WO2018078434A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2018078434A1
WO2018078434A1 PCT/IB2017/001299 IB2017001299W WO2018078434A1 WO 2018078434 A1 WO2018078434 A1 WO 2018078434A1 IB 2017001299 W IB2017001299 W IB 2017001299W WO 2018078434 A1 WO2018078434 A1 WO 2018078434A1
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WIPO (PCT)
Prior art keywords
lubricating oil
oil composition
mass
succinic acid
extreme pressure
Prior art date
Application number
PCT/IB2017/001299
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English (en)
Japanese (ja)
Inventor
貴文 森
剛久 佐藤
崇裕 福水
小川　仁志
純一 西ノ園
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 カンパ二ー
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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 カンパ二ー 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 カンパ二ー
Priority to US16/344,150 priority Critical patent/US20200071634A1/en
Priority to SG11201903317QA priority patent/SG11201903317QA/en
Priority to EP17829276.9A priority patent/EP3533857A1/fr
Publication of WO2018078434A1 publication Critical patent/WO2018078434A1/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
    • 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
    • C10M141/10—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 phosphorus-containing compound
    • 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
    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • 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
    • 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
    • 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
    • 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
    • C10M2223/043—Ammonium or amine 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
    • 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
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • 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
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/68—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76—Reduction of noise, shudder, or vibrations
    • 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
    • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]

Definitions

  • the present invention relates to a lubricating oil composition, and particularly to a lubricating oil composition characterized by being suitably used in an automobile transmission. More specifically, the present invention relates to a lubricating oil composition for a continuously variable transmission.
  • Lubricating oil compositions are widely used in the automotive field such as for internal combustion engines, automatic transmissions, and gear oils.
  • a continuously variable transmission (CTV) has been widely used instead of a stepped automatic transmission, and a metal bell-type CVT using a metal belt and pulley for power transmission is common.
  • Patent Documents 1 to 5 describe conventional lubricating oil compositions for continuously variable transmissions.
  • Japanese Patent Application Laid-Open No. 2 0 6-0 0 5 6 9 3 4 discloses that a specific succinic acid compound containing no boron and a phosphorus compound are blended, and a dialkyl zinc diphosphate A lubricating oil composition that does not contain any oil is described, the coefficient of friction between the metal belt or chain and the pulley is remarkably improved, and high friction over a long period of time. The friction coefficient can be maintained and the clutch plate is not clogged.
  • Patent Document 2 discloses a lubricant composition containing a sulfonate detergent, a salicylate detergent, and a boron-containing succinic acid imide additive in a specific amount and a specific amount ratio. It describes that it has sufficient torque transmission capacity and speed change characteristics and is excellent in anti-shudder performance.
  • JP 2009-2 15395 A Patent Document 3 has a boronated alkyl succinic acid imide and / or a boronated alkenyl succinic acid imide having a specific weight average molecular weight, and a linear alkyl group.
  • Patent Document 4 discloses a lubricating oil composition in which a specific amount of a specific sulfolane derivative, one or more selected from calcium sulfonate and calcium phenate, and a specific viscosity index improver are combined. It describes that it has a high metal friction coefficient, and achieves both fuel efficiency and component durability through low viscosity.
  • Patent Document 5 discloses that at least four kinds of additives, calcium salicylate, phosphorus-based antiwear agent, friction modifier, and dispersion type viscosity index improver, are blended as essential components. It states that a high coefficient of friction between metals and anti-shudder properties can be achieved at the same time.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2006-056934
  • Patent Document 2 JP 2007-1 2654 1
  • Patent Literature 3 Japanese Patent Publication No. 2 1395
  • Patent Document 4 Japanese Patent Laid-Open No. 201 0-1 80278
  • Patent Document 5 Opening 2000-355695
  • the first object of the present invention is to provide a lubricating oil composition having an extended shudder prevention life without lowering the coefficient of friction between metals even when the viscosity is lowered.
  • a lubricating oil composition comprising a phosphorus-based extreme pressure agent, wherein the lubricating oil composition does not contain zinc dithiophosphate, and may optionally contain a sulfur-based extreme pressure agent, However, in the lubricating oil composition, the content of the sulfur-based extreme pressure agent is 0.1% by mass or less in the lubricating oil composition.
