WO2012176484A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2012176484A1
WO2012176484A1 PCT/JP2012/051220 JP2012051220W WO2012176484A1 WO 2012176484 A1 WO2012176484 A1 WO 2012176484A1 JP 2012051220 W JP2012051220 W JP 2012051220W WO 2012176484 A1 WO2012176484 A1 WO 2012176484A1
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group
mass
lubricating oil
less
carbon atoms
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PCT/JP2012/051220
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English (en)
Japanese (ja)
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八木下　和宏
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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 US14/124,333 priority Critical patent/US20140113845A1/en
Priority to CN201280030596.9A priority patent/CN103620006B/zh
Priority to EP12802100.3A priority patent/EP2725088A4/fr
Publication of WO2012176484A1 publication Critical patent/WO2012176484A1/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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/06—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
    • 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
    • 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
    • C10M2207/26—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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • 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
    • C10M2223/042—Metal 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
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/40—Low content or no content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • 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
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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

Definitions

  • the present invention relates to a novel lubricating oil composition, and more particularly to a lubricating oil composition having excellent oxidation stability, which is produced by blending a metal salt of a thiophosphate having a specific structure with a base oil.
  • the present invention relates to a lubricating oil composition suitably used as a lubricating oil for an internal combustion engine.
  • lubricating oils and greases are used for internal combustion engines, automatic transmissions, and the like in order to facilitate their operation.
  • lubricating oil (engine oil) for internal combustion engines is required to have high performance as the performance of the engine increases, the output increases, and the operating conditions become severe.
  • various additives such as antiwear agents, metal detergents, ashless dispersants, and antioxidants are blended in conventional engine oils (see, for example, Patent Documents 1 to 3). .
  • engine oil is always in contact with peroxide, which is an active species of oxidative degradation, in the piston-cylinder region, and therefore, excellent oxidation resistance is required.
  • ZDTP zinc dialkyldithiophosphate
  • molybdenum compounds as other peroxide decomposing agents
  • ZDTP is also an excellent anti-wear agent
  • molybdenum compounds are also known as excellent friction modifiers that reduce friction and are used in many engine oils.
  • ZDTP acts as an antioxidant or an anti-wear agent.
  • ZDTP rather lowers the base number of the lubricating oil and causes deposits.
  • ZDTP is an extremely difficult additive in lubricating oils that require a long life.
  • various ZDTPs with different alkyl groups have been produced, and the lubricating oil composition to which these are added has been devised in various combinations with metallic detergents and other antioxidants. Not reached.
  • the present invention contains at least one phosphorus compound represented by the general formula (1) as the component (A) in the lubricating base oil, and is a sulfur element based on phosphorus in the oil and the compound of the general formula (1).
  • Lubricating oil composition having a ratio (S / P molar ratio) of 0.05 to 0.8 and an amount of phosphorus in oil based on component (A) of 0.01 to 0.5% by mass It is.
  • R 1 to R 4 in the formula (1) are a hydrocarbon group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or an alkylthioethyl group having an alkenyl group, which may be the same or different.
  • X 1 to X 4 each independently represents sulfur or oxygen, and Y represents a metal element.
  • lubricating oil for internal combustion engines, automatic transmissions, and the like can be obtained with excellent oxidation stability that was not possible with conventional lubricating oils containing zinc dialkyldithiophosphate (ZDTP). It becomes possible to provide a lubricating oil composition suitably used as an oil.
  • ZDTP zinc dialkyldithiophosphate
  • the lubricating base oil used in the lubricating oil composition of the present invention examples include mineral base oil and / or synthetic base oil.
  • Mineral oil base oils include, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation, and solvent removal, solvent extraction, hydrocracking, hydroisomerization, solvent dewaxing, catalytic dewaxing.
  • Examples include paraffinic mineral oil, normal paraffinic base oil, and isoparaffinic base oil that are refined by combining one or more of the refining treatments such as wax, hydrorefining, sulfuric acid washing, and clay treatment alone. It is done.
