WO2011083601A1 - Composition lubrifiante - Google Patents

Composition lubrifiante Download PDF

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Publication number
WO2011083601A1
WO2011083601A1 PCT/JP2010/066708 JP2010066708W WO2011083601A1 WO 2011083601 A1 WO2011083601 A1 WO 2011083601A1 JP 2010066708 W JP2010066708 W JP 2010066708W WO 2011083601 A1 WO2011083601 A1 WO 2011083601A1
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WIPO (PCT)
Prior art keywords
less
viscosity
oil
lubricating
base oil
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PCT/JP2010/066708
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English (en)
Japanese (ja)
Inventor
松井　茂樹
矢口　彰
明男 武藤
麻里 長永
Original Assignee
Ｊｘ日鉱日石エネルギー株式会社
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Application filed by Ｊｘ日鉱日石エネルギー株式会社 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Priority to EP10842116.5A priority Critical patent/EP2522709A4/fr
Priority to CN2010800609965A priority patent/CN102712869A/zh
Priority to US13/520,679 priority patent/US20120283159A1/en
Publication of WO2011083601A1 publication Critical patent/WO2011083601A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02—Specified values of viscosity or viscosity index
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2219/06—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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/019—Shear stability
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/252—Diesel engines
    • 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.
  • lubricating oil is used in internal combustion engines, transmissions, and other mechanical devices in order to make their operations smooth.
  • lubricating oil (engine oil) for internal combustion engines is required to have high performance as the performance of the internal combustion engine increases, the output increases, and the operating conditions become severe. Therefore, various additives such as antiwear agents, metal detergents, ashless dispersants, and antioxidants are blended in conventional engine oils in order to satisfy these required performances (for example, Patent Documents 1 to 5 listed below). 3).
  • Patent Documents 1 to 5 listed below listed below. 3
  • the HTHS viscosity at 150 ° C. (“HTHS viscosity” is also referred to as “high temperature high shear viscosity”) is high.
  • HTHS viscosity is also referred to as “high temperature high shear viscosity”
  • the coefficient of friction in the boundary lubrication region where metals are in contact with each other is increased only by reducing the viscosity. In order to improve fuel economy, it is necessary to reduce the friction coefficient in the boundary lubrication region.
  • the present invention has been made in view of such circumstances, and sufficiently maintains the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C. while maintaining the HTHS viscosity at 150 ° C.
  • Another object of the present invention is to provide a lubricating oil composition that can sufficiently suppress an increase in the friction coefficient in the boundary lubrication region and is excellent in fuel efficiency.
  • the present invention provides a lubricating base oil having a kinematic viscosity of 1 to 20 mm 2 / s at 100 ° C., and (A) a total area of all peaks in a spectrum obtained by 13 C-NMR.
  • a viscosity index improver in which the ratio M1 / M2 of the total area M1 of the peak between chemical shift 36 to 38 ppm and the total area M2 of the peak between chemical shift 64 to 66 ppm is 0.20 or more, and (B) friction
  • a lubricating oil composition comprising a regulator and (C) an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate.
  • the (A) viscosity index improver is preferably a poly (meth) acrylate viscosity index improver.
  • the (A) viscosity index improver preferably has a PSSI of 40 or less and a weight average molecular weight to PSSI ratio of 1 ⁇ 10 4 or more.
  • PSSI Permanent Shear Stable Property Index
  • ASTM D 6022-01 Standard Practicing for Calculation of Permanent Shear Stable Property Index
  • ASTM D 6278-02 Test Metal Stoford. Means the permanent shear stability index of a polymer, calculated based on data measured by European Diesel Injector Apparatus.
  • the (B) friction modifier is preferably an organic molybdenum compound.
  • an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate is an overbase obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal borate.
  • it is a basic alkaline earth metal salicylate.
  • the kinematic viscosity at 40 ° C., the kinematic viscosity at 100 ° C., and the HTHS viscosity at 100 ° C. can be sufficiently lowered, and boundary lubrication can be achieved.
  • An increase in the friction coefficient in the region can be sufficiently suppressed, and a lubricating oil composition excellent in fuel economy can be provided.
  • a desired HTHS viscosity at 150 ° C. can be obtained without using a synthetic oil such as a poly- ⁇ -olefin base oil or an ester base oil or a low viscosity mineral oil base oil. Sufficient fuel economy can be demonstrated while maintaining the value.
  • the lubricating oil composition of the present invention can also be suitably used for gasoline engines, diesel engines, gas engines, etc. for motorcycles, automobiles, power generation, cogeneration, etc. Not only can it be suitably used for these various engines using fuel of mass ppm or less, but it is also useful for various engines for ships and outboard motors.
  • the lubricating oil composition according to this embodiment comprises a lubricating base oil having a kinematic viscosity of 1 to 20 mm 2 / s at 100 ° C., and (A) a spectrum obtained by 13 C-NMR with respect to the total area of all peaks.
  • a lubricating base oil (hereinafter referred to as “the lubricating base oil according to the present embodiment”) having a kinematic viscosity at 100 ° C. of 1 to 20 mm 2 / s is used. .
  • a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, hydroisomerization.
  • isoparaffinic base oils those having a kinematic viscosity at 100 ° C. of 1 to 20 mm 2 / s can be mentioned.
  • the following base oils (1) to (8) are used as raw materials, and the raw oil and / or the lubricating oil fraction recovered from the raw oil is The base oil obtained by refine
  • recovering lubricating oil fractions can be mentioned.
  • Distilled oil by atmospheric distillation of paraffinic crude oil and / or mixed base crude oil (2) Distilled oil by vacuum distillation of atmospheric distillation residue of paraffinic crude oil and / or mixed base crude oil ( WVGO) (3) Wax (slack wax, etc.) obtained by the lubricant dewaxing process and / or synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by the gas-to-liquid (GTL) process, etc.
  • the above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay purification; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred.
  • one of these purification methods may be performed alone, or two or more may be combined.