  • the present inventors have further identified the constitution of the lubricating base oil and the viscosity index improver in the lubricating oil composition, thereby improving the anti-shoulder life without reducing the intermetallic friction coefficient. In addition to the above, it was found that shear stability can be improved. That is, the present invention further includes
  • a lubricating oil composition comprising a phosphorus-based extreme pressure agent, wherein the lubricating oil composition does not contain zinc dithiophosphate and may optionally contain a sulfur-based extreme pressure agent, However, the content of the sulfur-based extreme pressure agent is 0.1 mass% or less in the lubricating oil composition,
  • a poly ⁇ -age olefin or ⁇ -age olefin copolymer having kinematic viscosity SS Omm 2 , s at 100 ° C is added to the mass of the entire lubricating oil composition. With respect to 5 to 30% by mass, and
  • a lubricating oil composition further comprising polymethacrylate having a weight average molecular weight of 15,000 to 40,000.
  • a preferred embodiment of the lubricating oil composition of the present invention has at least the following features (1) to (10).
  • Part or all of the (1) (C-1) component and (C1-2) component are boronated succinimide compounds.
  • the component (C-1) and the component (C1-2) are each composed of 0.1 to 3 masses of boron with respect to the mass of the component (C-1) or the component (C1-2). % Content.
  • the succinic acid imide compound is represented by the following formula (1) or (2). [Chemical 1]
  • R 1 is independently an alkyl group or alkenyl group having 40 to 400 carbon atoms
  • m is an integer of ⁇ to 20
  • n is an integer of 0 to 20.
  • the phosphorus extreme pressure agent is selected from acidic phosphoric acid ester, acidic phosphorous acid ester, phosphoric acid ester, phosphorous acid ester, and their amine salts, phosphoric acid, and phosphorous acid At least one or more.
  • the phosphorus extreme pressure agent is at least one selected from acidic phosphoric acid ester, acidic phosphorous acid ester, phosphoric acid ester, phosphorous acid ester, and amine salts thereof; It is a combination with at least one selected from acid and phosphorous acid.
  • (E) contains a metal detergent.
  • the lubricating oil composition comprises a poly ⁇ -age olefin having a kinematic viscosity of 6 to 80 mm 2 / s at 100 ° C as part or all of the component (A). It is preferable that the ⁇ -aged lefin copolymer is contained in an amount of 5 to 30% by mass with respect to the total mass of the lubricating oil composition, and (ii) an ether sulfolane compound.
  • Synthetic base oils have a lower affinity with oil seal rubbers called packings and gaskets than mineral oils, and the higher the molecular weight (high viscosity) base oil, the lower the affinity.
  • the swelling of the seal rubber is reduced, and conversely, it tends to shrink. As a result, there is a problem that the sealing performance is lowered and oil leakage occurs.
  • the lubricating oil composition of the present invention can extend the anti-shudder life without lowering the coefficient of friction between metals. This effect can be achieved even when the kinematic viscosity of the lubricating oil composition at 100 ° C. is lowered to about 5.0. Moreover, according to the present invention, in addition to the effect, a lubricating oil composition having improved shear stability can be provided. Furthermore, the swelling property of the seal rubber can be ensured.
  • the lubricating oil composition of the present invention can be particularly suitably used as a lubricating oil composition for continuously variable transmissions.
  • a conventionally known lubricating base oil can be used, and there are mineral oil, synthetic oil, or a mixed oil thereof.
  • a poly ⁇ -age olefin or ⁇ -age olefin copolymer having a kinematic viscosity of 6 to 8 O mm 2 / s at 100 ° C. preferably contains 5-3 0% by weight relative to the lubricating oil composition total weight, and more preferably, the lower limit is 6 mass%, good Ri preferably 8 mass%, the upper limit is 2 5 mass 0/0 More preferably, it is 20% by mass.
  • the content of the base oil is less than the lower limit, a sufficient viscosity index, that is, In other words, it is not possible to achieve both fuel saving performance and protection performance for machine elements, and if the above upper limit is exceeded, there is a risk that the shear stability will deteriorate and the rubber compatibility will deteriorate (rubber shrinkage).
