EP3127993A1 - Composition d'huile de graissage pour un moteur à combustion interne - Google Patents

Composition d'huile de graissage pour un moteur à combustion interne Download PDF

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Publication number
EP3127993A1
EP3127993A1 EP15774018.4A EP15774018A EP3127993A1 EP 3127993 A1 EP3127993 A1 EP 3127993A1 EP 15774018 A EP15774018 A EP 15774018A EP 3127993 A1 EP3127993 A1 EP 3127993A1
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EP
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Prior art keywords
mass
composition
lubricating oil
meth
group
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Granted
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EP15774018.4A
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German (de)
English (en)
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EP3127993B1 (fr
EP3127993A4 (fr
Inventor
Toshimasa Utaka
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M141/06—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 nitrogen-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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—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
    • C10M145/12—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 monocarboxylic
    • C10M145/14—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
    • 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
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
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    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—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
    • 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
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • 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
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    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • 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
    • 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
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    • 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
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to a lubricating oil composition for an internal combustion engine.
  • an engine oil is desired to have an improved performance from various viewpoints.
  • it is desired to prevent coking that may be caused by carbonization of an engine oil, and to prevent copper release from engine parts.
  • PTL 1 discloses use of a hydrazide derivative having a specific structure as an additive for preventing copper release.
  • PTL 2 discloses combined use of a specific molybdenum-type additive and a sulfurized fatty acid ester for preventing coking.
  • formulations disclosed in PTLs 1 and 2 are techniques for separately and individually preventing coking and copper release, and therefore, it is difficult to effectively prevent both coking and copper release while base number reduction is prevented.
  • the present invention has been made in consideration of the above-mentioned problems, and an object of the present invention is to provide a lubricating oil composition for an internal combustion engine capable of preventing base number reduction, coking occurrence and copper release in a well-balanced manner.
  • the present inventors have assiduously studied and, as a result, have found that combined use of a boron-containing succinimide and a poly(meth)acrylate where the ratio of the weight-average molecular weight (Mw) of the polymer to the mean carbon number of the alkyl groups in the side chains is specifically defined can solve the above-mentioned problems, and have completed the present invention.
  • the present invention provides the following (1) to (9).
  • a lubricating oil composition for an internal combustion engine capable of preventing base number reduction, coking occurrence and copper release in a well-balanced manner.
  • the lubricating oil composition for an internal combustion engine (hereinafter this may be simply referred to as “lubricating oil composition”) of the present invention contains (A) a lubricant base oil, (B) a boron-containing alkenylsuccinimide and/or a boron-containing alkylsuccinimide (hereinafter these may be simply referred to as "boron-containing succinimide”), and (C) a poly(meth)acrylate.
  • a lubricant base oil (B) a boron-containing alkenylsuccinimide and/or a boron-containing alkylsuccinimide (hereinafter these may be simply referred to as "boron-containing succinimide”), and (C) a poly(meth)acrylate.
  • boron-containing succinimide boron-containing succinimide
  • the lubricant base oil (A) in the present composition is of a mineral oil and/or a synthetic oil, for which any one suitably selected from mineral oils and synthetic oils heretofore used as a base oil for lubricating oil can be used.
  • Examples of the mineral oil include a mineral oil refined by subjecting a lubricating oil distillate that is obtained by distilling under a reduced pressure the atmospheric residue given by atmospheric distillation of crude oil, to one or more treatments selected from solvent deasphalting, solvent extraction, hydro-cracking, solvent dewaxing, catalytic dewaxing, hydrorefining and the like, a lubricant base oil produced by isomerization of wax or GTL WAX, and the like.
  • a mineral oil treated by hydrorefining is preferred.
  • the mineral oil treated by hydrorefining can readily better the %C P and the viscosity index to be mentioned below.
