited, and conventionally known ones can be used.
  • sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate (MoDTP) and molybdenum dithiocarbamate (MoDTC), complexes of molybdenum compounds with sulfur-containing organic compounds or other organic compounds, and molybdenum sulfides and sulfurized molybdenum acids.
  • MoDTC molybdenum dithiophosphate
  • MoDTC molybdenum dithiocarbamate
  • molybdenum compounds examples include molybdenum oxides such as molybdenum dioxide and molybdenum trioxide, molybdenum acids such as orthomolybdic acid, paramolybdic acid and (poly) sulfurized molybdic acid, and molybdenum such as metal salts and ammonium salts of these molybdic acids.
  • Examples thereof include molybdenum sulfides such as acid salts, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide and polysulfide molybdenum, molybdenum sulfides, metal salts or amine salts of molybdenum sulfides, and molybdenum halides such as molybdenum chloride.
  • molybdenum sulfides such as acid salts, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide and polysulfide molybdenum, molybdenum sulfides, metal salts or amine salts of molybdenum sulfides, and molybdenum halides such as molybdenum chloride.
  • sulfur-containing organic compound examples include alkyl (thio) xanthate, thiadiazole, mercaptothiadiazole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, and organic (poly) sulfide. And sulfurized esters.
  • organic molybdenum compounds such as molybdenum dithiophosphate (MoDTP) and molybdenum dithiocarbamate (MoDTC) are preferable.
  • Molybdenum dithiocarbamate is a compound represented by the following formula [I]
  • Molybdenum dithiophosphate is a compound represented by the following [II].
  • R 1 to R 8 may be the same or different from each other, and are monovalent hydrocarbon groups having 1 to 30 carbon atoms.
  • the hydrocarbon group may be linear or branched.
  • Examples of the monovalent hydrocarbon group include a linear or branched alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; a cycloalkyl group having 4 to 30 carbon atoms; and an aryl having 6 to 30 carbon atoms.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group.
  • an alkyl group having 3 to 8 carbon atoms is preferable.
  • X 1 and X 2 are oxygen atoms or sulfur atoms
  • Y 1 and Y 2 are oxygen atoms or sulfur atoms.
  • an organic molybdenum compound containing no sulfur can also be used.
  • examples of such compounds include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols.
  • friction modifier (B) in the present invention a trinuclear molybdenum compound described in US Pat. No. 5,906,968 can also be used.
  • the component (B) is added in such an amount that the concentration [Mo] of molybdenum in the lubricating oil composition in terms of mass ppm is in the range of 500 to 1500 mass ppm, preferably 600 to 1200 mass ppm.
  • the amount of the component (B) exceeds the above upper limit, the cleanliness may be deteriorated, and when it is less than the above lower limit, the friction may not be sufficiently reduced or the cleanliness may be deteriorated. is there.
  • the amount of the component (B) is preferably the following formula (1): [Mg] / [Mo] ⁇ 2.4 (1) Meet.
  • the value of [Mg] / [Mo] is more preferably 2.0 or less, still more preferably 1.8 or less, and even more preferably 1.5 or less.
  • the lower limit of [Mg] / [Mo] is preferably 0.1, more preferably 0.2, and still more preferably 0.3.
  • the lubricating oil composition of the present invention comprises the above-mentioned lubricating base oil, component (A) and component (B) as essential components.
  • component (A) and component (B) as essential components.
  • component (A) and component (B) as essential components.
  • conventionally known antiwear agents, ashless dispersants and viscosity index improvers are used. May be included.
  • ZDTP zinc dithiophosphate
  • R 1 and R 2 may be the same as or different from each other, and are a hydrogen atom or a monovalent hydrocarbon group having 1 to 26 carbon atoms.
  • the monovalent hydrocarbon group includes a primary (primary) or secondary (secondary) alkyl group having 1 to 26 carbon atoms; an alkenyl group having 2 to 26 carbon atoms; a cycloalkyl group having 6 to 26 carbon atoms; carbon An aryl group, an alkylaryl group or an arylalkyl group of formula 6 to 26; or a hydrocarbon group containing an ester bond, an ether bond, an alcohol group or a carboxyl group.