  • the poly ⁇ -year-old refin and ⁇ -year-old olefin copolymer should have a kinematic viscosity of 6-8 Omm 2 / s at 100 ° C, preferably 8-80 mm 2 Z s. More preferably, it is 8-60 mm ⁇ 2 > / s, More preferably, it is 9-40 mm ⁇ 2> / s. If the kinematic viscosity at 100 is less than the above lower limit value, the viscosity index, that is, the fuel efficiency and the protection performance to the machine element cannot be achieved at the same time. Unfavorable because shear stability and rubber compatibility deteriorate (rubber shrinkage).
  • the poly ⁇ -year-old refin or ⁇ -year-old refin copolymer is a (co) polymer or (co) oligomer of ⁇ -year-old refin, and may have any of the above kinematic viscosities.
  • Conventionally known oils can be used.
  • the ⁇ -year-old refin is, for example, selected from linear or branched refin hydrocarbons having 2 to 14 carbon atoms, preferably 4 to 12 carbon atoms. Examples thereof include 1-year-old kuten oligomers, 1-decene oligomers, ethylene monopropylene oligomers, isobutene oligomers and hydrides thereof.
  • the poly ⁇ -age olefin or ⁇ -age olefin copolymer may be one produced using a meta-octane catalyst.
  • the (co) polymer or (co) oligomer may have a mass average molecular weight as long as the kinematic viscosity at 100 ° C. satisfies the above range. For example, it has a mass average molecular weight of 1,000 to 10,000, preferably 1,100 to 7,000.
  • the poly ⁇ -age olefin or ⁇ -age olefin copolymer may be used alone or in combination of two or more.
  • the lubricating oil composition of the present invention may contain another lubricating base oil in combination with the poly ⁇ -age olefin or ⁇ -age olefin copolymer.
  • These lubricating base oils are not particularly limited, and conventionally known mineral base oils and synthetic base oils other than the above-mentioned poly ⁇ -age olefins and ⁇ -age olefin copolymers can be used.
  • Mineral oil base oil includes a lubricating oil distillate obtained by atmospheric distillation and vacuum distillation of crude oil.
  • the paraffin-based, naphthenic-type, etc. were refined by appropriately combining the solvent desolvation, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrotreating, sulfuric acid washing, clay treatment, etc.
  • Examples include lubricating base oils and lubricating base oils obtained by isomerizing and dewaxing waxes obtained by solvent dewaxing.
  • the kinematic viscosity of the mineral oil base oil is not limited to waiting, but in order to obtain a lubricating oil composition having a low viscosity, it is preferably 1 to 5 mm 2 Zs.
  • the synthetic base oil isoparaffin, alkylbenzene, alkylnaphthalene, monoester, diester, polyol ester, polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl ether, GT L base oil and the like can be used.
  • the kinematic viscosity of the synthetic base oil is not particularly limited. It is also possible to use 1 00 ° kinematic viscosity at C is less than 6 mm 2 / s or 80 mm 2, s than a is poly ⁇ - old olefin or ⁇ - old olefin copolymer. In order to obtain a lubricating oil composition having a low viscosity, the kinematic viscosity of the synthetic base oil is preferably 1 to 6 mm 2 / s.
  • the base oils that can be used in combination may be used alone or in combination of two or more.
  • use two or more mineral base oils use two or more synthetic base oils, and use one or more mineral base oils and one or more synthetic base oils.
  • the entire lubricating base oil may have a kinematic viscosity at 100 ° C of 2 to 7 mm 2 / s, preferably 2.3-6. It is preferable to have mm 2 / s, particularly 2.5 to 5.6 mm 2 / s.
  • the lubricating oil composition of the present invention can contain a conventionally known viscosity index improver.
  • polymethacrylate relay having a weight average molecular weight of 15,000 to 40,000 is preferably included as a viscosity index improver.
  • Mass average molecular weight The lower limit of is preferably 1 7, 0 0 0, more preferably 1 8 0 0 0 0.
  • the upper limit of the mass average molecular weight is preferably 38,00,0, more preferably 36,000.
  • the content of the polymethacrylate is not limited, it is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass in the lubricating oil composition. .
  • Polymethacrylate may be used alone or in combination of two or more. Content in the case of using 2 or more types together is not limited.