  • the order in particular is not restrict
  • the lubricating base oil according to the present embodiment is obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment.
  • the following base oil (9) or (10) is particularly preferred.
  • the base oil selected from the above base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like.
  • dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lube oil fraction, or by distillation after the dewaxing treatment (10)
  • a lubricating oil fraction recovered from the base oil is hydroisomerized, and the product or the lubricating oil fraction recovered from the product by distillation or the like is subjected to solvent dewaxing or catalytic dewaxing.
  • Hydroisomerized mineral oil obtained by performing a dewaxing process such as or by distillation after the dewaxing process.
  • a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.
  • the catalyst used for the hydrocracking / hydroisomerization is not particularly limited, but a composite oxide having cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one kind of the composite oxide.
  • Hydrogenolysis with a combination of the above combined with a binder and supporting a metal having hydrogenation ability for example, one or more metals such as Group VIa metal or Group VIII metal in the periodic table
  • a hydroisomerization catalyst in which a catalyst or a support containing zeolite (eg, ZSM-5, zeolite beta, SAPO-11, etc.) is loaded with a metal having a hydrogenation ability containing at least one of the Group VIII metals are preferably used.
  • the hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.
  • reaction conditions for hydrocracking and hydroisomerization are not particularly limited, but hydrogen partial pressure 0.1 to 20 MPa, average reaction temperature 150 to 450 ° C., LHSV 0.1 to 3.0 hr-1, hydrogen / oil ratio 50 to 20000 scf / b is preferable.
  • the kinematic viscosity at 100 ° C. of the lubricating base oil according to this embodiment needs to be 20 mm 2 / s or less, preferably 10 mm 2 / s or less, more preferably 7 mm 2 / s or less, and still more preferably. It is 5.0 mm 2 / s or less, particularly preferably 4.5 mm 2 / s or less, and most preferably 4.0 mm 2 / s or less.
  • the kinematic viscosity at 100 ° C. needs to be 1 mm 2 / s or more, preferably 1.5 mm 2 / s or more, more preferably 2 mm 2 / s or more, and still more preferably 2.
  • the kinematic viscosity at 100 ° C. in the present invention refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
  • the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 20 mm 2 / s, the worse the low temperature viscosity characteristics, also there is a risk that can not be obtained sufficient fuel saving properties, the following cases 1 mm 2 / s Since the formation of an oil film at the lubrication site is insufficient, the lubricity is inferior, and the evaporation loss of the lubricating oil composition may increase.
  • a lubricating base oil having a kinematic viscosity at 100 ° C. in the following range by distillation or the like.
  • (I) less than the kinematic viscosity at 100 ° C. is 1.5 mm 2 / s or more 3.5 mm 2 / s, more preferably 2.0 ⁇ 3.0mm 2 / s lubricating base oils
  • (III) a kinematic viscosity at 100 ° C. is 4.5 ⁇ 10 mm 2 / s, more preferably 4.8 to 9 mm 2 / s, particularly preferably 5.5 to 8.0 mm 2 / s.
  • the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present embodiment is preferably 80 mm 2 / s or less, more preferably 50 mm 2 / s or less, still more preferably 20 mm 2 / s or less, and particularly preferably 18 mm 2. / S or less, most preferably 16 mm 2 / s or less.
  • the 40 ° C. kinematic viscosity is preferably 6.0 mm 2 / s or more, more preferably 8.0 mm 2 / s or more, further preferably 12 mm 2 / s or more, particularly preferably 14 mm 2 / s or more, and most preferably.
  • Lubricant base oil having a kinematic viscosity at 40 ° C. of 6.0 mm 2 / s or more and less than 12 mm 2 / s, more preferably 8.0 to 12 mm 2 / s
  • V A kinematic viscosity at 40 ° C. of 12 mm 2 / s s or more and less than 28 mm 2 / s, more preferably 13 to 19 mm 2 / s of lubricating base oil (VI)
  • the kinematic viscosity at 40 ° C. is 28 to 50 mm 2 / s, more preferably 29 to 45 mm 2 / s, particularly preferably Is a lubricating base oil of 30 to 40 mm 2 / s.
  • the viscosity index of the lubricating base oil according to this embodiment is preferably 120 or more.
  • the viscosity index of the lubricating base oils (I) and (IV) is preferably 120 to 135, more preferably 120 to 130.
  • the viscosity index of the lubricating base oils (II) and (V) is preferably 120 to 160, more preferably 125 to 150, and still more preferably 135 to 145.
  • the viscosity index of the lubricating base oils (III) and (VI) is preferably 120 to 180, more preferably 125 to 160.
  • the viscosity index is less than the lower limit, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and wear prevention properties tend to decrease. It is in. On the other hand, when the viscosity index exceeds the upper limit, the low-temperature viscosity characteristics tend to decrease.
  • the viscosity index as used in the present invention means a viscosity index measured according to JIS K 2283-1993.
  • the density ( ⁇ 15 ) at 15 ° C. of the lubricating base oil according to this embodiment is preferably 0.860 or less, more preferably 0.850 or less, still more preferably 0.840 or less, and particularly preferably. Is 0.822 or less.
  • the density at 15 ° C. in the present invention means a density measured at 15 ° C. in accordance with JIS K 2249-1995.
  • the pour point of the lubricating base oil according to the present embodiment depends on the viscosity grade of the lubricating base oil.
  • the pour point of the lubricating base oils (I) and (IV) is preferably ⁇ It is 10 ° C or lower, more preferably -12.5 ° C or lower, and further preferably -15 ° C or lower.
  • the pour points of the lubricating base oils (II) and (V) are preferably ⁇ 10 ° C. or lower, more preferably ⁇ 15 ° C. or lower, and still more preferably ⁇ 17.5 ° C. or lower.
  • the pour point of the lubricating base oils (III) and (VI) is preferably ⁇ 10 ° C.
  • the pour point as used in the present invention means a pour point measured according to JIS K 2269-1987.