  • the following base oils (1) to (7) and / or lubricating oil fractions recovered from the base oils (1) to (7) are obtained by a predetermined refining method.
  • recovering lubricating oil fractions can be mentioned.
  • Wax slack wax, etc.
  • synthetic wax Fischer-Tropsch wax, GTL wax, etc.
  • One or more mixed oils selected from base oils (1) to (2) and / or mild hydrocracked oils of the mixed oils Selected from base oils (1) to (3) Two or more kinds of mixed oils (5) Paraffinic crude oil and / or degassed oil (DAO) of vacuum distillation residual oil of atmospheric distillation residue of mixed base crude oil (6) Mild hydrocracking treatment oil (MHC) of base oil (5) (7) Two or more mixed oils selected from base oils (1) to (6).
  • DAO Paraffinic crude oil and / or degassed oil
  • MHC Mild hydrocracking treatment oil
  • 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 is preferable.
  • hydrorefining such as hydrocracking and hydrofinishing
  • solvent refining such as furfural solvent extraction
  • dewaxing such as solvent dewaxing and catalytic dewaxing
  • chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning is preferable.
  • one of these purification methods may be performed alone, or two or more may be combined.
  • the order in particular is not restrict
  • the base oil (8) shown below is particularly preferable.
  • the base oil selected from the above base oils (1) to (7) 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. Hydrocracked mineral oil obtained by performing dewaxing treatment such as solvent dewaxing or catalytic dewaxing on the lubricating oil fraction, or by performing distillation after the dewaxing treatment.
  • a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.
  • the sulfur content in the mineral oil base oil is not particularly limited, but from the viewpoint of further improving thermal and oxidation stability and reducing sulfur content, the sulfur content should be 100 mass ppm or less. Is preferably 50 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 5 ppm by mass or less.
  • the% C A of the mineral base oil is 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less, and most preferably 0. % If C A is more than 2, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.
  • a synthetic base oil may be used as the lubricating base oil according to the present invention.
  • Synthetic base oils include poly ⁇ -olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate , Di-2-ethylhexyl sebacate), polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyldiphenyl ether, Examples thereof include polyphenyl ether, and among them, poly
  • an ⁇ -olefin oligomer or co-oligomer (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms, and those Of the hydrides.
  • the viscosity index of the lubricating base oil according to the present invention is preferably 110 or more. More preferably, it is 120 or more, More preferably, it is 125 or more. Moreover, it is preferable that it is 160 or less.
  • the viscosity index is less than 110, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase and the wear prevention properties tend to decrease. .
  • the viscosity index exceeds 160, the low-temperature viscosity characteristics tend to deteriorate.
  • the viscosity index in the present invention means a viscosity index measured according to JIS K 2283-1993.
  • the kinematic viscosity at 100 ° C. of the lubricating base oil according to the present invention is preferably 20 mm 2 / s or less, more preferably 10 mm 2 / s or less, still more preferably 6 mm 2 / s or less, particularly preferably 5 mm 2 / s. s or less.
  • the 100 ° C. kinematic viscosity is preferably 1 mm 2 / s or more, more preferably 1.5 mm 2 / s or more, further preferably 2 mm 2 / s or more, and particularly preferably 2.5 mm 2. / S or more, most preferably 3 mm 2 / s or more.
  • kinematic viscosity at 100 ° C. refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445. If the 100 ° C. kinematic viscosity of the lubricating base oil component exceeds 20 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel economy, in the case of less than 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.
  • the lubricating base oil according to the present invention may be used alone, and the lubricating base oil according to the present invention may be one or more of other base oils. You may use together.
  • the ratio of the lubricating base oil according to the present invention in the mixed base oil is preferably 30% by mass or more. 50% by mass or more is more preferable, and 70% by mass or more is still more preferable.