  • the total content of polymethacrylate-soot is preferably 0.1 to 20% by mass in the lubricating oil composition, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass.
  • the lubricating oil composition of the present invention may contain other viscosity index improvers in addition to the polymethacrylate relay.
  • Such other viscosity index improvers include polymethacrylates having a weight average molecular weight of less than 15 000, polymethacrylates having a weight average molecular weight of more than 40,000, polyisobutylene and water thereof.
  • the blending amount is preferably an amount of 0.1 to 15% by mass in the lubricating oil composition.
  • the lubricating oil composition of the present invention is characterized by containing two kinds of specific succinic acid imide compounds or boronated succinic acid imide compounds as ashless dispersants. That is, the present invention provides a succinic acid composition in which the lubricating oil composition has (C-1) weight average molecular weight 4, 0 00 to 7, 0 0 0, preferably 5, 0 0 0 to 7, 0 0 0.
  • a boron compound or a boronated succinic acid imide compound and (C 1 2) weight average molecular weight of more than 7,00 to 1,0,0,0, preferably 7,10,0 to 9,600, It is characterized by containing a combination of existing succinic acid compounds or boronated succinic acid compounds.
  • the above (C 1 1) component is It is called a succinic acid imide compound, and the above (C-12) component is sometimes referred to as a second succinic acid imide compound.
  • At least one of the component (C1-1) and the component (C1-2) may be a part or all of a boronated succinic acid imide compound.
  • both (C 1 1) component and (C-2) component may be a boronated succinic acid imide compound.
  • the component (C) is preferably 0.5 to 3% by mass, more preferably 0.6 to 2.5% by mass, and still more preferably 0.9 to 2% by mass, based on the entire composition. Contained in the composition in an amount of. If it is less than the lower limit, it may not be possible to secure anti-shudder. Above the upper limit, the viscosity at low temperatures may be high
  • the amount ratio of (C 1 2) exceeds the above upper limit, the amount of (C-1) component is too small, and the characteristics at low temperatures, for example, 40 ° C, are insufficient for preventing shudder. A problem arises that it becomes apparent at an early stage.
  • the amount ratio of (C 1 2) is less than the above lower limit, there is a problem that the characteristics at high temperatures, for example, 120 ° C., are insufficient, and are manifested early in the durability test.
  • the first and second succinic acid imide compounds in the present invention may be succinic acid imide compounds or boronated succinic acid imide compounds known as ashless dispersants.
  • a boronated succinic acid imide compound is obtained by modifying (borating) a succinic acid imide compound having at least one alkyl group or alkenyl group in a molecule with a boron compound such as boric acid or borate.
  • a boron compound such as boric acid or borate.
  • alkyl group or alkenyl group include olefins such as propylene, 1-butene and isopylene, or oligomers thereof, and ethylene and propylene co-oligomers.
  • the succinic acid imide compound is more specifically, succinic anhydride is added to the polyamine. It is an added compound.
  • the monotype succinic acid imide compound can be represented by, for example, the following formula (1).
  • the bis-type succinic acid imide compound can be represented, for example, by the following formula (2).
  • R ′ is independently an alkyl group or an alkenyl group having 40 to 40 carbon atoms, m is an integer from ⁇ to 20 and n is an integer from 0 to 20;
  • a bis-type succinic acid imide compound is particularly preferable.
  • the succinic acid imide compound may be a combination of monotype and bistype, a combination of two or more monotypes, or a combination of two or more bistypes.
  • the boronated succinic acid imide compound is a compound obtained by reacting a succinic acid imide compound represented by the above formula with a boron compound.
  • Boron compounds include boric acid, boric anhydride, boric acid ester, boron oxide, and boron halide.
  • the boronated succinic acid imide compound may be a single type or a combination of two or more types.
  • the first and second succinic acid imide compounds are Each may be part or all of a boronated succinic acid imide compound.
  • the first and second succinic acid imide compounds in the present invention are independent of each other, and are singly or in combination of non-borated succinic acid imide compounds, fluorinated succinic acid imides.
  • the compound may be any one selected from the group consisting of a single compound or two or more compounds, and a combination of one or more non-borated succinic acid compounds and one or more boronated succinic acid compounds.