  • R 1 and R 2 are preferably a primary or secondary alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 8 to 18 carbon atoms, and an alkylaryl group having 8 to 18 carbon atoms, They may be the same or different.
  • zinc dialkyldithiophosphate is preferable, and the primary alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms.
  • the secondary alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms.
  • the said zinc dithiophosphate may be used individually by 1 type, and may mix and use 2 or more types. Further, zinc dithiocarbamate (ZnDTC) may be used in combination.
  • At least one compound selected from phosphates represented by the following formulas (4) and (5), phosphite-based phosphorus compounds, and metal salts and amine salts thereof can be used.
  • R 3 is a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 4 and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.
  • m is 0 or 1.
  • R 6 is a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 7 and R 8 are independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.
  • N is 0 or 1.
  • examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms represented by R 3 to R 8 include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkyl-substituted cyclohexane. Mention may be made of alkyl groups, aryl groups, alkyl-substituted aryl groups, and arylalkyl groups. In particular, it is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably an alkyl group having 3 to 18 carbon atoms, and most preferably an alkyl group having 4 to 15 carbon atoms. It is.
  • Examples of the phosphorus compound represented by the general formula (4) include phosphorous acid monoester and (hydrocarbyl) phosphonous acid having one hydrocarbon group having 1 to 30 carbon atoms; A phosphite diester having two hydrocarbon groups, a monothiophosphite diester, and a (hydrocarbyl) phosphonous monoester; a phosphite triester having three hydrocarbon groups having 1 to 30 carbon atoms, and (Hydrocarbyl) phosphonous acid diesters; and mixtures thereof.
  • the metal salt or amine salt of the phosphorus compound represented by the general formula (4) or (5) is a metal oxide, metal hydroxide, phosphorus compound represented by the general formula (4) or (5), Remains after acting with a metal base such as metal carbonate, metal chloride, ammonia, nitrogen compound such as amine compound having only 1-30 hydrocarbon group or hydroxyl group-containing hydrocarbon group in the molecule. It can be obtained by neutralizing part or all of the acidic hydrogen.
  • a metal base such as metal carbonate, metal chloride, ammonia, nitrogen compound such as amine compound having only 1-30 hydrocarbon group or hydroxyl group-containing hydrocarbon group in the molecule. It can be obtained by neutralizing part or all of the acidic hydrogen.
  • the metal in the metal base include alkali metals such as lithium, sodium, potassium and cesium, alkaline earth metals such as calcium, magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver and manganese. (However, excluding molyb
  • the antiwear agent is usually blended in the lubricating oil composition at 0.1 to 5.0% by mass, preferably 0.2 to 3.0% by mass.
  • Examples of the ashless dispersant include nitrogen-containing compounds having at least one linear or branched alkyl group or alkenyl group having 40 to 500 carbon atoms, preferably 60 to 350, or derivatives thereof, and Mannich dispersants. Or a mono- or bissuccinimide (eg, alkenyl succinimide), an alkyl group having 40 to 500 carbon atoms or a benzylamine having at least one alkenyl group in the molecule, or an alkyl group or alkenyl group having 40 to 400 carbon atoms And polyamines having at least one in the molecule, or modified products of these compounds with boron compounds, carboxylic acids, phosphoric acids, and the like. One type or two or more types arbitrarily selected from these can be blended. In particular, alkenyl succinimide is preferably contained.
  • alkenyl succinimide is preferably contained.
  • the method for producing the succinimide is not particularly limited.
  • an alkyl succinic acid or alkenyl succinic acid obtained by reacting a compound having an alkyl group or alkenyl group having 40 to 500 carbon atoms with maleic anhydride at 100 to 200 ° C. It is obtained by reacting an acid with a polyamine.
  • examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • Examples of the derivative of the nitrogen-containing compound exemplified as the above ashless dispersant include, for example, monocarboxylic acids such as fatty acids having 1 to 30 carbon atoms, oxalic acid, phthalic acid, trimellitic acid, pyromellitic to the aforementioned nitrogen-containing compounds.
  • monocarboxylic acids such as fatty acids having 1 to 30 carbon atoms, oxalic acid, phthalic acid, trimellitic acid, pyromellitic to the aforementioned nitrogen-containing compounds.