  • the aniline point (AP (° C.)) of the lubricating base oil of the present invention depends on the viscosity grade of the lubricating base oil, but is not less than the value of A represented by the following formula (B), that is, AP ⁇ A is preferred.
  • A 4.3 ⁇ kv100 + 100 (B) [Wherein, kv100 represents the kinematic viscosity (mm 2 / s) of the lubricating base oil at 100 ° C. ]
  • the AP of the lubricating base oils (I) and (IV) is preferably 108 ° C. or higher, more preferably 110 ° C. or higher.
  • the AP of the lubricating base oils (II) and (V) is preferably 113 ° C. or higher, more preferably 119 ° C. or higher.
  • the AP of the lubricating base oils (III) and (VI) is preferably 125 ° C. or higher, more preferably 128 ° C. or higher.
  • the aniline point in the present invention means an aniline point measured according to JIS K 2256-1985.
  • the iodine value of the lubricating base oil according to this embodiment is preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, particularly preferably 0.9 or less, and most preferably 0. 8 or less. Further, it may be less than 0.01, but from the viewpoint of small effect corresponding to it and economic efficiency, it is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.03. Above, especially preferably 0.05 or more.
  • the iodine value as used in the field of this invention means the iodine value measured by the indicator titration method of JIS K0070 "acid value, saponification value, iodine value, hydroxyl value, and unsaponification value of a chemical product".
  • the sulfur content in the lubricating base oil according to the present embodiment depends on the sulfur content of the raw material.
  • a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
  • a lubricating base oil that does not substantially contain sulfur can be obtained.
  • the sulfur content in the obtained lubricating base oil is usually 100 mass ppm. That's it.
  • the content of sulfur content is preferably 100 ppm by mass or less, and from 50 ppm by mass or less, from the viewpoint of further improvement in thermal and oxidation stability and low sulfur content. More preferably, it is more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.
  • the nitrogen content in the lubricating base oil according to this embodiment is preferably 7 ppm by mass or less, more preferably 5 ppm by mass or less, and even more preferably 3 ppm by mass or less. If the nitrogen content exceeds 5 ppm by mass, the thermal and oxidation stability tends to decrease.
  • the nitrogen content in the present invention means a nitrogen content measured according to JIS K 2609-1990.
  • The% C p of the lubricating base oil according to this embodiment is preferably 70 or more, preferably 80 to 99, more preferably 85 to 95, still more preferably 87 to 94, and particularly preferably 90 to 90. 94.
  • % C p of lubricating base oil is less than the above lower limit, viscosity-temperature characteristics, thermal / oxidative stability, and friction characteristics tend to decrease, and when additives are added to lubricating base oil In addition, the effectiveness of the additive tends to decrease. Further, when the% C p value of the lubricating base oil exceeds the upper limit value, the additive solubility will tend to be lower.
  • % C A of the lubricating base oil of the present embodiment is preferably 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less.
  • % C A of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.
  • % C N of the lubricating base oil of the present embodiment is preferably 30 or less, more preferably 4 to 25, more preferably 5-13, particularly preferably from 5 to 8. If the% C N value of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties will tend to be reduced. Moreover, when% CN is less than the said lower limit, it exists in the tendency for the solubility of an additive to fall.
  • % C P in the present invention % C A N and% C A, obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number
  • is% C N may indicate a value greater than zero.
  • the content of the saturated component in the lubricating base oil according to this embodiment is preferably 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass, based on the total amount of the lubricating oil base oil.
  • the ratio of the cyclic saturated component in the saturated component is preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass. % Or less, and more preferably 21% by mass or less.
  • annular saturated part which occupies for the said saturated part becomes like this. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more.
  • the viscosity-temperature characteristics and the heat / oxidation stability can be improved.
  • the function of the additive can be expressed at a higher level while the additive is sufficiently stably dissolved and held in the lubricating base oil. Furthermore, according to the present invention, it is possible to improve the friction characteristics of the lubricating base oil itself, and as a result, it is possible to achieve an improvement in the friction reduction effect and an improvement in energy saving.
  • the saturated part as used in the field of this invention is measured by the method described in said ASTM D 2007-93.
  • ASTM Examples thereof include a method described in D 2425-93, a method described in ASTM D 2549-91, a method by high performance liquid chromatography (HPLC), a method obtained by improving these methods, and the like.
  • the aromatic content in the lubricating base oil according to the present embodiment is preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, based on the total amount of the lubricating base oil.
  • it is 2 mass% or less, Preferably it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Most preferably, it is 1.5 mass% or more. If the aromatic content exceeds the above upper limit, the viscosity-temperature characteristics, thermal / oxidative stability, friction characteristics, volatilization prevention characteristics and low-temperature viscosity characteristics tend to decrease.
  • the lubricating base oil according to the present embodiment may not contain an aromatic component, but the solubility of the additive is further increased by setting the aromatic content to be equal to or higher than the above lower limit value. be able to.
  • the aromatic content in the present invention means a value measured according to ASTM D 2007-93.
  • the aromatic component includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylated products thereof, as well as compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols and naphthols. Aromatic compounds having atoms are included.
  • a synthetic base oil may be used as the lubricating base oil according to this embodiment.
  • Synthetic base oils include poly ⁇ -olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate) having a kinematic viscosity at 100 ° C. of 1 to 20 mm 2 / s.
  • the production method of poly- ⁇ -olefin is not particularly limited.
  • Friedel Crafts containing a complex of aluminum trichloride or boron trifluoride with water, alcohol (ethanol, propanol, butanol, etc.), carboxylic acid or ester examples thereof include a method of polymerizing ⁇ -olefin in the presence of a polymerization catalyst such as a catalyst.
  • the lubricating base oil according to the present embodiment may be used alone, and the lubricating base oil according to the present embodiment may be one of other base oils or You may use together with 2 or more types.