  • the ratio of the boronated succinic acid imide compound is not particularly limited, but is preferably 5 to 100% by mass with respect to the mass of each component, Furthermore, 20 to 100% by mass is preferable, and further 50 to 100% by mass is preferable.
  • the first succinic acid imide compound has a mass average molecular weight of 4,000 to
  • the mass average molecular weight is preferably 5,000 to 7,000, more preferably 5,200-6,800.
  • the mass average molecular weight of the first succinic acid imide compound is as follows: solvent: THF (tetrahydrofuran), packed column: styrene • divinylbenzene copolymer, set temperature: 40 ° C, set flow rate 1.
  • solvent THF (tetrahydrofuran)
  • packed column styrene • divinylbenzene copolymer
  • set temperature 40 ° C
  • set flow rate 1.
  • Om I minutes measured in RI (differential refraction) detector, in terms of polystyrene
  • the boron content in the component (C-1) is not limited, but the component (C-1) preferably from 0.1 to 3% by weight, based on the weight of the borated succinic acid imide compound is, further from 0.2 to 2.5 mass 0/0 are preferred, in a further 0.2 to 2 wt% In particular, 0.2 to 1.5% by mass is preferable.
  • the nitrogen content in the (C-1) component is not limited, but it is preferably 0.3 to 10% by mass based on the mass of the boronated succinic acid imide compound that is the (C-1) component.
  • the content of the first succinic acid compound in the lubricating oil composition is not limited, but is preferably 0.05 to 2 mass% with respect to the total mass of the lubricating oil composition. 0.08 to 1.8% by mass is more preferable, and 0.1 to 1.5% by mass is more preferable. If the content is less than the lower limit, sufficient cleanliness may not be ensured, and if the content exceeds the upper limit, sludge may be generated.
  • the second succinic acid imide compound has a mass average molecular weight of more than 7,000 to 10,000.
  • the mass average molecular weight is preferably 7,100-9,600, more preferably 7,500-9,200. If the molecular weight of the second succinic acid imide compound is more than 10,000, the low-temperature viscosity will deteriorate.
  • the mass average molecular weight of the second succinic acid imide compound is as follows: solvent: THF (tetrahydrofuran), packed column: styrene-divinylbenzene copolymer, set temperature: 40 ° C, set flow rate 1. It is a polystyrene equivalent value measured with an RI (differential refraction) detector at Oml / min.
  • the boron content in the component (C1-2) is not limited, but the component (C-2)
  • the boron content is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass with respect to the mass of the boronated succinic acid imide compound. / 0 is preferable, more preferably 0.2 to 2% by mass, and particularly preferably 0.2 to 1.5% by mass.
  • the nitrogen content in the component (C1-2) is not limited, but is preferably 0.2-5% by mass relative to the mass of the boronated succinic acid imide compound as the component (C1-2). Is preferably 0.3 to 2.5% by mass, and more preferably 0.5 to 2% by mass.
  • the content of the second succinic acid imide compound in the lubricating oil composition include, but are not limited to, 0.1 is preferably 05-2 wt%, 0.1 08 ⁇ . 8 mass 0/0 Gayo More preferred is 0.1 to 1.5% by mass. If it is less than the lower limit, sufficient cleanliness may not be ensured, and if it exceeds the upper limit, low temperature viscosity is generated.
  • the lubricant composition of the present invention may further contain another ashless dispersant in combination with the component (C1-1) and the component (C1-2). Other ashless dispersants typically include succinic acid amide compounds.
  • the lubricating oil composition of the present invention essentially contains (D) a phosphorus extreme pressure agent.
  • the phosphorus extreme pressure agent is an extreme pressure agent having phosphorus, and may be a conventionally known one.
  • the content of the phosphorus-based extreme pressure agent in the lubricating oil composition is not limited, but is preferably from 0. 01 to 2.5% by mass based on the total mass of the lubricating oil composition, and from 0. 02 to 1 5% by mass is more preferable, and 0.02 to 1.0% by mass is more preferable.
  • the phosphorus-based extreme pressure agent in the present invention may have sulfur. Phosphorus-sulfur-based extreme pressure agents such as citrate phosphate are included in the phosphorus-based extreme pressure agent. Not included. However, in the present invention, the phosphorus-based extreme pressure agent does not include zinc dithiophosphate. Particularly preferably, the phosphorus extreme pressure agent in the present invention does not have a metal element.