  • kinematic viscosity in 100 degreeC exceeds 20 mm ⁇ 2 > / s, for example, 200 mm ⁇ 2 > / s or less solvent refined mineral oil, hydrocracked mineral oil, hydrorefined mineral oil, solvent dewaxed mineral oil and the like.
  • the synthetic base oil include synthetic base oils having a kinematic viscosity at 100 ° C. outside the range of 1 to 20 mm 2 / s.
  • the component (A) in the lubricating oil composition of the present invention is a metal salt of a phosphate ester represented by the general formula (1).
  • R 1 to R 4 in the general formula (1) are hydrocarbon groups having 1 to 30 carbon atoms or alkylthioethyl groups having an alkyl group or alkenyl group having 1 to 30 carbon atoms, which are the same or different. May be.
  • X 1 to X 4 represent sulfur or oxygen, and may be the same or different.
  • Y represents a metal element.
  • hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 4 include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, and an alkyl-substituted aryl group. And arylalkyl groups.
  • alkyl group examples include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups (these alkyl groups are linear or branched) May be).
  • Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, Examples thereof include alkylcycloalkyl groups having 6 to 11 carbon atoms such as dimethylcycloheptyl group, methylethylcycloheptyl group, and diethylcycloheptyl group (the substitution position
  • alkenyl group examples include, for example, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.
  • aryl groups such as a phenyl group and a naphthyl group
  • alkylaryl group examples include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl group.
  • alkylaryl groups having 7 to 18 carbon atoms such as undecylphenyl group and dodecylphenyl group (the alkyl group may be linear or branched, and the position of substitution with the aryl group is arbitrary). it can.
  • the arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group (these alkyl groups are linear Or may be branched).
  • the hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 4 is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 carbon atoms.
  • the metal represented by Y include alkali metals such as lithium, sodium, potassium and cesium, alkaline earth metals such as calcium, magnesium and barium, zinc, copper, iron, lead, nickel, silver, Examples include heavy metals such as manganese and molybdenum. Of these, alkaline earth metals such as zinc, molybdenum and calcium are preferred. In particular, zinc or molybdenum or a combination of zinc and molybdenum is preferable.
  • the coordination number of the phosphorus compound varies depending on the valence of the metal. For example, in divalent zinc and calcium, two phosphorus compounds coordinate to one metal atom. It is thought to form a complex.
  • the ratio of sulfur element (S / P molar ratio) based on phosphorus in the oil and the compound of the general formula (1) needs to be 0.05 or more. Preferably it is 0.07 or more, More preferably, it is 0.1 or more. On the other hand, it is 0.8 or less, preferably 0.7 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.
  • S / P molar ratio is less than 0.05, the sulfur content is insufficient, so that a sufficient antioxidant effect cannot be obtained.
  • the S / P molar ratio exceeds 0.8 the amount of sulfur is too large and the oxidation stability is deteriorated. Therefore, it is not preferable.
  • the formula (1) X 4 are all from X 1 is oxygen in the compound or (A) a phosphorus compound containing no sulfur other than the component It is necessary to use together.
  • a phosphorus compound represented by the general formula (2) As the phosphorus compound containing no sulfur other than the component (A) in the present invention, a phosphorus compound represented by the general formula (2), a phosphorus compound represented by the general formula (3), amine salts thereof, and these Examples thereof include at least one compound selected from the group consisting of derivatives.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • R 4 , R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • hydrocarbon group having 1 to 30 carbon atoms represented by R 1 to R 6 in the above formulas (2) and (3) include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkyl-substituted cycloalkyl. Groups, aryl groups, alkyl-substituted aryl groups, and arylalkyl groups.
  • Such a hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 4 carbon atoms. Is an alkyl group of ⁇ 12.
  • Examples of the phosphorus compound represented by the general formula (2) include phosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; and hydrocarbon having 1 to 30 carbon atoms. Mention may be made of phosphorous acid diesters having two groups; phosphorous acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof. In addition, phosphonic acid esters which are tautomers of phosphorous acid esters and phosphorous acid esters are also included in this compound.