  • Examples of the synthetic oil include polybutene, poly-alpha-olefins such as ⁇ -olefin homopolymers and copolymers (e.g., ethylene- ⁇ -olefin copolymers), etc., various kinds of esters, for example, polyol esters, dibasic acid esters, phosphate esters, etc., various kinds of ethers, for example, polyphenyl ethers, etc., polyglycols, alkylbenzenes, alkylnaphthalenes, a lubricant base oil produced through isomerization of GTL WAX.
  • poly-alpha-olefins and esters are particularly preferred and the combination of two kinds of these is also preferably used for the synthetic oil.
  • the above mineral oils may be used alone or in combination of two or more thereof.
  • the above synthetic oils may be used alone or in combination of two or more thereof.
  • one or more of the mineral oils and one or more of the synthetic oils may be used in combination thereof.
  • the lubricant base oil (A) is to be a main component, and is contained, relative to the total amount of the lubricating oil composition, generally in an amount of 50% by mass or more, preferably 60 to 97% by mass, more preferably 65 to 95% by mass.
  • the viscosity of the lubricant base oil (A) is not specifically limited.
  • the kinematic viscosity thereof at 100°C is within a range of 1.0 to 20 mm 2 /s, more preferably within 1.5 to 15 mm 2 /s, even more preferably within 2.0 to 13 mm 2 /s.
  • the kinematic viscosity of the lubricant base oil (A) is a relatively low viscosity as mentioned above, the energy-saving performance can be readily realized.
  • the kinematic viscosity is measured according to the method described in the section of Examples to be given hereinunder.
  • the viscosity index of the lubricant base oil (A) is preferably 90 or more, more preferably 95 or more, even more preferably 100 or more.
  • the upper limit of the viscosity index of the lubricant base oil is not specifically limited, but is preferably 170 or less, more preferably 160 or less, even more preferably 150 or less.
  • the viscosity index of the lubricant base oil falls within the above range, the viscosity characteristics of the lubricating oil composition can be readily bettered.
  • the viscosity index is measured according to the method described in the section of Examples to be given hereinunder.
  • the paraffin content according to ring analysis (%C P ) of the mineral oil is preferably 60% or more, more preferably 65% or more.
  • the paraffin content is 60% or more, the oxidation stability of the base oil can be bettered and base number reduction and coking occurrence in the lubricating oil composition can be thereby prevented.
  • Measurement of the paraffin content (%C P ) will be described hereinunder.
  • the boron-containing succinimide (B) for use in the present invention includes an alkenyl or alkylsuccinic monoimide boride, and an alkenyl or alkyl succinic bisimide boride.
  • the example of alkenyl or alkylsuccinic monoimide includes compounds represented by the following general formula (1).
  • the example of alkenyl or alkylsuccinic bisimide includes, compounds represented by the following general formula (2).
  • the good detergency of the composition is exhibited by blending the component (B).
  • combined use with the component (C) can prevent coking occurrence and copper release.
  • R 1 , R 3 and R 4 each represent an alkenyl group or an alkyl group, and the weight-average molecular weight of the group is preferably 500 to 3,000, more preferably 1,000 to 3,000, respectively.
  • R 3 and R 4 When the weight-average molecular weight of R 1 , R 3 and R 4 is 500 or more, the solubility in the base oil is high and when it is 3,000 or less, the effect to be given by the compound is expected to be suitably exhibited.
  • R 3 and R 4 may be the same or different.
  • R 2 , R 5 and R 6 each represent an alkylene group having 2 to 5 carbon atoms, and R 5 and R 6 may be the same or different.
  • m indicates an integer of 1 to 10
  • n indicates 0 or an integer of 1 to 10.
  • m is preferably 2 to 5, more preferably 3 to 4.
  • m is 2 or more, the effect to be given by the compound is expected to be suitably exhibited.
  • m is 5 or less, the solubility in the base oil can be further bettered.
  • n is preferably 1 to 4, more preferably 2 to 3.
  • n is 1 or more, the effect to be given by the compound is expected to be suitably exhibited.
  • n is 4 or less, the solubility in the base oil can be further bettered.
  • the alkenyl group includes, for example, a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer.