  • the remaining amino group and / or the reaction of a polycarboxylic acid having 2 to 30 carbon atoms such as an acid, or an anhydride thereof, or an ester compound, an alkylene oxide having 2 to 6 carbon atoms, or a hydroxy (poly) oxyalkylene carbonate.
  • Modified compounds by so-called oxygen-containing organic compounds, in which some or all of the imino groups are neutralized or amidated; one of the remaining amino groups and / or imino groups by reacting boric acid with the nitrogen-containing compounds described above A so-called boron-modified compound obtained by neutralizing a part or the whole or amidated; A so-called phosphoric acid-modified compound obtained by neutralizing or amidating part or all of the amino group and / or imino group; a sulfur-modified compound obtained by allowing a sulfur compound to act on the nitrogen-containing compound described above; and the nitrogen-containing compound described above
  • modified compounds in which two or more kinds of modifications selected from modification with oxygen-containing organic compounds, boron modification, phosphoric acid modification, and sulfur modification are combined a boric acid-modified compound of alkenyl succinimide, particularly a boric acid-modified compound of bis-type alkenyl succinimide, can further improve heat resistance when used in combination with the above base oil.
  • the amount of the ashless dispersant is 20% by mass or less, preferably 15% by mass or less, more preferably 5% by mass or less, based on the total amount of the composition.
  • a boron-containing ashless dispersant may be used by mixing with an ashless dispersant not containing boron.
  • the content ratio is not particularly limited, but the boron amount contained in the composition is preferably 0.001 to 0.2% by mass based on the total amount of the composition, More preferably, it is 0.003 to 0.1% by mass, and most preferably 0.005 to 0.05% by mass.
  • the number average molecular weight (Mn) of the ashless dispersant is preferably 2000 or more, more preferably 2500 or more, still more preferably 3000 or more, most preferably 5000 or more, and preferably 15000 or less. . If the number average molecular weight of the ashless dispersant is less than the above lower limit, dispersibility may not be sufficient. On the other hand, when the number average molecular weight of the ashless dispersant exceeds the above upper limit, the viscosity is too high, the fluidity becomes insufficient, and the deposit increases.
  • viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, olefin copolymer (polyisobutylene, ethylene-propylene copolymer), dispersed olefin copolymer, polyalkylstyrene, styrene-butadiene hydrogenated copolymer. Styrene-maleic anhydride copolymer, star-like isoprene, and the like.
  • a comb polymer containing at least a repeating unit based on a polyolefin macromer and a repeating unit based on an alkyl (meth) acrylate having an alkyl group having 1 to 30 carbon atoms in the main chain can also be used.
  • Viscosity index improvers usually consist of the polymer and diluent oil.
  • the content of the viscosity index improver is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, and most preferably 0.05 to 5% by mass as a polymer amount based on the total amount of the composition. %. If the content of the viscosity index improver is less than the lower limit, the viscosity temperature characteristics and the low temperature viscosity characteristics may be deteriorated. On the other hand, if it exceeds the upper limit, the viscosity temperature characteristics and the low temperature viscosity characteristics may be deteriorated, and the product cost will be significantly increased.
  • the lubricating oil composition of the present invention can further contain other additives depending on the purpose in order to improve its performance.
  • additives those generally used in lubricating oil compositions can be used.
  • antioxidants, friction modifiers other than the above component (B), corrosion inhibitors, rust inhibitors, flow Examples thereof include additives such as point depressants, demulsifiers, metal deactivators and antifoaming agents.
  • antioxidants examples include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum.
  • phenolic ashless antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), isooctyl- 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like
  • amine-based ashless antioxidants include phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine, dialkyldiphenylamine and the like. It is done.
  • the antioxidant is usually blended at 0.1 to 5% by mass in the lubricating oil composition.
  • Examples of the friction modifier other than the component (B) include esters, amines, amides, and sulfurized esters.
  • the friction modifier is usually blended at 0.01 to 3% by mass in the lubricating oil composition.
  • Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
  • Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
  • the corrosion inhibitor is usually blended in the lubricating oil composition at 0.01 to 5% by mass.
  • pour point depressant for example, a polymethacrylate polymer compatible with the lubricating base oil to be used can be used.