  • Examples of the phosphorus compound represented by the general formula (3) include phosphoric acid; phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; and 2 hydrocarbon groups having 1 to 30 carbon atoms. And phosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof.
  • the content of the component (A) is 0.005% by mass or more, preferably 0.02% by mass or more, particularly preferably 0.8% by mass in terms of phosphorus element based on the total amount of the composition. It is 05 mass% or more. On the other hand, the content is 0.5% by mass or less, preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the content of the component (A) is less than 0.005% by mass as the phosphorus element, there is no effect on the wear resistance, and when it exceeds 0.5% by mass, it is added to the exhaust gas aftertreatment device with phosphorus. Since there are concerns about adverse effects, they are not preferable.
  • content of phosphorus is 0.005 mass% or more as phosphorus element conversion amount on the basis of a composition whole quantity, Preferably it is 0.02 mass%. As mentioned above, it is 0.05 mass% or more especially preferably. On the other hand, the content is 0.5% by mass or less, preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.
  • the amount of phosphorus is less than 0.005% by mass, there is no effect on the wear resistance, and when it exceeds 0.5% by mass, there is a concern about the adverse effect of phosphorus on the exhaust gas aftertreatment device. Absent.
  • the blending amount is 0.03 mass% or less in terms of Mo amount. Preferably it is 0.02 mass% or less, More preferably, it is 0.01 mass% or less. If it exceeds 0.03% by mass, the antioxidant effect is rather lowered, which is not preferable.
  • molybdenum dithiophosphate represented by the following general formula (4) can be used.
  • R 5 , R 6 , R 7 and R 8 may be the same or different and each have 2 to 30 carbon atoms, preferably 5 to 18 carbon atoms, more preferably 5 to 12 carbon atoms. Or a hydrocarbon group such as an aryl group having 6 to 18 carbon atoms (including an alkylaryl group).
  • Y 1 , Y 2 , Y 3 and Y 4 may be the same or different and each represents a sulfur atom or an oxygen atom.
  • alkyl group examples include, for example, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group.
  • (alkyl) aryl groups include phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, decylphenyl, Examples thereof include a decylphenyl group and a dodecylphenyl group, and the alkyl group may be a primary alkyl group, a secondary alkyl group, or a tertiary alkyl group, and may be linear or branched. Furthermore, these (alkyl) aryl groups include all substituted isomers having different substitution positions of alkyl groups on aryl groups.
  • molybdenum dithiophosphate examples include molybdenum diethyldithiophosphate, molybdenum dipropyldithiophosphate, molybdenum dibutyldithiophosphate, molybdenum dipentyldithiophosphate, molybdenum dihexyldithiophosphate, molybdenum dioctyldithiophosphate, molybdenum didecyl sulfide.
  • the lubricating oil composition of the present invention preferably contains an ashless antioxidant as the component (B).
  • the antioxidant can be used as long as it is generally used for lubricating oils such as ashless antioxidants such as phenolic antioxidants and amine antioxidants.
  • ashless antioxidants such as phenolic antioxidants and amine antioxidants.
  • the antioxidant properties of the lubricating oil composition according to the present invention can be further enhanced, and the lubricating oil composition of the present invention can suppress deposit formation, corrosion or corrosive wear of lead-containing metals. Prevention performance, base number maintenance property, etc. can be improved more.
  • phenolic antioxidants examples include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′.
  • amine antioxidants include aromatic amine antioxidants such as phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine, and dialkyldiphenylamine. You may use these in mixture of 2 or more types.
  • phenolic antioxidant and amine antioxidant may be blended in combination, but it is particularly preferable to use an aromatic amine antioxidant alone.
  • any additive generally used in lubricating oils can be contained depending on the purpose.
  • Such additives include, for example, viscosity index improvers, metal detergents, ashless dispersants, antiwear agents (or extreme pressure agents), corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators. And additives such as antifoaming agents.