  • the alkyl group includes ones derived from hydrogenation of those groups.
  • a preferred alkenyl group there is mentioned a polybutenyl group or a polyisobutenyl group.
  • a polybutenyl group a polymerized product of a mixture of 1-butene and isobutene or high-purity isobutene is favorably used.
  • Representative examples of a preferred alkyl group include those prepared though hydrogenation of a polybutenyl group or a polyisobutenyl group.
  • the boron-containing succinimide (B) may be produced according to a conventionally-known method. For example, a polyolefin is reacted with a maleic anhydride to give an alkenylsuccinic anhydride, and this is further reacted with an intermediate prepared through reaction of a polyamine with a boron compound such as a boron oxide, a boron halide, a boric acid, a boric anhydride, a borate ester, an ammonium borate or the like and is imidated.
  • the monoimide or the bisimide may be produced by varying the ratio of the alkenylsuccinic anhydride or the alkylsuccinic anhydride to the polyamine.
  • the boron-containing succinimide (B) may be obtained by treating a boron-free alkenyl or alkylsuccinic monoimide or alkenyl or alkylsuccinic bisimide with the above-mentioned boron compound.
  • olefin monomer to form the above polyolefin usable is/are one alone or two or more of ⁇ -olefins having 2 to 8 carbon atoms, either singly or as combined. Preferred is use of a mixture of isobutene and 1-butene.
  • the polyamine includes a simple diamine such as ethylenediamine, propylenediamine, butylenediamine, and pentylenediamine; a polyalkylenepolyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, and pentapentylenehexamine; a piperazine derivative such as aminoethylpiperazine.
  • a simple diamine such as ethylenediamine, propylenediamine, butylenediamine, and pentylenediamine
  • a polyalkylenepolyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, and pentapentylenehexamine
  • a piperazine derivative such
  • the above component (B) is contained in an amount of 0.001 to 0.1% by mass as a boron-equivalent amount based on the total amount of the composition.
  • the content of the component (B) is, as a boron-equivalent amount based on the total amount of the composition, more preferably 0.005 to 0.08% by mass, even more preferably 0.010 to 0.06% by mass.
  • the ratio by mass of boron to nitrogen (B/N ratio) in the component (B) is preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.1 or more.
  • the upper limit of the B/N ratio is not specifically limited, the B/N ratio is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.3 or less.
  • the content of the component (B) may be such that the boron-equivalent content thereof falls within the above range, and is generally 0.1 to 10% by mass or so based on the total amount of the composition, preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass.
  • the poly(meth)acrylate (C) to be contained in the lubricating oil composition of the present invention has Mw of 100,000 to 700,000 and Mw/X of 30,000 or more, in which the weight-average molecular weight thereof is represented by Mw and the mean carbon number of the alkyl groups therein, as measured through 13 C-NMR, is represented by X.
  • the alkyl group means all the alkyl groups existing in the poly(meth)acrylate, and for example, in the general formula (3) to be mentioned below, it means R 7 and R 8 . In the case where an alkyl group bonds to COO- of the (meth)acrylate via any other substituent, such an alkyl group is also included.
  • the mean carbon number means an arithmetic mean value.
  • the component (C) is contained in addition to the above-mentioned component (B) and therefore the lubricating oil composition can be protected from copper release and coking occurrence in a well-balanced manner.
  • the principle could be presumed as follows. It is presumed that a part of poly(meth)acrylate (hereinafter this may also be referred to as "PMA”) may form a complex with copper through decomposition or the like, to thereby often cause copper release from alloys of members such as engine bearing parts, etc. When PMA has a structure capable of being entangled with each other, the amount of PMA to adhere to the metal surface of an engine and, as a result, copper release can be thereby prevented.