  • the ratio of the lubricating base oil which concerns on this embodiment in those mixed base oils is 30 mass% or more Is more preferable, it is more preferable that it is 50 mass% or more, and it is still more preferable that it is 70 mass% or more.
  • Other base oil used in combination with the lubricating base oil of the present embodiment is not particularly limited, examples of mineral base oils, for example, a kinematic viscosity at 100 ° C. is 20 mm 2 / s, greater 200 mm 2 / s or less Solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil, solvent dewaxing base oil, and the like.
  • Other synthetic base oils used in combination with the lubricating base oil according to this embodiment include the above-described synthetic base oils having a kinematic viscosity at 100 ° C. outside the range of 1 to 20 mm 2 / s. It is done.
  • the (A) viscosity index improver used in the present invention has a total peak area (M1) between 36 and 38 ppm in chemical shift with respect to the total area of all peaks. ) And the chemical shift of 64-66 ppm, the ratio of the total peak area (M2), that is, M1 / M2 is 0.20 or more.
  • the (A) viscosity index improver that satisfies the above conditions is specifically a non-dispersed or dispersed ester group-containing viscosity index improver, for example, a non-dispersed or dispersed poly (meth) acrylate viscosity index.
  • a non-dispersed or dispersed poly (meth) acrylate viscosity index examples include improvers, non-dispersed or dispersed olefin- (meth) acrylate copolymer viscosity index improvers, styrene-maleic anhydride copolymer viscosity index improvers, and mixtures thereof. It is preferably a mold-type or dispersion-type poly (meth) acrylate viscosity index improver.
  • a non-dispersed or dispersed polymethacrylate viscosity index improver is particularly preferable.
  • M1 / M2 is preferably 0.3 or more, more preferably 0.4 or more, particularly preferably 0.5 or more, and most preferably 0.6 or more.
  • M1 / M2 is preferably 3.0 or less, more preferably 2.0 or less, particularly preferably 1.0 or less, and most preferably 0.8 or less.
  • M1 / M2 is less than 0.20, not only the required fuel-saving property cannot be obtained, but also the low-temperature viscosity characteristics may be deteriorated.
  • M1 / M2 exceeds 3.0, there exists a possibility that the required fuel-saving property may not be acquired, and there exists a possibility that solubility and storage stability may deteriorate.
  • the nuclear magnetic resonance analysis ( 13 C-NMR) spectrum is obtained for a polymer obtained by separating the diluent oil by rubber membrane dialysis or the like when the viscosity index improver contains diluent oil.
  • the total area of the peak (M1) between 36-38 ppm chemical shift relative to the total area of all peaks is the total carbon integral as measured by 13 C-NMR when the viscosity index improver is, for example, poly (meth) acrylate.
  • the ratio of the integrated intensity derived from a specific ⁇ -branched structure of the poly (meth) acrylate side chain to the total intensity, and the total area (M2) of the peak between chemical shifts 64-66 ppm relative to the total area of all peaks is , Means the ratio of the integrated intensity derived from the specific linear structure of the poly (meth) acrylate side chain to the total integrated intensity of all carbons, as measured by 13 C-NMR.
  • M1 / M2 means the ratio of the specific ⁇ -branched structure of the poly (meth) acrylate side chain and the specific linear structure, but other methods may be used as long as equivalent results are obtained.
  • 13 C-NMR measurement 0.5 g of a sample diluted with 3 g of deuterated chloroform was used as a sample, the measurement temperature was room temperature, the resonance frequency was 125 MHz, and the measurement method was a gated decoupling method. It was used.
  • the poly (meth) acrylate viscosity index improver that can be used in the present embodiment is a general term for polyacrylate compounds and polymethacrylate compounds
  • a polymer of a polymerizable monomer containing a (meth) acrylate monomer represented by the general formula (1) (hereinafter referred to as “monomer M-1”).
  • R 1 represents hydrogen or a methyl group
  • R 2 represents a linear or branched hydrocarbon group having 1 to 200 carbon atoms.
  • the poly (meth) acrylate compound obtained by homopolymerization of two or more types of monomers represented by the general formula (1) is a so-called non-dispersed poly (meth) acrylate.
  • the poly (meth) acrylate compound according to the embodiment includes a monomer represented by the general formula (1) and one or more monomers selected from the general formulas (2) and (3) (hereinafter referred to as “monomer M-2”). And a so-called dispersed poly (meth) acrylate obtained by copolymerization of “monomer M-3”).
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkylene group having 1 to 18 carbon atoms
  • E 1 represents 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
  • Each represents an amine residue or a heterocyclic residue
  • a represents 0 or 1.
  • R 5 represents a hydrogen atom or a methyl group
  • E 2 represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
  • Specific examples of the group represented by E 1 and E 2 include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, and a benzoylamino group.
  • Morpholino group pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidono group, imidazolino group, pyrazino group and the like.
  • Preferable examples of the monomer M-2 and the monomer M-3 are specifically dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate. Morpholinoethyl methacrylate, N-vinylpyrrolidone, and mixtures thereof.
  • the production method of the poly (meth) acrylate is arbitrary, but for example, in the presence of a polymerization initiator such as benzoyl peroxide, the monomer (M-1) and the monomers (M-2) to (M-3) It can be easily obtained by radical solution polymerization of the mixture.
  • a polymerization initiator such as benzoyl peroxide
  • the PSSI (Permanent Cystability Index) of the (A) viscosity index improver is preferably 40 or less, more preferably 35 or less, still more preferably 30 or less, and particularly preferably 25 or less. Moreover, it is preferable that it is 0.1 or more, More preferably, it is 0.5 or more, More preferably, it is 2 or more, Especially preferably, it is 5 or more.
  • PSSI Permanent Cystability Index
  • PSSI Permanent Cystability Index of the (A) viscosity index improver is preferably 40 or less, more preferably 35 or less, still more preferably 30 or less, and particularly preferably 25 or less. Moreover, it is preferable that it is 0.1 or more, More preferably, it is 0.5 or more, More preferably, it is 2 or more, Especially preferably, it is 5 or more.