  • the lubricating oil composition of the present invention may further contain a sulfur-based extreme pressure agent in addition to the phosphorus-based extreme pressure agent.
  • the sulfur-based extreme pressure agent is an extreme pressure agent having sulfur and may be a conventionally known one. Further, as described above, the lubricating oil composition of the present invention does not contain zinc dithiophosphate. Therefore, the sulfur-based extreme pressure agent in the present invention does not include ditian zinc phosphate. Particularly preferably, the sulfur-based extreme pressure agent in the present invention does not have a metal element.
  • the content of the sulfur type extreme pressure agent in the lubricating oil composition of the present invention is 0.1% by mass or less, preferably 0.08% by mass or less, more preferably 0.06% by mass in the lubricating oil composition. It is the amount that is less than or equal to mass%. If the lubricating oil composition contains a sulfur-based extreme pressure agent in the lubricating oil composition in an amount exceeding the above upper limit, the shudder characteristics will be poor.
  • the lubricating oil composition of the present invention does not contain zinc dithiophosphate. This is because the presence of zinc phosphate in the lubricating oil composition deteriorates the shudder characteristics of the lubricating oil composition.
  • the phosphorus extreme pressure agent is preferably a phosphate ester or an acidic phosphate ester. , Phosphites, acidic phosphites, and their amine salts, phosphoric acid, and phosphorous acid. These may be used alone or in combination of two or more. Particularly preferably, the phosphorus extreme pressure agent is at least one selected from phosphoric acid ester, acidic phosphoric acid ester, phosphite ester, acidic phosphite ester and their amine salts, and phosphoric acid. And a combination of at least one selected from phosphorous acid. In addition to these phosphorus-based extreme pressure agents, sulfur-based extreme pressure agents may be included, but the content thereof must satisfy the above-mentioned conditions.
  • b is 0 1 or 2;
  • R 2 is independently a monovalent hydrocarbon group having a carbon number of 430.
  • the phosphoric acid ester and the acidic phosphoric acid ester are preferably a monoalkyl phosphate, a dialkyl phosphate, and a phosphoric acid trialkyl ester, but are not limited thereto.
  • the phosphite and acidic phosphite are preferably monoalkyl phosphite and dialkyl phosphite, but are not limited thereto.
  • phosphorus-based extreme pressure agent a compound in which a part of oxygen atoms of the above-described phosphoric acid ester, phosphorous acid ester, acidic phosphoric acid ester or acidic phosphorous acid ester is substituted with a sulfur atom, for example, Also included are thiophosphate, citrus phosphite, citrate phosphate, and citrate phosphite.
  • alkylamine salts and alkenylamine salts of the above compounds which are partial esters can also be suitably used. That is, an amine salt of an acidic phosphate ester and an amine salt of an acidic phosphite ester can be used, but are not limited thereto.
  • phosphoric acid and phosphorous acid are preferably used as phosphorus-based extreme pressure agents other than those described above.
  • At least selected from phosphoric acid In combination with at least one kind is preferred.
  • the ratio of phosphoric acid and phosphorous acid when used in combination is not particularly limited, but phosphoric acid and phosphorous acid are 0.02 to 0.5 mass% with respect to the total mass of the phosphorous extreme pressure agent. Is preferred.
  • it is selected from an acidic phosphate, phosphoric acid and phosphorous acid.
  • the acidic phosphate ester is preferably at least one selected from acidic phosphoric acid butyl ester, acidic phosphoric acid hexyl ester, acidic phosphoric acid-containing ethyl ester, and acidic phosphoric acid dodecyl ester.
  • sulfur-based extreme pressure agent examples include sulfurized olefins, sulfurized fats and oils, sulfurized esters, and polysulfide.
  • Sulfurated refin is a compound obtained by sulphurizing refins.
  • the sulfurized olefin is obtained, for example, by sulfurizing olefins such as polyisobutylenes and terpenes with sulfur or other sulfiding agents.
  • Sulfurized fat and oil is a reaction product of fat and sulfur.
  • it can be obtained by sulfurizing animal and vegetable oils such as lard, beef tallow, whale oil, palm oil, coconut oil and rapeseed oil.