  • PMA poly(meth)acrylate
  • the balance between Mw and the size of the alkyl groups in the side chains of PMA is important. It is presumed that, when a large number of small alkyl groups exist in the side chains, PMA may be readily entangled even though Mw is relatively low, while on the other hand, in the case where large alkyl groups exist in the side chains in a predetermined ratio or more, PMA could hardly be entangled even though Mw is relatively high. Further, in the case where large alkyl groups exist in the side chains in a predetermined ratio or more and where Mw is relatively high, it is presumed that PMA could also be hardly entangled but PMA would readily decompose. Accordingly, when Mw/X is less than 30,000, adhesion of PMA to the metal surface of an engine could not be fully reduced but rather PMA decomposition may readily occur and, as a result, copper release and coking occurrence could hardly be prevented.
  • the reactivity of PMA could be small even though alkyl groups having certain size exist in the side chains in large numbers, but when Mw is more than 700,000, it is presumed that the reactivity of PMA increases even though a large number of small alkyl groups exist in the side chains, therefore easily causing coking and copper release.
  • the molecular weight is less than 100,000, it is presumed that the polymer would be hardly entangled even though many small alkyl groups exist in the side chains and copper release could not be prevented sufficiently.
  • Mw/X is preferably 30,000 to 200,000, more preferably 30,000 to 130,000; and from the viewpoint of more suitably preventing copper release, the ratio is still more preferably 30,000 to 100,000.
  • the weight-average molecular weight (Mw) is preferably 100,000 to 700,000, more preferably 150,000 to 600,000, even more preferably 180,000 to 550,000.
  • the poly(meth)acrylate (C) is preferably a polymer of polymerizable monomers that include a (meth)acrylate monomer represented by the following general formula (3).
  • R 7 represents a hydrogen atom or a methyl group
  • R 8 represents a linear or branched alkyl group having 1 to 200 carbon atoms.
  • R 8 is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 28 carbon atoms, even more preferably an alkyl group having 1 to 25 carbon atoms.
  • examples of R 8 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group,
  • the component (C) is preferably a non-dispersive one.
  • the non-dispersive poly(meth)acrylate specifically, there is mentioned a homopolymer of one kind of a monomer represented by the general formula (3), or a (poly)methacrylate obtained through copolymerization of two or more kinds of the monomer.
  • the poly(meth)acrylate (C) may also be a dispersive poly(meth)acrylate.
  • the dispersive poly(meth)acrylate there is mentioned those produced through copolymerization of a monomer represented by the general formula (3) and one or more kinds of monomers selected from the following general formulae (4) and (5).
  • R 9 represents a hydrogen atom or a methyl group
  • R 10 represents an alkylene group having 1 to 28 carbon atoms
  • E 1 represents an amine residue or a heterocyclic residue having 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms
  • a is 0 or 1.
  • R 11 represents a hydrogen atom or a methyl group
  • E 2 represents an amine residue or a heterocyclic residue having 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms.
  • examples of the group represented by E 1 and E 2 include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, a pyrrolino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinolyl group, a pyrrolidonyl group, a pyrrolidono group, an imidazolino group, a pyrazino group, etc.
  • preferred examples of the monomer represented by the general formulae (4) and (5) include dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, N-vinylpyrrolidone and their mixtures, etc.
  • the copolymerization molar ratio in the copolymer of the monomer (M1) represented by the general formula (3) and the monomer (M2) represented by the general formulae (4) and/or (5) is not specifically limited.
  • M1/M2 molar ratio is 99/1 to 80/20 or so, more preferably 98/2 to 85/15, even more preferably 95/5 to 90/10.
  • the monomer represented by the general formula (3) preferably accounts for 70% by mass or more in all monomers constituting the component (C), more preferably 85% by mass or more, even more preferably 90% by mass or more.
  • the component (C) may contain a constituting unit derived from a monomer except those of the above general formulae (3) to (5) within a range not contradictory to the object of the present invention.
  • the monomer component of this type accounts for 10% by mass or less of all monomers.