  • alkali salts / basic salts such as alkali metal / alkaline earth metal salicylate, alkali metal / alkaline earth metal sulfonate, alkali metal / alkaline earth metal phenate, and alkali metal / alkaline earth metal salicylate Mention may be made of salts.
  • the 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. Of these, metal salicylate detergents are preferred from the standpoint of antioxidant properties and friction reduction.
  • the metal salicylate detergent is a neutral salicylic acid metal salt obtained by allowing an equivalent metal salt or metal base to act on salicylic acid having one hydrocarbon group having 8 to 30 carbon atoms, and further, the neutral salicylic acid metal.
  • a basic salt obtained by heating an excess metal salt or metal base (metal hydroxide or oxide) in the presence of water, carbon dioxide gas or boron in the presence of the neutral salicylic acid metal salt.
  • overbased salts superbasic salts obtained by reacting an acid or borate with a base such as a metal hydroxide.
  • Examples of the metal in the metal salt or metal base of salicylate include alkali metals such as sodium and potassium, alkaline earth metals such as calcium, magnesium and barium, and the like. It is preferably an earth metal, particularly calcium.
  • a salicylic acid metal salt having a hydrocarbon group having 8 to 19 carbon atoms eg, an alkyl group having 8 to 19 carbon atoms
  • salicylic acid metal salt Ca a salicylic acid metal salt having a hydrocarbon group having 20 to 30 carbon atoms (for example, an alkyl group having 20 to 30 carbon atoms)
  • salicylic acid metal salt Cb a salicylic acid metal salt having a hydrocarbon group having 20 to 30 carbon atoms alone.
  • the salicylic acid metal salt Cb is preferable from the viewpoint of friction reduction.
  • salicylic acid metal salt Ca and salicylic acid metal salt Cb in combination.
  • the base number of the metal salicylate detergent is preferably adjusted to a lower limit of preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, still more preferably 150 mgKOH / g or more, particularly preferably 200 mgKOH / g or more. It is desirable to use a basic salicylate detergent as the main component.
  • the upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, more preferably 250 mgKOH / g or less, and more preferably an overbased salicylate-based detergent used as a main component.
  • the base number referred to here is JIS K2501 "Petroleum products and lubricants-Neutralization number test method". Means the base number measured by the perchloric acid method according to the above.
  • the metal ratio of the metal salicylate detergent is not particularly limited, and usually 20 or less can be used alone or in combination.
  • the metal ratio is preferably less than 4.5, more preferably 3 or less.
  • the metal ratio referred to here is expressed by (valence of metal element in salicylate detergent) ⁇ (metal element content (mol%)) / (soap group content (mol%)).
  • the term “soap group” means a salicylic acid group such as calcium and magnesium.
  • the lower limit is preferably 0.1% by mass or more, more preferably 0.5%, based on the total amount of the lubricating oil composition. It is at least 1% by mass, more preferably at least 1% by mass. Moreover, as an upper limit, Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 6 mass% or less, Most preferably, it is 4 mass% or less. If the content is less than 0.1% by mass, the friction reduction effect may last only for a short period, and if it exceeds 15% by mass, the effect commensurate with the content may not be obtained. is there.
  • the lower limit of the amount of metal is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more. is there.
  • the upper limit Preferably it is 1.5 mass% or less, More preferably, it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less, Most preferably, it is 0.3 mass% or less. If the amount of metal is less than 0.01% by mass, the friction reduction effect may last only for a short period of time, and if it exceeds 1.5% by mass, an effect commensurate with the content cannot be obtained. There is a fear.
  • the lubricating oil composition of the present invention preferably contains an ashless dispersant.
  • the ashless dispersant include nitrogen-containing compounds having at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms or derivatives thereof, or modified products of alkenyl succinimide. It is done. One type or two or more types arbitrarily selected from these can be blended.
  • the carbon number of the alkyl group or alkenyl group of the ashless dispersant is preferably 40 to 400, more preferably 60 to 350.
  • the carbon number of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil tends to be reduced.