  • the product obtained by the reaction is not a single substance species but may be a mixture of various substances. Therefore, the chemical structure is not always clear.
  • sulfurized esters are obtained by converting ester compounds obtained by the reaction of various organic acids (saturated fatty acids, unsaturated fatty acids, dicarboxylic acids, aromatic carboxylic acids, etc.) with various alcohols to sulfur and other sulfurized compounds. And those obtained by sulfurization with an agent. Like sulfurized fats, the chemical structure is not always clear.
  • the lubricating oil composition of the present invention preferably further comprises (E) a metal detergent and / or (F) an ether sulfolane compound in addition to the components (A) to (D).
  • metal detergents include detergents having an alkali metal or an alkaline earth metal.
  • sulfonates containing alkali metals or alkaline earth metals, salicylates containing alkali metals or alkaline earth metals examples include, but are not limited to, phenates containing Lucari metal or alkaline earth metal.
  • alkali metal or alkaline earth metal examples include, but are not limited to, magnesium, barium, sodium, and calcium.
  • the sulfonate containing alkali metal or alkaline earth metal is not limited, but calcium sulfonate and magnesium sulfonate are preferably used.
  • the salicylate containing an alkali metal or an alkaline earth metal is not limited, but calcium salicylate and magnesium salicylate are preferably used.
  • the phenate containing an alkali metal or an alkaline earth metal is not limited, but calcium phenate and magnesium phenate are preferably used.
  • the amount of alkali metal or alkaline earth metal contained in the metal detergent include, but are not limited to, 0.1 is preferably 1 to 20 mass%, 0.5 to 1 5 weight 0/0 Gayori preferably 1.0 to 15% by mass is more preferable.
  • the metal detergent is not limited, but preferably has a total base number of 10 to 50 Omg KOH / g, more preferably 50 to 40 Omg KOH / g, and 150 to 400 mg KOH / g is more preferred.
  • a total base number 10 to 50 Omg KOH / g, more preferably 50 to 40 Omg KOH / g, and 150 to 400 mg KOH / g is more preferred.
  • it is 200 to 400 mg KOHZg, more preferably 300 to 40 Omg KOH / g, most preferably, when it is 310 to 400 mg KOH / g, the cleansing effect is also obtained. Most preferable because it is high and sludge generation can be suppressed.
  • the metal detergent may be contained in the lubricating oil composition in an arbitrary ratio. For example, it is 0 to 5% by mass, more preferably 0.1 to 2% by mass, and still more preferably 0.2 to 1% by mass.
  • the metal detergents may be used alone or in combination of two or more. Even if they are used together, there is no limitation on the type.
  • the lysylate compound and the phenate compound may be used, but a combination of a sulfadate compound and a salicylate compound, a sulfonate compound and a phenoate compound, or a combination of a sulcillate compound and a phenoate compound may be used.
  • the lubricating oil composition of the present invention can further ensure appropriate seal rubber swelling.
  • the ether sulfolane compound is the following compound.
  • R is an alkyl group having ⁇ -20 carbon atoms, preferably an alkyl group having 8-16 carbon atoms.
  • the blending amount of the ether sulfolane compound is preferably 0 to 5% by mass, more preferably 0.2 to 2% by mass, and more preferably 0.2 to 1% by mass in the lubricating oil composition.
  • the lubricating oil composition of the present invention may further contain other additives other than the above (B) to (F).
  • additives other than the above (B) to (F).
  • Various lubricating oil package additives containing at least one of these can also be added.
  • the kinematic viscosity at 100 ° C of the lubricating oil composition of the present invention is not limited, but is preferably 3 to 10 mm 2 / s, and 3 to 8 mm 2 / s. More preferably, it is more preferably 4 to 7.5 mm 2 / s, and 4 to 6 m. More preferably, m 2 / s. If the kinematic viscosity at 100 ° C of the lubricating oil composition is less than the above lower limit value, the friction coefficient may not be sufficiently secured. Further, if it exceeds the above upper limit value, the shudder characteristic may be deteriorated.
  • the viscosity index of the lubricating oil composition of the present invention is not limited, but is preferably 150 or more, and more preferably 60 or more. If the viscosity index of the lubricating oil composition is less than the above lower limit, it may not be possible to secure sufficient low shear characteristics.