  • the above component (C) includes those produced through copolymerization of at least an alkyl (meth)acrylate monomer where the carbon number of the alkyl group is 1 to 4, and an alkyl (meth)acrylate monomer where the carbon number of the alkyl group is 12 to 40, or those produced through copolymerization of at least an alkyl (meth)acrylate monomer where the carbon number of the alkyl group is 1 to 4, an alkyl (meth)acrylate monomer where the carbon number of the alkyl group is 5 to 11, and an alkyl (meth)acrylate monomer where the carbon number of the alkyl group is 12 to 40.
  • the content of the poly(meth)acrylate (C) is 0.1 to 30% by mass based on the total amount of the composition. When the content is less than 0.1% by mass, it would be difficult to prevent base number reduction, coking occurrence and copper release in a well-balanced manner. When it is more than 30% by mass, the effect balanced with the content could hardly be exhibited.
  • the content of the above component (C) is preferably 0.3 to 25% by mass, more preferably 0.5 to 10% by mass.
  • the content of the component (C) means the content of the resin fraction in the component.
  • the lubricating oil composition of the present invention may contain (D) a zinc dithiophosphate.
  • D a zinc dithiophosphate
  • the incorporation of a zinc dithiophosphate (D) betters wear-resistant properties and oxidation stability.
  • As the zinc dithiophosphate there are mentioned compounds represented by the following general formula (6).
  • R 12 , R 13 , R 14 and R 15 each independently represent a hydrocarbon group having 1 to 24 carbon atoms.
  • the hydrocarbon group is any of a linear or branched alkyl group having 2 to 24 carbon atoms, a linear or branched alkenyl group having 3 to 24 carbon atoms, a cycloalkyl group or a linear or branched alkylcycloalkyl group having 5 to 13 carbon atoms, an aryl group or a linear or branched alkylaryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 19 carbon atoms.
  • an alkyl group is preferred.
  • the zinc dithiophosphate is preferably a zinc dialkyldithiophosphate, and more preferably a zinc secondary dialkyldithiophosphate.
  • the content of the zinc dithiophosphate is preferably 0.005 to 0.30% by mass as a phosphorus-equivalent amount relative to the total amount of the composition, more preferably 0.01 to 0.15% by mass. Falling within the above range, the wear-resistant properties and the oxidation stability of the lubricating oil composition can be bettered without having influences on the detergency and the coking resistance.
  • the lubricating oil composition may further contain (E) a metallic detergent selected from an alkali metal detergent or an alkaline earth metal detergent.
  • a metallic detergent selected from an alkali metal detergent or an alkaline earth metal detergent.
  • one or more metallic detergents selected from an alkali metal sulfonate or an alkaline earth metal sulfonate, an alkali metal phenate or an alkaline earth metal phenate, an alkali metal salicylate or an alkaline earth metal salicylate, and so on.
  • the alkali metal includes sodium and potassium
  • the alkaline earth metal includes magnesium and calcium.
  • Sodium as the alkali metal, and magnesium and calcium as the alkaline earth metals are preferably used, and calcium is more preferred.
  • the alkali metal detergent or the alkaline earth metal detergent may be neutral, basic or overbased, and basic or overbased ones are preferred.
  • those having a total base number of 10 to 500 mgKOH/g are used, and those having a total base number of 150 to 450 mgKOH/g are more preferred.
  • the total base number is measured according to a perchloric acid method of JIS K-2501.
  • the metallic detergent (E) for example, one having a total base number of 150 to 450 mgKOH/g may be used singly, or an alkali metal detergent or an alkaline earth metal detergent having a total base number of 150 to 450 mgKOH/g and an alkali metal detergent or an alkaline earth metal detergent having a total base number of 5 to 100 mgKOH/g may be used as combined.
  • the content of the metallic detergent (E) is preferably 0.05 to 0.5% by mass as a metal-equivalent amount relative to the total amount of the composition, more preferably 0.1 to 0.3% by mass.
  • the incorporation of the component in an amount not lower than the lower limit can more readily prevent base number reduction, coking occurrence and copper release.