  • the pour point depressant is usually placed in the lubricating oil composition at 0.01 to 3% by weight.
  • the demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl naphthyl ether, and the like.
  • the demulsifier is usually blended in the lubricating oil composition at 0.01 to 5% by mass.
  • the metal deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5- Examples thereof include bisdialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, ⁇ - (o-carboxybenzylthio) propiononitrile.
  • the metal deactivator is usually blended in the lubricating oil composition at 0.01 to 3% by mass.
  • the antifoaming agent examples include silicone oil having a kinematic viscosity at 25 ° C. of 1,000 to 100,000 mm 2 / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o -Hydroxybenzyl alcohol and the like.
  • the antifoaming agent is usually blended in the lubricating oil composition at 0.001 to 1% by mass.
  • alkali borate additives can be added.
  • An alkali borate-based additive contains an alkali metal borate hydrate and can be represented by the following general formula. M 2 O ⁇ xB 2 O 3 ⁇ yH 2 O
  • M is an alkali metal
  • x is 2.5 to 4.5
  • y is 1.0 to 4.8.
  • Specific examples include lithium borate hydrate, sodium borate hydrate, potassium borate hydrate, rubidium borate hydrate, cesium borate hydrate, and the like. Hydrates and sodium borate hydrate are preferable, and potassium borate hydrate is particularly preferable.
  • the average particle size of the alkali metal borate hydrate particles is generally 1 micron ( ⁇ ) or less.
  • the ratio of boron to alkali metal is preferably in the range of about 2.5: 1 to 4.5: 1.
  • the addition amount of the alkali borate-based additive is 0.002 to 0.05 mass% as the boron amount based on the total amount of the lubricating oil composition.
  • the CCS viscosity at ⁇ 35 ° C. of the lubricating oil composition of the present invention is not limited, but is preferably 6.2 Pa. s or less, more preferably 5.0 Pa.s. s or less, more preferably 4.0 Pa.s. s or less, most preferably 3.5 Pa.s. s or less.
  • the amount of molybdenum contained in the lubricating oil composition and the CCS viscosity at ⁇ 35 ° C. satisfy the following formula (6).
  • [CCS viscosity] / [Mo] ⁇ 0.01 (6) ([CCS viscosity] indicates the value (Pa ⁇ s) of the CCS viscosity at ⁇ 35 ° C.
  • the value of [CCS viscosity] / [Mo] is more preferably 0.008 or less, and still more preferably 0.005 or less. If the above value exceeds 0.01, the torque reduction rate may be reduced or the cleanliness may be deteriorated.
  • the lower limit value of [CCS viscosity] / [Mo] is not limited, but is preferably 0.002 and more preferably 0.003.
  • the high temperature high shear viscosity (HTHS viscosity) at 150 ° C. of the lubricating oil composition of the present invention is not limited, but is preferably 1.7 to 2.9 mPa.s, more preferably 2.0 to 2.6 mPa.s. is there.
  • the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is not limited, but is preferably less than 9.3 mm 2 / s, more preferably less than 8.2 mm 2 / s.
  • the lubricating oil composition of the present invention has sufficient frictional characteristics and wear characteristics even when the viscosity is low, and has an effect of obtaining a high torque reduction rate, and can be suitably used for an internal combustion engine. .
  • Magnesium detergent (A) Magnesium-based detergent 1: Magnesium salicylate (total base number 340 mgKOH / g, magnesium content 7.5% by mass) Magnesium detergent 2: Magnesium sulfonate (total base number 400 mgKOH / g, magnesium content 9.0% by mass)
  • Calcium detergent (A ') Calcium detergent 1: Calcium salicylate (total base number 350 mgKOH / g, calcium content 12.0% by mass)
  • Calcium-based detergent 2 calcium salicylate (total base number 220 mgKOH / g, magnesium content 8.0% by mass)
  • Molybdenum friction modifier Molybdenum friction modifier: MoDTC (molybdenum content 10% by mass)
  • Antiwear agent Antiwear agent 1 pri-ZnDTP (primary alkyl type)
  • Antiwear agent 2 sec-ZnDTP (secondary alkyl type)
  • Antioxidant Phenolic antioxidant
  • Ashless dispersant Succinimide viscosity index improver: Polymethacrylate antifoaming agent: Dimethyl silicone
  • Lubricating oil compositions were prepared by mixing the components in the amounts shown in Table 1.