  • PSSI is less than 0.1, the effect of improving the viscosity index is small and the cost may increase.
  • PSSI exceeds
  • the weight average molecular weight of the viscosity index improver (M W) is preferably at least 100,000, more preferably 200,000 or more, even more preferably 250,000 or more, particularly preferably 300 1,000 or more. Moreover, it is preferably 1,000,000 or less, more preferably 700,000 or less, further preferably 600,000 or less, and particularly preferably 500,000 or less. When the weight average molecular weight is less than 100,000, the effect of improving the viscosity temperature characteristics and the effect of improving the viscosity index may be small and the cost may increase. When the weight average molecular weight exceeds 1,000,000, the shear stability There is a risk that the solubility in water and base oil and the storage stability may deteriorate.
  • the number average molecular weight (M N ) of the viscosity index improver is preferably 50,000 or more, more preferably 800,000 or more, still more preferably 100,000 or more, and particularly preferably 120. 1,000 or more. Further, it is preferably 500,000 or less, more preferably 300,000 or less, further preferably 250,000 or less, and particularly preferably 200,000 or less. If the number average molecular weight is less than 50,000, the effect of improving the viscosity temperature characteristics and the effect of improving the viscosity index may be small and the cost may increase. If the weight average molecular weight exceeds 500,000, shear stability and There is a possibility that solubility in oil and storage stability may deteriorate.
  • the ratio of the weight average molecular weight of the viscosity index improver to the PSSI is preferably 1.0 ⁇ 10 4 or more, preferably 1.5 ⁇ 10 4 or more, more preferably 2 0.0 ⁇ 10 4 or more, more preferably 2.5 ⁇ 10 4 or more, and particularly preferably 3.0 ⁇ 10 4 or more. If M W / PSSI is below 1.0 ⁇ 10 4, there is a possibility that the viscosity-temperature characteristic is deteriorated i.e. deteriorates fuel efficiency.
  • the ratio of the weight average molecular weight to the number average molecular weight (M W / M N ) of the viscosity index improver is preferably 0.5 or more, preferably 1.0 or more, more preferably 1.5 or more. More preferably, it is 2.0 or more, and particularly preferably 2.1 or more. Further, it is preferred that the M W / M N is 6.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, particularly preferably 3.0 or less. When MW / MN is less than 0.5 or exceeds 6.0, the viscosity temperature characteristic may be deteriorated, that is, the fuel economy may be deteriorated.
  • the kinematic viscosity thickening ratio ⁇ KV40 / ⁇ KV100 at 40 ° C. and 100 ° C. of the viscosity index improver is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less. Particularly preferred is 2.5 or less, and most preferred is 2.3 or less. Further, ⁇ KV40 / ⁇ KV100 is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, and particularly preferably 2.0 or more. If ⁇ KV40 / ⁇ KV100 is less than 0.5, the effect of increasing viscosity and solubility may be small and the cost may increase.
  • ⁇ KV40 means an increase in kinematic viscosity at 40 ° C. when 3.0% of a viscosity index improver is added to YUBASE4 manufactured by SK, and ⁇ KV100 is 3.0% of viscosity index improver added to YUBASE4 manufactured by SK. It means an increase in kinematic viscosity at 100 ° C. when added in%.
  • HTHS viscosity increase ratio ⁇ HTHS100 / ⁇ HTHS150 at 100 ° C. and 150 ° C. of the viscosity index improver is preferably 2.0 or less, more preferably 1.7 or less, and even more preferably 1.6 or less. Particularly preferably, it is 1.55 or less.
  • ⁇ HTHS100 / ⁇ HTHS150 is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.2 or more, and particularly preferably 1.4 or more. If it is less than 0.5, the viscosity increasing effect and solubility may be small and the cost may increase, and if it exceeds 2.0, the viscosity temperature characteristic improving effect and the low temperature viscosity characteristic may be inferior. .
  • ⁇ HTHS100 means an increase in HTHS viscosity at 100 ° C. when 3.0% of a viscosity index improver is added to SK YUBASE4, and ⁇ HTHS150 is SKBASE YUBASE4 with a viscosity index improver of 3.0%. It means an increase in HTHS viscosity at 150 ° C. when added in%.
  • ⁇ HTHS100 / ⁇ HTHS150 means the ratio of the increase in HTHS viscosity at 100 ° C. to the increase in HTHS viscosity at 150 ° C.
  • the HTHS viscosity at 100 ° C. referred to in the present invention indicates the high temperature and high shear viscosity at 100 ° C. as defined in ASTM D4683.
  • the HTHS viscosity at 150 ° C. indicates the high temperature and high shear viscosity at 150 ° C. defined in ASTM D4683.
  • the content of the (A) viscosity index improver in the lubricating oil composition according to the present embodiment is preferably 0.01 to 50% by mass, more preferably 0.5 to 40%, based on the total amount of the lubricating oil composition. % By mass, more preferably 1-30% by mass, particularly preferably 3-20% by mass, most preferably 5-10% by mass.
  • viscosity index improvers in addition to the component (A) described above, other viscosity index improvers can be used as the viscosity index improver.
  • examples include non-dispersed or dispersed ethylene- ⁇ -olefin copolymers or hydrogenated products thereof, polyisobutylene or hydrogenated products thereof, styrene-diene hydrogenated copolymers, and polyalkylstyrenes.
  • the lubricating oil composition according to this embodiment contains (B) a friction modifier.
  • B a friction modifier.
  • As a friction modifier 1 or more types of friction modifiers chosen from an organic molybdenum compound and an ashless friction modifier are mentioned.
  • organic molybdenum compound used in the present embodiment examples include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, and orthomolybdic acid.
  • sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC)
  • molybdenum compounds for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide
  • orthomolybdic acid examples include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxid
  • Molybdenum such as paramolybdic acid, (poly) sulfurized molybdate, metal salts of these molybdates, molybdates such as ammonium salts, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polysulfide molybdenum , Sulfurized molybdic acid, metal salts or amine salts of sulfurized molybdic acid, molybdenum halides such as molybdenum chloride, etc.) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mercaptothia Azole, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide,
  • organic molybdenum compound an organic molybdenum compound that does not contain sulfur as a constituent element can be used.
  • organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.
  • the lubricating oil composition when an organic molybdenum compound is used, its content is not particularly limited, but based on the total amount of the lubricating oil composition, preferably in terms of molybdenum element, preferably 0.001% by mass or more, More preferably 0.005% by mass or more, further preferably 0.01% by mass or more, particularly preferably 0.03% by mass or more, and preferably 0.2% by mass or less, more preferably 0.1% by mass. % Or less, more preferably 0.08 mass% or less, and particularly preferably 0.06 mass% or less.
  • the thermal and oxidation stability of the lubricating oil composition becomes insufficient, and in particular, it tends to be impossible to maintain excellent cleanliness over a long period of time.
  • the content exceeds 0.2% by mass, an effect commensurate with the content cannot be obtained, and the storage stability of the lubricating oil composition tends to decrease.
  • any compound usually used as a friction modifier for lubricating oil can be used.
  • one or two selected from oxygen atom, nitrogen atom, sulfur atom in the molecule examples thereof include compounds having 6 to 50 carbon atoms and containing at least a hetero element. More specifically, it has at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a straight chain alkyl group, straight chain alkenyl group, branched alkyl group or branched alkenyl group having 6 to 30 carbon atoms in the molecule.
  • Ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, fatty alcohols, aliphatic ethers, urea compounds, hydrazide compounds, and the like.
  • the content of the ashless friction modifier in the lubricating oil composition according to this embodiment is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably, based on the total amount of the lubricating oil composition. Is 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.
  • the content of the ashless friction modifier is less than 0.01% by mass, the effect of reducing friction due to the addition tends to be insufficient, and when the content exceeds 3% by mass, the effect of an antiwear additive or the like. Tends to be inhibited, or the solubility of the additive tends to deteriorate.
  • the friction modifier is preferably a molybdenum friction modifier, more preferably an organic molybdenum compound containing sulfur, and even more preferably molybdenum dithiocarbamate.
  • (C) 1st overbased metal salt used by this embodiment is oil-soluble metal salts, such as oil-soluble alkaline-earth metal sulfonate, alkaline-earth metal salicylate, alkaline-earth metal phenate, alkaline-earth metal phosphonate And an alkaline earth metal hydroxide or oxide and boric acid or boric anhydride.
  • alkaline earth metals include magnesium, calcium, barium and the like, with calcium being preferred.
  • alkaline earth metal salicylate is preferably used as the oil-soluble metal salt.
  • the base number of the first overbased metal salt is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, further preferably 150 mgKOH / g or more, 200 or more. It is particularly preferred that Moreover, it is preferable that it is 500 mgKOH / g or less, It is more preferable that it is 400 mgKOH / g or less, It is especially preferable that it is 300 mgKOH / g or less.
  • the base number in the present invention is a value measured according to JIS K 2501 5.2.3.
  • the particle size of the (C) first overbased metal salt is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
  • the manufacturing method of the 1st overbased metal salt is arbitrary, for example, said oil-soluble metal salt, alkaline earth metal hydroxide or oxide, and boric acid or anhydrous boric acid are mixed with water, methanol.
  • alcohol such as ethanol, propanol and butanol and diluting solvents such as benzene, toluene and xylene
  • the reaction is carried out at 20 to 200 ° C. for 2 to 8 hours, then heated to 100 to 200 ° C. with water and if necessary It is obtained by removing alcohol and diluting solvent.
  • the particle size of the overbased metal salt obtained by overbasing the oil-soluble metal salt produced by the above method with an alkaline earth metal borate is usually 0.1 ⁇ m or less, and the total base number is usually 100 mgKOH / g or more.
  • the lubricating oil composition according to this embodiment can be preferably used.
  • the content of the (C) first overbased metal salt in the lubricating oil composition according to the present embodiment is preferably 0.01 to 30% by mass, more preferably 0.05, based on the total amount of the lubricating oil composition. ⁇ 5% by mass. If the content is less than 0.01% by mass, the fuel saving effect may last only for a short period, and if it exceeds 30% by mass, the effect corresponding to the content may not be obtained. There is not preferable.
  • an overbased metal obtained by overbasing an oil-soluble metal salt with an alkaline earth metal carbonate in addition to (C) the first overbased metal salt, (E) an overbased metal obtained by overbasing an oil-soluble metal salt with an alkaline earth metal carbonate. More preferably, a salt (hereinafter referred to as “(E) second overbased metal salt”) is used in combination.
  • an overbased alkaline earth metal sulfonate obtained by overbasing an alkaline earth metal sulfonate with an alkaline earth metal carbonate, or an alkaline earth metal phenate as an alkaline earth metal examples include overbased alkaline earth metal phenates overbased with carbonates, overbased alkaline earth metal salicylates obtained by overbasing alkaline earth metal salicylates with alkaline earth metal carbonates, and the like.
  • alkaline earth metals include magnesium, calcium, barium and the like, with calcium being preferred. Among these, it is particularly preferable to use together an overbased calcium salicylate obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal carbonate.
  • the base number is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, further preferably 150 mgKOH / g or more, and particularly preferably 200 mgKOH / g or more. Moreover, it is preferable that it is 500 mgKOH / g or less, It is more preferable that it is 400 mgKOH / g or less, It is especially preferable that it is 300 mgKOH / g or less.
  • the lubricating oil composition according to this embodiment may contain any additive generally used in lubricating oils depending on the purpose in order to further improve its performance.
  • additives include metal detergents other than the first and second overbased metal salts, ashless dispersants, antiwear agents (or extreme pressure agents), antioxidants, and corrosion inhibitors.