  • the incorporation of the component in an amount not higher than the upper limit makes it possible to exhibit the effect comparable to the content thereof.
  • the lubricating oil composition contains the zinc dithiophosphate (D) in an amount of 0.01 to 0.15% by mass as a phosphorus-equivalent amount and the metallic detergent (E) in an amount of 0.1 to 0.3% by mass as a metal-equivalent amount, based on the total amount of the composition.
  • the lubricating oil composition may contain a boron-free succinimide in addition to the boron-containing succinimide (B).
  • the boron-free succinimide is an alkenylsuccinimide and/or an alkylsuccinimide not containing boron.
  • alkenylsuccinimide and/or the alkylsuccinimide there are mentioned the above-mentioned alkenyl or alkylsuccinic monoimide and alkenyl or alkylsuccinic bisimide.
  • the amount of the boron-free succinimide is not specifically defined, but is generally 0.1 to 10% by mass or so based on the total amount of the composition, more preferably 0.5 to 5% by mass or so.
  • the lubricating oil composition may further contain an antioxidant.
  • the antioxidant includes an amine-type antioxidant, a phenolic antioxidant, a sulfur-type antioxidant, a phosphorus-type antioxidant, a molybdenum amine complex-type antioxidant, and so on.
  • an amine-type antioxidant and a phenolic antioxidant are preferred.
  • any one or more may be suitably selected from known antioxidants that are heretofore used as an antioxidant for a lubricating oil.
  • amine-type antioxidant examples include diphenylamine-type ones such as diphenylamine, a dialkyldiphenylamine where the alkyl group has 3 to 20 carbon atoms, naphthylamine-type ones such as ⁇ -naphthylamine, an alkyl-substituted phenyl- ⁇ -naphthylamine where the alkyl group has 3 to 20 carbon atoms, etc.
  • phenolic antioxidant examples include monophenol-type ones such as 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.; diphenol-type ones such as 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), etc.
  • monophenol-type ones such as 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.
  • diphenol-type ones such as 4,4'-methylenebis(2,6-di-tert-buty
  • the sulfur-type antioxidant includes dilauryl-3,3'-thiodipropionate, etc.; the phosphorus-type antioxidant includes phosphites, etc.
  • the molybdenum amine complex-type antioxidant includes 6-valent molybdenum compounds, specifically those produced through reaction of molybdenum trioxide and/or molybdic acid and an amine compound, for example, compounds obtained according to the production method described in JP 2003-252887A .
  • antioxidants may be used either singly or as combined, but in general, two or more kinds are preferably used as combined.
  • the content of the antioxidant is preferably 0.01 to 10% by mass or so based on the total amount of the composition, more preferably 0.1 to 5% by mass or so.
  • the lubricating oil composition may contain at least one additive selected from any other friction modifier and anti-wear agent than those mentioned hereinabove.
  • sulfur-type compounds such as sulfurized olefins, dialkyl polysulfides, diarylalkyl polysulfides, diaryl polysulfides, etc.
  • phosphorus-type compounds such as phosphates, thiophosphates, phosphites, alkylhydrogen phosphites, phosphate amine salts, phosphite amine salts, etc.
  • organic metallic compounds such as zinc dithiocarbamate (ZnDTC), sulfurized oxymolybdenum organophosphorodithioate (MoDTP), sulfurized oxymolybdenum dithiocarbamate (MoDTC), etc.
  • ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic ethers, urea compounds, hydrazide compounds, etc.
  • ashless friction modifiers such as amine compounds, fatty acid esters, fatty acid
  • the content of these friction modifier and anti-wear agent is preferably 0.01 to 8% by mass or so based on the total amount of the composition, more preferably 0.1 to 5% by mass.
  • the lubricating oil composition may further contain other component such as a pour point depressant, a metal deactivator, a pour point depressant, a defoaming agent, etc.
  • the kinematic viscosity at 100°C of the lubricant oil composition of the present invention is not specifically limited, and is generally 2 to 25 mm 2 /s or so, preferably 3 to 22 mm 2 /s, more preferably 4 to 17 mm 2 /s. Having such a low viscosity, the composition can readily realize fuel-saving performance.