  • the amounts of magnesium-based detergent, calcium-based detergent and molybdenum-based friction modifier are shown in ppm by mass with respect to the total amount of the lubricating oil composition converted to the contents of magnesium, calcium and molybdenum, respectively, and wear inhibitors and other additives are added.
  • the amount of the agent is expressed in parts by mass with respect to the total amount (100 parts by mass) of the lubricating oil composition.
  • the amount of magnesium-based detergent and calcium-based detergent was such that the total molar amount of magnesium and calcium contained in these detergents was as identical as possible in all examples and comparative examples. The following test was done about the obtained composition. The results are shown in Table 1.
  • HTHS150 High temperature high shear viscosity at 150 ° C.
  • Torque reduction rate was measured in a motoring test using a gasoline engine using the lubricating oil compositions obtained in the examples and comparative examples as test compositions.
  • the engine was a Toyota 2ZR-FE1.8L inline 4-cylinder engine, a torque meter was installed between the motor and the engine, and the torque at an oil temperature of 80 ° C. and an engine speed of 700 RPM was measured.
  • Torque was measured in the same manner using a commercially available GF-50O-20 oil as a standard oil.
  • the torque (T) of the test composition was compared with the torque (T 0 ) of the standard oil, and the reduction rate ( ⁇ (T 0 ⁇ T) / T 0 ⁇ ⁇ 100) (%) from the torque of the standard oil was calculated. It shows that fuel consumption is so favorable that a reduction rate is large. A reduction rate of 5.5% or more was accepted.
  • Hot tube test evaluation of high temperature cleanliness
  • the lubricating oil composition was continuously supplied at a rate of 0.3 ml / hour, air at 10 ml / second, and the temperature of the glass tube at 270 ° C. for 16 hours in a glass tube having an inner diameter of 2 mm.
  • the lacquer adhering in the glass tube was compared with the color sample, and the score was given as 10 points for transparent and 0 points for black. The higher the score, the better the high temperature cleanliness. A score of 5.0 or higher was accepted.
  • the lubricating oil composition of the present invention has low wear, high torque reduction rate and high temperature cleanliness despite the low kinematic viscosity at 100 ° C.
  • compositions of Comparative Examples 1 to 3 that do not contain the magnesium-based detergent (A) have a low torque reduction rate and the amount of the magnesium-based detergent (A) is greater than the upper limit of the present invention. Wear is great. Further, the compositions of Comparative Examples 4 and 5 in which the amount of the molybdenum friction modifier (B) is less than the lower limit of the present invention has a low torque reduction rate and is inferior in high temperature cleanliness.

Abstract

L'invention fournit une composition d'huile lubrifiante qui tout en assurant une prévention de l'abrasion permet de réduire le frottement, y compris en cas de réduction de viscosité. Plus précisément, l'invention concerne une composition d'huile lubrifiante qui comprend une huile de base d'huile lubrifiante, (A) un décapant à base de magnésium, et (B) un modificateur de frottement à base de molybdène. Cette composition d'huile lubrifiante est caractéristique en ce que la quantité de composant (A) est comprise dans une plage de ２００ à １２００ｐｐｍ en masse en tant que concentration ［Ｍｇ］ en termes de ppm en masse de magnésium contenu dans cette composition d'huile lubrifiante, et la quantité de composant (B) est comprise dans une plage de ５００ à １５００ｐｐｍ en masse en tant que concentration ［Ｍo］ en termes de ppm en masse de molybdène contenu dans cette composition d'huile lubrifiante.
PCT/JP2016/086429 2015-12-07 2016-12-07 Composition d'huile lubrifiante WO2017099140A1 (fr)

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US16/060,340 US20180355272A1 (en) 2015-12-07 2016-12-07 Lubricating oil composition
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SG11201804612XA (en) 2018-06-28
JP2017105875A (ja) 2017-06-15
US20180355272A1 (en) 2018-12-13
EP3388500A1 (fr) 2018-10-17
JP6235549B2 (ja) 2017-11-22
CN108699480A (zh) 2018-10-23
EP3388500A4 (fr) 2019-05-01

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