  • additives such as rust preventives, demulsifiers, metal deactivators and antifoaming agents.
  • metal detergents other than the first and second overbased metal salts include alkali metal / alkaline earth metal sulfonate, alkali metal / alkaline earth metal phenate, and alkali metal / alkaline earth metal salicylate. Mention may be made of normal or basic salts.
  • alkali metal include sodium and potassium
  • examples of the alkaline earth metal include magnesium, calcium, and barium. Magnesium or calcium is preferable, and calcium is more preferable.
  • any ashless dispersant used in lubricating oils can be used.
  • any antiwear agent / extreme pressure agent used for lubricating oil can be used.
  • sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used.
  • zinc dialkyldithiophosphate (ZnDTP) phosphites, thiophosphites, dithiophosphites Acid esters, trithiophosphites, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithio Carbamate, MoDTC, disulfides, polysulfides, sulfurized olefins, sulfurized fats and oils, and the like can be given.
  • addition of a sulfur-based extreme pressure agent is preferable, and sulfurized fats and oils are particularly preferable.
  • antioxidants examples include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum.
  • phenol-based ashless antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-
  • amine-based ashless antioxidants include phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine, and dialkyldiphenylamine.
  • corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
  • rust preventive examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
  • demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylene alkyl naphthyl ether.
  • metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
  • metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
  • Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and ⁇ - (o-carboxybenzylthio) propiononitrile.
  • 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- Examples thereof include hydroxybenzyl alcohol.
  • the content of each additive is preferably 0.01 to 10% by mass based on the total amount of the lubricating oil composition.
  • the kinematic viscosity at 100 ° C. of the lubricating oil composition according to this embodiment is preferably 4 to 12 mm 2 / s, preferably 9 mm 2 / s or less, more preferably 8 mm 2 / s or less, and even more preferably 7 .8mm 2 / s or less, particularly preferably not more than 7.6 mm 2 / s. Further, the kinematic viscosity at 100 ° C. of the lubricating oil composition according to this embodiment is preferably 5 mm 2 / s or more, more preferably 6 mm 2 / s or more, still more preferably 6.5 mm 2 / s or more, particularly preferably. 7 mm 2 / s or more.
  • the kinematic viscosity at 100 ° C. in the present invention refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the kinematic viscosity at 100 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and if it exceeds 12 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
  • the kinematic viscosity at 40 ° C. of the lubricating oil composition according to this embodiment is preferably 4 to 50 mm 2 / s, preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less, and particularly preferably 32 mm. 2 / s or less, most preferably 30 mm 2 / s or less.
  • the kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present embodiment is preferably 10 mm 2 / s or more, more preferably 20 mm 2 / s or more, further preferably 25 mm 2 / s or more, and particularly preferably 27 mm 2. / S or more.
  • the kinematic viscosity at 40 ° C. in the present invention refers to the kinematic viscosity at 40 ° C. as defined in ASTM D-445. If the kinematic viscosity at 40 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and if it exceeds 50 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
  • the viscosity index of the lubricating oil composition according to this embodiment is preferably in the range of 140 to 400, preferably 190 or more, more preferably 200 or more, still more preferably 210 or more, and particularly preferably 220 or more.
  • the viscosity index of the lubricating oil composition according to this embodiment is less than 140, it may be difficult to improve fuel economy while maintaining the HTHS viscosity of 150 ° C., and further at ⁇ 35 ° C. It may be difficult to reduce the low temperature viscosity.
  • the viscosity index of the lubricating oil composition according to the present embodiment is 400 or more, there is a possibility that the evaporability may be deteriorated, and further, a problem due to insufficient solubility of the additive and compatibility with the sealing material. May occur.
  • the HTHS viscosity at 100 ° C. of the lubricating oil composition according to this embodiment is preferably 5.5 mPa ⁇ s or less, more preferably 5.0 mPa ⁇ s or less, even more preferably 4.8 mPa ⁇ s or less, particularly Preferably, it is 4.7 mPa ⁇ s or less. Further, it is preferably 3.0 mPa ⁇ s or more, more preferably 3.5 mPa ⁇ s or more, particularly preferably 4.0 mPa ⁇ s or more, and most preferably 4.2 mPa ⁇ s or more.
  • referred to in the present invention indicates a high temperature and high shear viscosity at 100 ° C. as defined in ASTM D4683.
  • the HTHS viscosity at 100 ° C. is less than 3.0 mPa ⁇ s, there is a risk of insufficient lubricity, and when it exceeds 5.5 mPa ⁇ s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.
  • the HTHS viscosity at 150 ° C. of the lubricating oil composition according to this embodiment is preferably 3.5 mPa ⁇ s or less, more preferably 3.0 mPa ⁇ s or less, even more preferably 2.8 mPa ⁇ s or less, particularly
  • the pressure is preferably 2.7 mPa ⁇ s or less. Further, it is preferably 2.0 mPa ⁇ s or more, more preferably 2.3 mPa ⁇ s or more, further preferably 2.4 mPa ⁇ s or more, particularly preferably 2.5 mPa ⁇ s or more, and most preferably 2.6 mPa ⁇ s or more. It is.
  • the HTHS viscosity at 150 ° C. referred to in the present invention indicates the high temperature and high shear viscosity at 150 ° C. defined in ASTM D4683.
  • the HTHS viscosity at 150 ° C. is less than 2.0 mPa ⁇ s, there is a risk of insufficient lubricity, and when it exceeds 3.5 mPa ⁇ s, the necessary low temperature viscosity and sufficient fuel saving performance cannot be obtained. There is a fear.
  • the ratio of the HTHS viscosity at 150 ° C. to the HTHS viscosity at 100 ° C. (HTHS viscosity at 150 ° C./HTHS viscosity at 100 ° C.) of the lubricating oil composition according to the present embodiment is preferably 0.50 or more. More preferably, it is 0.52 or more, More preferably, it is 0.54, Especially preferably, it is 0.55 or more, Most preferably, it is 0.56 or more. If the ratio is less than 0.50, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained.