  • the viscosity index of the lubricating oil composition is preferably 150 or more, more preferably 170 to 300 or so, even more preferably 180 to 250 or so.
  • the lubricating oil composition of the present invention is a lubricating oil composition for an internal combustion engine, which is used in various kinds of internal combustion engines such as those in four-wheeled vehicles, two-wheeled vehicles, etc.
  • a lubricating oil composition used in the internal combustion engine has been often troubled by problems of coking and copper release, but the lubricating oil composition of the present invention can prevent coking and copper release in a well-balanced manner.
  • a lubricating oil composition is produced by blending the above-mentioned components (B) and (C) into the lubricant base oil (A).
  • the above-mentioned components (D), (E) and/or any other components than the components (B) and (C) may be blended into the lubricant base oil.
  • the amount of the lubricant base oil (A) and the amounts (namely, the blending amounts) of the above-mentioned components (B) to (E) and other components are the same as the content of each component mentioned above, and the properties of the lubricating oil composition and the details of the constituent components are also the same as those mentioned above, and therefore describing them is omitted here.
  • the components may be blended into the base oil in any mode and the means for the addition is not limited.
  • the lubricating oil composition produced by blending the components (B) and (C) and optionally by further blending the components (D) and (E) and any other component than these, generally contains these components that are blended thereto, but as the case may be, at least a part of the blended additives may be converted into any other compound through reaction or the like.
  • the weight-average molecular weight (Mw) is measured under the following conditions, and is a value obtained based on a calibration curve of polystyrene. Precisely, the value is measured under the following conditions.
  • each oil composition is tested under a condition at a panel temperature of 300°C and an oil temperature of 100°C, and in a cycle of a splash time of 15 seconds and a cessation time of 45 seconds, for 3 hours. After the test, the coked substance adhering to the panel is evaluated.
  • the lubricant base oil was a mixture of the lubricant base oil (A3) and the lubricant base oil (A4), and the kinematic viscosity at 100°C of the mixed base oil was 4.3 mm 2 /s and the viscosity index thereof was 130.
  • B1 Boron-containing succinimide (B1); polybutenylsuccinimide boride, boron content 1.3% by mass, nitrogen content 1.2% by mass, weight-average molecular weight of polybutenyl group 1,800, B/N ratio 1.1
  • ZnDTP (D1) zinc dialkyldithiophosphate, zinc content 9.0% by mass, phosphorus content 8.2% by mass, sulfur content 17.1% by mass, alkyl group: mix of secondary butyl group and secondary hexyl group
  • the lubricating oil compositions of Examples 1 to 9 each contained a boron-containing succinimide and a polyalkyl (meth)acrylate having a specific Mw and a specific Mw/X, and therefore could suppress coking occurrence and copper release in the degradation test while preventing base number reduction therein.
  • the lubricating oil composition for an external combustion engine of the present invention can prevent base number reduction, coking occurrence and copper release in a well-balanced manner, and therefore can be favorably used, for example, in an internal combustion engine for automobiles.

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EP3075821A4 (fr) * 2013-11-25 2017-08-09 Idemitsu Kosan Co., Ltd. Composition d'huile lubrifiante pour moteur à combustion interne à allumage commandé
WO2017146867A1 (fr) * 2016-02-25 2017-08-31 Afton Chemical Corporation Lubrifiants destinés à être utilisés dans des moteurs suralimentés

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JP2015196696A (ja) 2015-11-09
US20170183601A1 (en) 2017-06-29
KR20160138020A (ko) 2016-12-02
EP3127993B1 (fr) 2019-07-03
CN106164231A (zh) 2016-11-23
WO2015152226A1 (fr) 2015-10-08
CN106164231B (zh) 2020-03-03
JP6420964B2 (ja) 2018-11-07
EP3127993A4 (fr) 2017-11-29

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