  • the carbon number of the alkyl group or alkenyl group exceeds 400, the lubricating oil composition The low-temperature fluidity of the product tends to deteriorate.
  • the alkyl group or alkenyl group may be linear or branched, but specific examples thereof are derived from olefin oligomers such as propylene, 1-butene and isobutylene, and ethylene and propylene co-oligomers. And a branched alkyl group and a branched alkenyl group.
  • the succinimide includes a so-called mono-type succinimide having succinic anhydride added to one end of the polyamine and a so-called bis-type succinimide having succinic anhydride added to both ends of the polyamine. .
  • the lubricating oil composition of the present invention may contain either monotype or bistype succinimide, or may contain both.
  • benzylamine can also be used as an ashless dispersant.
  • preferable benzylamine include compounds represented by the following general formula (5).
  • R 12 represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350 carbon atoms, and r is 1 to 5, preferably 2 to 4 Indicates an integer.
  • polyamine as the ashless dispersant examples include compounds represented by the following general formula (6).
  • R 13 represents an alkyl or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl or alkenyl group having 60 to 350, and s is an integer of 1 to 5, preferably 2 to 4. Indicates.
  • the above-mentioned nitrogen-containing compounds may contain 1 to 30 carbon atoms such as monocarboxylic acids (fatty acids, etc.), oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid, etc.
  • Oxygenated compounds such as 2 to 30 polycarboxylic acids and hydroxy (poly) alkylene carbonates are allowed to act to neutralize some or all of the remaining amino groups and / or imino groups, and amidated organic acids, etc.
  • a sulfur-modified compound obtained by allowing a sulfur compound to act on the aforementioned nitrogen-containing compound.
  • denatured with the boron compound is also mentioned.
  • the boronated ashless dispersant is a borated ashless dispersant used in lubricating oils. Boronation is generally performed by allowing boric acid to act on the aforementioned nitrogen-containing compound to neutralize part or all of the remaining amino group and / or imino group.
  • boric acid-modified succinimide methods for producing boric acid-modified succinimide are disclosed in JP-B-42-8013 and JP-A-42-8014, JP-A-51-52381, JP-A-51-130408, and the like.
  • organic compounds such as alcohols, hexane and xylene, light lubricating base oils, polyamines and polyalkenyl succinic acid (anhydrides), boric acid, boric acid esters, or boron compounds such as borates.
  • the boric acid content of the boric acid succinimide thus obtained can usually be 0.1 to 4.0% by mass.
  • a boric acid-modified compound (boron-containing succinimide) of alkenyl succinimide is excellent in heat resistance, oxidation resistance and wear resistance.
  • the content of the ashless dispersant is preferably 0.01 to 20% by mass, more preferably 0.1%, based on the total amount of the lubricating oil composition. ⁇ 10% by mass.
  • the content of the ashless dispersant is less than 0.01% by mass, the effect of improving the friction reduction property may be insufficient.
  • the content exceeds 20% by mass, the low-temperature fluidity of the lubricating oil composition is low. There is a risk of significant deterioration.
  • the boron content is not particularly limited and is usually 0.1 to 3% by mass.
  • the boron content is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.025% by mass, based on the total amount of the composition. Further, it is 0.15% by mass or less, preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less.
  • the boron / nitrogen mass ratio (B / N ratio) is not particularly limited and is usually 0.05 to 5, but As one aspect, the B / N ratio is preferably 0.1 or more, more preferably 0.2 or more, and preferably 1 or less, more preferably 0.7 or less, and further preferably 0.5 or less. It is desirable to use boron-containing ashless dispersants, preferably boron-containing succinimides, especially boron-containing bissuccinimides.
  • the boron content is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.025% by mass, based on the total amount of the composition. Further, it is 0.15% by mass or less, preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less.
  • the B / N ratio is 0.1 or more, preferably 0.2.
  • a boron-containing ashless dispersant preferably less than 0.5, more preferably 0.4 or less, preferably boron-containing succinimide, particularly boron-containing bissuccinimide.