  • the lubricating oil composition according to the present embodiment is excellent in fuel economy and lubricity, and it is not necessary to use a synthetic oil such as a poly- ⁇ -olefin base oil or an ester base oil or a low viscosity mineral oil base oil.
  • a synthetic oil such as a poly- ⁇ -olefin base oil or an ester base oil or a low viscosity mineral oil base oil.
  • the kinematic viscosity at 40 ° C. and 100 ° C. and the HTHS viscosity at 100 ° C. of the lubricating oil which are effective for improving fuel efficiency, while maintaining the HTHS viscosity at 0 ° C. at a constant level, are remarkably reduced.
  • the lubricating oil composition according to this embodiment having such excellent characteristics can be suitably used as a fuel-saving engine oil such as a fuel-saving gasoline engine oil and a fuel-saving diesel engine oil.
  • Example 1 to 5 Comparative Examples 1 to 3
  • lubricating oil compositions having the compositions shown in Table 2 were prepared using the base oils and additives shown below, respectively.
  • Table 1 shows the properties of the base oils O-1, O-2, and O-3.
  • lubricating oil compositions of Examples 1 to 5 using a polymethacrylate having a specific structure and adding an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate The thing shows that the motoring friction improvement rate (friction reduction rate) is large, and is excellent in fuel efficiency.
  • the lubricating oil composition of Comparative Example 1 that does not contain an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate has the same HTHS viscosity at 150 ° C. Despite being, motoring friction is large (improvement rate is small).
  • the lubricating oil composition of Comparative Example 2 which does not contain an overbased metal salt obtained by overbasing an oil-soluble metal salt with an alkaline earth metal borate and does not contain the predetermined polymethacrylate of the present application is also motoring friction. Is large (improvement rate is small).
  • the lubricating oil composition of Comparative Example 3 containing no friction modifier also has high motoring friction (small improvement rate).
  • the lubricating oil composition of the present invention maintains a high temperature and high shear viscosity at 150 ° C. without using a synthetic oil such as a poly- ⁇ -olefin base oil or an ester base oil or a low viscosity mineral oil base oil. In addition to being able to reduce the 100 ° C. HTHS viscosity, it can be seen that the addition of a friction modifier and a specific metal detergent significantly improves fuel economy.

Abstract

La présente invention concerne une composition lubrifiante incluant : une huile de base lubrifiante de viscosité cinématique comprise entre 1 et 20 mm²/s à 100 °C ; un agent améliorant l'indice de viscosité (A) dont le rapport entre l'aire totale (M1) d'un pic de déplacement chimique compris entre 36 et 38 ppm et l'aire totale (M2) d'un pic de déplacement chimique compris entre 64 et 66 ppm dans le spectre RMN 13C est supérieur ou égal à 0,20 (M1/M2) par rapport à l'aire totale de tous les pics ; un agent modificateur de friction (B) ; et un sel de métal surbasique (C) obtenu en surbasifiant un sel métallique oléosoluble par un sel d'acide borique d'un métal alcalino-terreux.
PCT/JP2010/066708 2010-01-07 2010-09-27 Composition lubrifiante WO2011083601A1 (fr)

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EP10842116.5A EP2522709A4 (fr) 2010-01-07 2010-09-27 Composition lubrifiante
CN2010800609965A CN102712869A (zh) 2010-01-07 2010-09-27 润滑油组合物
US13/520,679 US20120283159A1 (en) 2010-01-07 2010-09-27 Lubricant composition

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JP2010002270A JP2011140573A (ja) 2010-01-07 2010-01-07 潤滑油組成物

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EP2878655A4 (fr) * 2012-07-24 2016-03-09 Jx Nippon Oil & Energy Corp Composition d'huile pour moteur

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WO2014010462A1 (fr) * 2012-07-13 2014-01-16 Ｊｘ日鉱日石エネルギー株式会社 Composition d'huile lubrifiante pour moteur à combustion interne
WO2014017558A1 (fr) * 2012-07-24 2014-01-30 Ｊｘ日鉱日石エネルギー株式会社 Améliorant d'indice de viscosité à base de poly(méth)acrylate, et composition d'huile lubrifiante et additif pour huile lubrifiante le contenant
EP2878656B1 (fr) 2012-07-24 2018-01-10 JX Nippon Oil & Energy Corporation Améliorant d'indice de viscosité à base de poly(méth)acrylate, additif pour lubrifiant et composition lubrifiante le contenant
WO2014017556A1 (fr) * 2012-07-24 2014-01-30 Ｊｘ日鉱日石エネルギー株式会社 Composition d'huile lubrifiante
JP6097296B2 (ja) * 2012-07-31 2017-03-15 出光興産株式会社 内燃機関用潤滑油組成物
JP6059531B2 (ja) * 2012-12-28 2017-01-11 Ｊｘエネルギー株式会社 潤滑油組成物
JP6050716B2 (ja) * 2013-03-29 2016-12-21 Ｊｘエネルギー株式会社 潤滑油基油の製造方法
JP6375117B2 (ja) 2014-01-27 2018-08-15 出光興産株式会社 内燃機関用潤滑油組成物
EP3369802B1 (fr) * 2017-03-01 2019-07-10 Infineum International Limited Améliorations apportées et relatives à des compositions de lubrification
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US11634655B2 (en) 2021-03-30 2023-04-25 Afton Chemical Corporation Engine oils with improved viscometric performance
US11814599B2 (en) 2022-03-31 2023-11-14 Afton Chemical Corporation Durable magnet wires and lubricating fluids for electric and hybrid vehicle applications
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CN102712869A (zh) 2012-10-03
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US20120283159A1 (en) 2012-11-08
JP2011140573A (ja) 2011-07-21
EP2522709A4 (fr) 2014-03-12

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