  • the upper limit is not limited, but is preferably 250.
  • the lubricating oil composition of the present invention has an effect that it has a sufficiently large coefficient of friction between metals and can secure a shudder characteristic despite its low viscosity. Further, as described above, shear stability can be ensured by further specifying the composition of the base oil and the viscosity index improver according to the present invention. Furthermore, by containing an ether sulfolane compound, it is possible to ensure an appropriate seal rubber swelling property. Furthermore, the use of a metal detergent having a total base number of 200 to 40 Omg KO H / g is preferable because it can suppress the generation of sludge while ensuring cleanliness.
  • the lubricating oil composition of the present invention can be suitably used for a continuously variable transmission.
  • each component used in Examples and Comparative Examples is as follows. Each component shown below was mixed in the composition shown in Table 1 or Table 2 to prepare a lubricating oil composition.
  • KV 100 means kinematic viscosity at 100 ° C
  • VI means viscosity index
  • PMA means polymethacrylate.
  • Antiwear agent friction modifier, antioxidant, antifoam agent, metal deactivator, and colorant
  • Viscosity index test method Measured according to ASTM D 2270.
  • Anti-shudder life test method 40 ° C, 60 ° C, 80 ° C, 1 2 (evaluated at TC d xZd v (1.0 0-2
  • Friction coefficient (compared with commercial products): Made by Optimol, S RV friction and wear tester, SU J ball (diameter 1 Omm), SU J disk (diameter 24mmx height 6.9) mm s lapping), load: 1 O ON, temperature: 100 ° C, frequency: 5 OH z, amplitude: 0.5 mm, and the average value of the coefficient of friction after 30 minutes Asked.
  • the friction coefficient of the commercial oil (Comparative Example 5) is 1
  • Rubber swelling test method ASTM D47 1 C type dumbbell-shaped ACM rubber (NOK T945) was immersed in sample oil at 150 ° C and volume change after 70 hours The rate was determined.
  • Comparative Example 5 a commercially available lubricating oil composition for a transmission was evaluated.
  • Example 1 Example 2
  • Example 3 Example 4 Actual base oil V100 4.0 4 0 4.0 3.7
  • the lubricating oil composition of the present invention contains two types of succinic acid imides, and contains a phosphorus-based extreme pressure agent. Therefore, despite the low kinematic viscosity at 100 ° C., the anti-shudder life can be extended without lowering the coefficient of friction between metals.
  • the (C-2) component is not included, the shudder characteristic is deteriorated.
  • the dilute zinc phosphate is included, the shudder characteristic is deteriorated.
  • the sulfur-based extreme pressure agent is contained in excess of the upper limit of the present invention, the shudder characteristic is deteriorated.
  • Example 1 (A) the composition of the component is specified, and (F) further containing ether sulfolane further improves the seal rubber swelling property in addition to the above effects. can do.
  • the lubricating oil composition of the present invention can be particularly suitably used for automobile transmissions, particularly for continuously variable transmissions.

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

Abstract

Le premier but de la présente invention est de fournir une composition d'huile lubrifiante qui permet d'obtenir une durabilité anti-vibration prolongée sans provoquer une diminution du coefficient de frottement métal-métal, même lorsque la viscosité de la composition est réduite. L'invention concerne une composition d'huile lubrifiante caractérisée en ce qu'elle comprend (A) une huile de base lubrifiante, (C) (C-1) un composé de succinimide ou un composé de succinimide boré ayant une masse moléculaire moyenne en poids comprise entre 4 000 à 7000, (C-2) un composé de succinimide ou un composé de succinimide boré ayant une masse moléculaire moyenne en poids de plus de 7000 à 10 000, et (D) un agent de pression extrême à base de phosphore, la composition d'huile lubrifiante ne comprenant pas de dithiophosphate de zinc et pouvant éventuellement comprendre un agent de pression extrême à base de soufre, à condition que la teneur en agent de pression extrême à base de soufre ne soit pas supérieure à 0,1 pour cent en poids de la composition d'huile lubrifiante.
PCT/IB2017/001299 2016-10-27 2017-10-27 Composition d'huile lubrifiante WO2018078434A1 (fr)

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