  • B / N ratio exceeds 1, not only there is a concern about stability, but the amount of boron in the composition becomes too large, and there is a concern about the influence on the exhaust gas aftertreatment device as the sulfated ash content increases. Therefore, it is not preferable.
  • the B / N ratio is less than 0.1, the effect of improving the friction reduction performance is small, and it is desirable to use another boron compound in combination.
  • the viscosity index improver 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 improver, non-dispersed or dispersed Type olefin- (meth) acrylate copolymer system viscosity index improver, styrene-maleic anhydride copolymer system viscosity index improver, and mixtures thereof.
  • non-dispersed or dispersed poly (meth) An acrylate viscosity index improver is preferred.
  • a non-dispersed or dispersed polymethacrylate viscosity index improver is particularly preferable.
  • 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. Can be mentioned.
  • any antiwear agent / extreme pressure agent used in lubricating oils can be used.
  • sulfur-based, phosphorus-based, sulfur-phosphorus-based extreme pressure agents and the like can be used.
  • the phosphorus content in the oil is 0.01 to 0.5% by mass, and the molar ratio of phosphorus to sulfur derived from the component (A) is 0.05 to 0.8%. Is allowed within a range that satisfies the above.
  • corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, or 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 deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
  • metal deactivator examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and ⁇ - (o-carboxybenzylthio) propiononitrile.
  • antifoaming agents examples include silicone oils having a kinematic viscosity of 1000 to 100,000 mm 2 / s at 25 ° C., alkenyl succinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, methyl salicylates and o- Examples thereof include hydroxybenzyl alcohol.
  • the content of the antifoaming agent is 0.0001 to 0.01% by mass, and the other additives are 0.00% based on the total amount of the lubricating oil composition.
  • the content is preferably from 01 to 10% by mass.
  • Examples 1 to 4 A lubricating oil composition of the present invention (Examples 1 to 4) and a comparative lubricating oil composition (Comparative Examples 1 to 5) were prepared, respectively, and subjected to an engine test (high temperature oxidation stability test) based on JASO M333-93. And evaluated. The results are shown in Table 1.
  • the lubricating oil composition of the present invention is suitably used as a lubricating oil for internal combustion engines, automatic transmissions and the like.

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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

La présente invention concerne une composition d'huile lubrifiante ayant une excellente stabilité à l'oxydation, la composition étant adaptée en tant qu'huile lubrifiante pour un moteur à combustion interne, une transmission automatique, ou similaire, et en particulier en tant qu'huile lubrifiante pour moteur à combustion interne, dans laquelle une huile de base d'huile lubrifiante contient un ou plusieurs types de composé phosphoreux représenté par la formule générale (1) en tant que composant (A), le rapport (molaire) de soufre élémentaire, sur la base du composé de formule générale (1), et le phosphore élémentaire dans l'huile étant de 0,05 à 0,8 et la teneur en phosphore dans l'huile, sur la base du composant (A), étant de 0,01 à 0,5 % en masse. (Dans la formule (1), R1 à R4 sont un groupe hydrocarboné en C1-30, un groupe alkyle en C1-30, ou un groupe alkylthioéthyle ayant un groupe alcényle, et peuvent être identiques ou différents. X1 à X4 représentent indépendamment chacun du soufre ou de l'oxygène, et Y représente un élément métallique.)
PCT/JP2012/051220 2011-06-21 2012-01-20 Composition d'huile lubrifiante WO2012176484A1 (fr)

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US14/124,333 US20140113845A1 (en) 2011-06-21 2012-01-20 Lubricating oil composition
CN201280030596.9A CN103620006B (zh) 2011-06-21 2012-01-20 润滑油组合物
EP12802100.3A EP2725088A4 (fr) 2011-06-21 2012-01-20 Composition d'huile lubrifiante

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JP2013001884A (ja) 2013-01-07
EP2725088A4 (fr) 2015-05-06
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